WO2016067539A1 - Particules de graphite pour matériaux d'électrode négative de batterie secondaire au lithium-ion, électrode négative de batterie secondaire au lithium-ion et batterie secondaire au lithium-ion - Google Patents

Particules de graphite pour matériaux d'électrode négative de batterie secondaire au lithium-ion, électrode négative de batterie secondaire au lithium-ion et batterie secondaire au lithium-ion Download PDF

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WO2016067539A1
WO2016067539A1 PCT/JP2015/005207 JP2015005207W WO2016067539A1 WO 2016067539 A1 WO2016067539 A1 WO 2016067539A1 JP 2015005207 W JP2015005207 W JP 2015005207W WO 2016067539 A1 WO2016067539 A1 WO 2016067539A1
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graphite particles
negative electrode
secondary battery
lithium ion
ion secondary
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PCT/JP2015/005207
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English (en)
Japanese (ja)
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江口　邦彦
間所　靖
▲高▼木　嘉則
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Ｊｆｅケミカル株式会社
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Priority to KR1020177011154A priority Critical patent/KR101957074B1/ko
Priority to CN201580058234.4A priority patent/CN107078288B/zh
Publication of WO2016067539A1 publication Critical patent/WO2016067539A1/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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • 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 lithium ion secondary battery negative electrode material, a lithium ion secondary battery negative electrode containing the negative electrode material, and a lithium ion secondary battery using the negative electrode.
  • a lithium ion secondary battery mainly includes a negative electrode, a positive electrode, and an electrolyte (non-aqueous electrolyte).
  • the negative electrode is generally composed of a current collector made of copper foil and a negative electrode material (active substance (working substance for the anode)) bound by a binder.
  • a carbon material is used for the negative electrode material.
  • graphite having excellent charge-discharge characteristics and high discharge capacity and potential flatness is widely used.
  • Lithium ion secondary batteries installed in recent portable electronic devices are required to have high energy density and excellent rapid chargeability and rapid discharge performance, as well as an initial discharge capacity even after repeated charge and discharge. No deterioration (cycle characteristics) is required.
  • Patent Document 1 discloses a graphitized mesocarbon microsphere composed of a Brooks-Taylor type single crystal in which basal planes of graphite are arranged in layers in a direction perpendicular to the diameter direction.
  • Patent Document 2 proposed by the applicant so far includes a composite graphite material in which a graphite granule is filled and / or coated with a carbonaceous layer having lower crystallinity than the graphite granule and containing carbon fine particles. Particles are disclosed.
  • Patent Document 3 discloses a composite graphite material in which a spherical graphite granule is epiboly coated with a graphite coating material and has a graphite surface layer with low crystallinity on the outer surface.
  • Patent Document 4 discloses a graphite composite mixed powder of a graphite composite powder and an artificial graphite powder made of a part of the graphite composite powder.
  • Patent Document 5 describes an invention in which a mixture of three types of graphite particles A, B, and C having different hardness and shape is used for the negative electrode to improve the penetration rate of the electrolytic solution.
  • the graphite particles A an artificial graphite block made of coke and binder pitch is used, and a graphite powder whose outermost shell surface is less crystalline than the inside is used.
  • Patent Document 6 describes that a mixture of graphite particles (A) and (B) having different physical properties is used as a negative electrode material.
  • graphite particles (A) obtained by firing at 1000 ° C. and further fired at 3000 ° C. are used as graphite particles (B).
  • the carbonization yield of the carbonaceous material in the graphite particles (B) fired at a higher temperature is smaller, so the amount of graphitized carbonaceous material in the graphite particles (B) is graphite. It is thought that it is less than the carbonaceous material in the particles (A).
  • the battery characteristics of the lithium secondary battery are considered to be influenced by the physical properties of the graphite particles constituting the mixture. In order to obtain it, it is desired to consider a combination of more appropriate graphite particles.
  • the graphitized material is spherical, the orientation of the basal plane of graphite can be suppressed to some extent even when the density is increased.
  • the graphitized material is dense and hard, high pressure is required to increase the density, and problems such as deformation, elongation, and breakage of the copper foil of the current collector occur. Further, the contact area with the electrolytic solution is small. Therefore, quick chargeability is particularly low. The decrease in chargeability causes the electrodeposition of lithium on the negative electrode surface during charging and causes a decrease in cycle characteristics.
  • the negative electrode material using the graphite composite mixed powder described in Patent Document 4 had insufficient discharge capacity per mass. In addition, the initial charge / discharge efficiency was low, and the rapid chargeability was insufficient.
  • the object of the present invention is to eliminate the problems of conventional negative electrode materials. That is, an object of the present invention is to provide a negative electrode material having the following characteristics and having at least one of excellent initial charge / discharge efficiency, rapid chargeability, rapid discharge characteristics, and long-term cycle characteristics. 1) Having high crystallinity and high discharge capacity per mass 2) Obtaining high active material density at low press pressure 3) While being high density, crushing, breaking and orientation of graphite can be suppressed, It must have the shape of graphite particles that do not impair the permeability and retention of the electrolyte. 4) Excellent lithium ion acceptability on the graphite surface, and it does not have a reactive surface. It can be suppressed. Moreover, it is providing the lithium ion secondary battery negative electrode using this negative electrode material, and the lithium ion secondary battery which has this negative electrode.
  • Composite graphite having a carbonaceous material (B1) inside and at least a part of the surface of the spherical graphite particles (A) that are spherically or substantially spherically shaped (A).
  • the interplanar spacing (d 002 ) of the carbon network layer is 0.3360 nm or less, (2) The tap density is 1.0 g / cm 3 or more, (3) The average particle size is 5 to 25 ⁇ m, (4) The average aspect ratio is 1.2 or more and less than 4.0, and (5) the pore volume with a pore diameter of 0.5 ⁇ m or less by a mercury porosimeter is 0.08 ml / g or less.
  • the content of the carbonaceous material (B1) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the spheroidized graphite particles (A) in the composite graphite particles (C1).
  • the content of the carbonaceous material (B2) is 5 to 30 parts by mass with respect to 100 parts by mass of the spheroidized graphite particles (A) in the composite graphite particles (C2).
  • Graphite particles for negative electrode materials for lithium ion secondary batteries [3] The lithium ion secondary particle according to [1] or [2], wherein the ratio of the composite graphite particles (C1) to the composite graphite particles (C2) is 1:99 to 90:10 by mass ratio.
  • Graphite particles for secondary battery negative electrode material [4] A lithium ion secondary battery negative electrode comprising the graphite particles for a lithium ion secondary battery negative electrode material described in any one of [1] to [3] above.
  • the present invention can provide a negative electrode material having the following characteristics and having at least one of excellent initial charge / discharge efficiency, rapid chargeability, rapid discharge characteristics, and long-term cycle characteristics. 1) Having high crystallinity and high discharge capacity per mass 2) Obtaining high active material density at low press pressure 3) While being high density, crushing, breaking and orientation of graphite can be suppressed, It must have the shape of graphite particles that do not impair the permeability and retention of the electrolyte. 4) Excellent lithium ion acceptability on the graphite surface, and it does not have a reactive surface. It can be suppressed.
  • FIG. 1 is a cross-sectional view schematically showing the structure of a button-type evaluation battery for use in a charge / discharge test in Examples.
  • FIG. 3 is a graph showing a rapid charging rate with respect to the mixing ratio (C2) / [(C1) + (C2)].
  • FIG. 4 is a graph showing the rapid discharge rate with respect to the mixing ratio (C2) / [(C1) + (C2)].
  • FIG. 5 is a graph showing cycle characteristics with respect to the mixing ratio (C2) / [(C1) + (C2)).
  • the flaky graphite particles constituting the spheroidized graphite particles (A) used in the present invention are artificial graphite or natural graphite such as flaky, plate-like or tablet-like. Natural graphite having high crystallinity is particularly preferable, and the average lattice spacing (d 002 ) is preferably less than 0.3360 nm, and particularly preferably 0.3358 nm or less. By setting it to less than 0.3360 nm, the discharge capacity per mass can be increased.
  • the above scaly graphite particles are shaped into a spherical shape or a substantially spherical shape.
  • substantially spherical refers to an ellipsoidal shape, a lump shape, etc., and means a state where there are no large dents or sharp projections on the surface.
  • the spheroidized graphite particles (A) may be obtained by aggregating, laminating, granulating, and adhering a plurality of scaly graphite particles, and a single scaly graphite particle is curved, bent, folded, and rounded. It may be.
  • a concentric or cabbage-like structure in which a flat portion (basal surface) of scaly graphite is disposed on the surface of the spheroidized graphite particles is preferable.
  • the average particle size (average particle size in terms of volume) of the spheroidized graphite particles (A) is preferably 5 to 25 ⁇ m, particularly preferably 10 to 20 ⁇ m. If it is 5 micrometers or more, the density of an active material layer can be made high and the discharge capacity per volume will improve. When it is 25 ⁇ m or less, quick chargeability and cycle characteristics are improved.
  • the average particle diameter in terms of volume means a particle diameter at which the cumulative frequency of the particle size distribution measured by a laser diffraction particle size distribution meter is 50% by volume percentage.
  • the average aspect ratio of the spheroidized graphite particles (A) is preferably 1.2 or more and less than 4.0. In the case of a shape close to a true sphere of less than 1.2, when the active material layer is pressed, the graphite particles are greatly deformed, and the graphite particles may be cracked. And if it is 4.0 or more, the diffusibility of lithium ions may decrease, and rapid discharge and cycle characteristics may deteriorate.
  • the average aspect ratio means the ratio of the major axis length of one particle to the minor axis length.
  • the long axis length means the longest diameter of the particle to be measured
  • the short axis length means a short diameter perpendicular to the long axis of the particle to be measured.
  • the average aspect ratio is a simple average value of the aspect ratio of each particle measured by observing 100 particles with a scanning electron microscope.
  • the magnification at the time of observing with a scanning electron microscope is a magnification at which the shape of the particles to be measured can be confirmed.
  • the method for producing the spheroidized graphite particles (A) can be produced by applying mechanical external force to flat or scale-like natural graphite. Specifically, it can be spheroidized by applying a high shearing force, bending by applying a rolling operation, or spheroidizing by concentric granulation. Before and after the spheronization treatment, a binder can be added to promote granulation.
  • Spheroidizers that can be spheroidized include “Counter Jet Mill”, “ACM Pulverizer” (manufactured by Hosokawa Micron Corporation), “Current Jet” (manufactured by Nissin Engineering Co., Ltd.), “SARARA” (Kawasaki) Granulators such as Heavy Industries Co., Ltd.), “GRANUREX” (Freund Sangyo Co., Ltd.), “New Gramachine” (manufactured by Seishin Corporation), “Agromaster” (manufactured by Hosokawa Micron Co., Ltd.), Kneaders such as pressure kneaders and two rolls, “Mechano Micro System” (manufactured by Nara Machinery Co., Ltd.), Extruder, Ball Mill, Planetary Mill, “Mechano Fusion System” (manufactured by Hosokawa Micron Corporation), “Nobilta” (Hosokawa Micron Co., Ltd.), “Hybridization” (
  • the inside of the particles of the spheroidized graphite particles can be densified by performing a press treatment.
  • the surface of the spheroidized graphite particles (A) is oxidized, low-crystallized, or functional groups by heat treatment in an oxidizing atmosphere, immersion in an acidic liquid, fluorination treatment, or the like. Can also be given.
  • the composite graphite particles (C1) used in the present invention have a carbonaceous material (B1) in the inside of the particles and at least a part of the particle surface of the spheroidized graphite particles (A).
  • the adhesion of the carbonaceous material (B1) can prevent the spheroidized graphite particles (A) from being crushed, enhance the lithium ion acceptability, and exhibit excellent rapid chargeability.
  • the carbonaceous material (B1) attached to the spheroidized graphite particles (A) for example, coal-based or petroleum-based heavy oil, tars, pitches, and resins such as phenol resins are finally 500 Carbides formed by heat treatment at a temperature of °C to less than 1500 °C are exemplified.
  • the adhesion amount of the carbonaceous material (B1) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass with respect to 100 parts by mass of the spheroidized graphite particles (A). Most preferably, it is 5 parts by mass.
  • the spheroidized graphite particles (A) When the amount is less than 0.1 parts by mass, the spheroidized graphite particles (A) are liable to be crushed, and the initial charge / discharge efficiency and rapid discharge properties are reduced. In addition, long-term cycle characteristics may deteriorate. In the case of more than 10 parts by mass, the composite graphite particles (C1) become hard, and a high pressure is required when pressing the active material layer. For this reason, the copper foil as the current collector is broken or elongated, and the irreversible capacity of the carbonaceous material (B1) is increased, leading to a decrease in initial charge / discharge efficiency.
  • the composite graphite particles (C2) used in the present invention have the graphite material (B2) in at least a part of the inside and / or the particle surface of the spheroidized graphite particles (A).
  • the adhesion of the graphite material (B2) prevents the spheroidized graphite particles (A) from being crushed, allows the active material layer to be densified with a low pressing pressure, and has excellent initial charge / discharge efficiency and rapid discharge properties. Can be expressed.
  • Examples of the graphite material (B2) attached to the spheroidized graphite particles (A) include, for example, coal-based or petroleum-based heavy oil, tars, pitches, and resins such as phenolic resins, as described above. Is finally graphitized by heat treatment at 1500 ° C. or more and less than 3300 ° C.
  • the adhesion amount of the graphite material (B2) is preferably 5 to 30 parts by mass, particularly preferably 10 to 25 parts by mass with respect to 100 parts by mass of the spheroidized graphite particles (A). When the amount is less than 5 parts by mass, the spheroidized graphite particles (A) are liable to be crushed, and the initial charge / discharge efficiency and rapid discharge properties are reduced.
  • the composite graphite particles (C2) are hardened, and a high pressure is required to press the active material layer, and the copper foil as a current collector is broken or elongated. Further, the composite graphite particles (C2) are likely to be fused with each other during the heat treatment, resulting in a crushing surface in the graphite material (B2), resulting in a decrease in initial charge / discharge efficiency. Moreover, it is preferable that [A in composite graphite particle C1 and adhesion amount of carbonaceous material B1 with respect to 100 parts by mass ⁇ A deposition amount with respect to A in composite graphite particle C2 and graphite material B2 with respect to 100 parts by mass].
  • the carbonaceous material (B1) is harder and has lower initial efficiency than the graphite material (B2), so the amount of adhesion to the spheroidized graphite particles (A) is relatively small and thin. It is preferable to coat.
  • the feature of the rapid chargeability of the composite graphite particles (C1) is derived from the interfacial reaction between the carbonaceous material (B1) coated in a film and the electrolytic solution.
  • the composite graphite particles (C1) alone cause crushing and fracture at high active material density, so combined graphite particles (C2) reinforced with a relatively large amount of graphite material (B2) are used in combination. By doing so, this problem is solved.
  • the spheroidized graphite particles (A) may be used.
  • a precursor of carbonaceous material (B1) or graphite material (B2), for example, petroleum-based or coal-based heavy oil, tars, pitches, resins such as phenol resin, etc. are liquid phase method, solid phase It can be produced by depositing or coating by any of the methods followed by heat treatment.
  • liquid phase method examples include coal tar, tar light oil, tar medium oil, tar heavy oil, naphthalene oil, anthracene oil, coal tar pitch, pitch oil, mesophase pitch, oxygen-crosslinked petroleum pitch, naphtha cracked fraction, ethylene bottom oil
  • Petroleum-based or coal-based tar pitches such as, thermoplastic resins such as polyvinyl alcohol and polyacrylic acid, thermosetting resins such as phenolic resins and furan resins, saccharides, and celluloses (hereinafter also referred to as carbonaceous material precursors) ), Etc., or a solution thereof, or the like, is dispersed, mixed and impregnated into the spheroidized graphite particles (A), and then light components such as a solvent are removed if necessary, and finally a non-oxidizing or oxidizing atmosphere
  • the composite graphite particles (C2) to which the graphite material (B2) is adhered can be produced by finally performing heat treatment at 1500 ° C. or more and less than 3300 ° C. in a non-oxidizing atmosphere.
  • stirring, heating, and decompression can be performed.
  • a plurality of different carbonaceous material precursors may be used.
  • the carbonaceous material precursor may contain an oxidizing agent or a crosslinking agent.
  • the carbonaceous material precursor powder exemplified in the description of the liquid phase method and the spheroidized graphite particles (A) are mixed, or simultaneously compressed, compressed, sheared, impacted, frictioned, etc.
  • a carbonaceous material precursor powder is pressure-bonded to the surface of the spheroidized graphite particles (A) by a mechanochemical treatment that imparts the mechanical energy of.
  • the mechanochemical treatment the carbonaceous material precursor is melted or softened, and is adhered by being rubbed against the spheroidized graphite particles (A).
  • the apparatus capable of mechanochemical treatment include the various compression shearing processing apparatuses described above.
  • the carbonaceous material (B1) is finally heat-treated at 500 ° C. or more and less than 1500 ° C. in a non-oxidizing or oxidizing atmosphere to the spheroidized graphite particles (A) to which the powder of the carbonaceous material precursor is attached.
  • a method for producing the attached composite graphite particles (C1) is mentioned.
  • the composite graphite particles (C2) to which the graphite material (B2) is adhered can be produced by finally performing heat treatment at 1500 ° C. or more and less than 3300 ° C. in a non-oxidizing atmosphere.
  • the composite graphite particles (C1) and (C2) of the present invention preferably have substantially no crushed surface derived from pulverization.
  • a rotary kiln is used as part of the heat treatment process. It is desirable to adopt a method. By stirring the spheroidized graphite particles (A) in a temperature range where the carbonaceous material precursor shifts from a molten state to carbonization, the composite graphite particles (C1) and (C2) having a smooth surface and no fusion are obtained. Obtainable.
  • the composite graphite particles (C1) and (C2) after finishing the final heat treatment are in a powder form, and the whole is fused, with substantially no crushing surface derived from pulverization. It means not. Part of the carbonaceous material (B1) and the graphite material (B2) adhering to the composite graphite particles (C1) and (C2) is peeled off, and those observed as individual powders are excluded. . Although it is in powder form, it does not exclude the case where the fused material is slightly included.
  • Crushing the material fused at the time of heat treatment into a particulate form causes the degradation of the initial charge / discharge efficiency because the crushing surface derived from the pulverization is the starting point for the decomposition reaction of the electrolyte. .
  • conductive materials such as carbon fiber and carbon black, carbon or graphite fine particles, flat artificial graphite or natural graphite may be used together with the carbonaceous material precursor.
  • conductive materials such as carbon fiber and carbon black, carbon or graphite fine particles, flat artificial graphite or natural graphite may be used together with the carbonaceous material precursor.
  • composite graphite particles (C2) to which the graphite material (B2) is adhered together with the carbonaceous material precursor, Fe, Co, Ni, Al, Ti, etc. that have an effect of increasing the degree of graphitization.
  • These metals, metalloids such as Si and B, and compounds thereof may be used.
  • the composite graphite particles (C1) to which the carbonaceous material (B1) is attached or the composite graphite particles (C2) to which the graphite material (B2) is attached are the carbonaceous material (B1) or the graphite material.
  • the inside or the surface of (B2) may have a conductive material such as carbon fiber or carbon black, fine particles of other carbonaceous material or graphite material, flat artificial graphite or natural graphite.
  • a metal oxide such as silica, aluminum oxide (alumina), titanium oxide (titania) or the like may be attached or embedded (for example, in fine particles).
  • a metal or metal compound that can be an active material such as Si, Sn, Co, Ni, SiO, SnO, or lithium titanate may be attached or embedded.
  • the graphite particles for secondary battery negative electrode material of the present invention (hereinafter sometimes referred to as mixed graphite particles) is a mixture of the composite graphite particles (C1) and the composite graphite particles (C2).
  • the mixture the intensity ratio of 1360 cm -1 near the peak intensity (I 1360) and 1580 cm -1 near peak intensity of a Raman spectrum (I 1580) (I 1360 / I 1580) in the distribution, 0.01-0.08 And those having maximum points in both ranges of 0.12 to 0.30.
  • the composite graphite particles (C1) show a maximum peak in the range of intensity ratio (I 1360 / I 1580 ) 0.12 to 0.30, and the composite graphite particles (C 2) have an intensity ratio (I 1360 / I 1580). ) A maximum peak is shown in the range of 0.01 to 0.08.
  • the intensity ratio (I 1360 / I 1580 ) is measured for any 200 points of the mixture, and the corresponding points are counted at intervals of 0.004. .
  • the mass ratio of composite graphite particles (C1): composite graphite particles (C2) is generally 20 to 80:80 to 20.
  • the active material layer can be densified with a low pressing pressure, the balance between rapid chargeability and rapid discharge property is improved, and excellent cycle characteristics can be obtained.
  • the interplanar spacing (d 002 ) of the carbon network layer is 0.3360 nm or less. In particular, it is preferably 0.3358 nm or less.
  • the discharge capacity when the mixed graphite particles are used as the negative electrode material varies depending on the production conditions and evaluation conditions of the negative electrode and the evaluation battery, but is approximately 355 mAh / g or more, preferably 360 mAh / g. That's it.
  • the mixed graphite particles of the present invention have a 300 times tap density of 1.00 g / cm 3 or more. In particular, it is preferably 1.10 g / cm 3 or more.
  • the tap density becomes an index of the sphericity and surface smoothness of the graphite particles, and the mixed graphite particles do not substantially have a crushing surface derived from pulverization, thereby increasing the tap density.
  • the higher the tap density the higher the density before pressing the active material layer, the smaller the deformation of the graphite particles due to the press, and the lower the deformation and destruction of the graphite particles when the density is increased.
  • the tap density is an increased bulk density obtained after mechanically tapping a container containing a powder sample.
  • the mixed graphite particles of the present invention have an average particle size of 5 to 25 ⁇ m. 10 to 20 ⁇ m is particularly preferable. If it is 5 micrometers or more, the density of an active material layer can be made high and the discharge capacity per volume will improve. And if it is 25 micrometers or less, quick charge property and cycling characteristics will improve.
  • the mixed graphite particles of the present invention have an average aspect ratio of 1.2 or more and less than 4.0.
  • the deformation of the graphite particles becomes large, and the graphite particles are cracked or expanded due to rebound after pressing. There is. And if it is 4.0 or more, the diffusibility of lithium ions is reduced, and rapid discharge and cycle characteristics are reduced.
  • the mixed graphite particles of the present invention have a pore volume of not more than 0.08 ml / g with a pore diameter of 0.5 ⁇ m or less as measured by a mercury porosimeter. In particular, it is preferably 0.05 ml / g or less. If the pore volume is 0.08 ml / g or less, the long-term cycle characteristics are good.
  • the definition of the pore volume by the mercury porosimeter was determined to be a pore diameter of 0.5 ⁇ m or less, in order to measure the pore volume, the void between particles when filling the measurement cell with the graphite particles was excluded. Because. If the pore diameter to be measured is 0.5 ⁇ m or less, voids between the particles are not included, and only the pores of the graphite particles can be detected.
  • pore volume adjustment method is as follows.
  • the density inside the particles depends on the operating conditions of the spheroidizing device (for example, rolling time, pressure applied simultaneously with spheronization, etc.).
  • a method of controlling the degree a method of compressing the produced spheroidized graphite particles (A), a composite graphite particles (C1), a carbonaceous material (B1) as a coating material of (C2), and a graphite material
  • a method for controlling the degree of impregnation of (B2) into the spheroidized graphite particles (A) (for example, by reducing the viscosity of the precursor of the carbonaceous material (B1) or the graphite material (B2), (A) Impregnation into the interior, and in that case, a method of promoting impregnation by heating, decompression, etc.).
  • the negative electrode material for a lithium ion secondary battery of the present invention (hereinafter also simply referred to as negative electrode material) is obtained by using the above mixed graphite particles alone or as a main material as an active material.
  • a secondary material various known conductive materials, carbonaceous particles, graphite particles, metallic particles or composite particles thereof can be mixed as long as the effects of the present invention are not impaired. It is preferable to keep the ratio at 30% or less.
  • Secondary materials include, for example, carbonaceous or graphite fibers, carbon black, conductive materials such as scaly artificial graphite and natural graphite, carbonaceous particles such as soft carbon and hard carbon, and spherical mesocarbon microsphere graphite.
  • Examples thereof include graphitized particles such as composite graphitized material having fine pores and spheroidized natural graphite.
  • These sub-materials may be a carbon material, an organic material, an inorganic material, a mixture with a metal material, a coating, or a composite. It may be one that adheres or coats an organic compound such as a surfactant or resin, or one that adheres or embeds fine particles of metal oxide such as silica, alumina, titania, etc., silicon, tin, cobalt
  • a metal or a metal compound such as nickel, copper, silicon oxide, tin oxide, or lithium titanate may be attached, embedded, combined, or encapsulated.
  • the negative electrode for a lithium ion secondary battery of the present invention (hereinafter also simply referred to as a negative electrode) can be produced in accordance with a normal method for producing a negative electrode, but a chemically and electrochemically stable negative electrode is obtained. There is no limitation as long as it is a manufacturing method capable of satisfying the requirements.
  • a negative electrode mixture obtained by adding a binder to the negative electrode material can be used.
  • the binder those having chemical stability and electrochemical stability with respect to the electrolyte are preferably used.
  • fluorine resins such as polyvinylidene fluoride and polytetrafluoroethylene, polyethylene, polyvinyl alcohol, and styrene. Butadiene rubber, carboxymethyl cellulose and the like are used. These can also be used together.
  • the binder is preferably in a proportion of 1 to 20% by mass in the total amount of the negative electrode mixture.
  • N-methylpyrrolidone, dimethylformamide, water, alcohol and the like which are ordinary solvents for producing the negative electrode, can be used.
  • the negative electrode is produced, for example, by dispersing a negative electrode mixture in a solvent to prepare a paste-like negative electrode mixture, applying the negative electrode mixture to one or both sides of a current collector, and drying. Thereby, a negative electrode in which the negative electrode mixture layer (active material layer) is uniformly and firmly bonded to the current collector is obtained. More specifically, for example, after mixing the negative electrode material particles, fluorine resin powder or styrene butadiene rubber water dispersant and solvent into a slurry, a known stirrer, mixer, kneader, kneader or the like is used. The mixture is stirred and mixed to prepare a negative electrode mixture paste.
  • the film thickness of the negative electrode mixture layer is 10 to 200 ⁇ m, preferably 30 to 100 ⁇ m.
  • the negative electrode mixture layer can also be produced by dry-mixing the particles of the negative electrode material and resin powder such as polyethylene and polyvinyl alcohol and hot pressing in a mold. However, dry mixing requires a large amount of binder to obtain sufficient negative electrode strength, and if the binder is excessive, the discharge capacity and rapid charge / discharge efficiency may be reduced. When the negative electrode mixture layer is formed and then pressure bonding such as pressurization is performed, the adhesive strength between the negative electrode mixture layer and the current collector can be further increased.
  • Density of the negative electrode mixture layer since increasing the volumetric capacity of the negative electrode, 1.70 ⁇ 1.85g / cm 3, and particularly preferably a 1.75 ⁇ 1.85g / cm 3.
  • the shape of the current collector used for the negative electrode is not particularly limited, but is preferably a foil, a mesh, a net-like material such as expanded metal, or the like.
  • the material for the current collector is preferably copper, stainless steel, nickel or the like.
  • the thickness of the current collector is preferably 5 to 20 ⁇ m.
  • the lithium ion secondary battery of the present invention is formed using the negative electrode.
  • the secondary battery of the present invention is not particularly limited except that the negative electrode is used, and other battery components conform to the elements of a general secondary battery. That is, an electrolytic solution, a negative electrode, and a positive electrode are the main battery constituent elements, and these elements are enclosed in, for example, a battery can.
  • the negative electrode and the positive electrode each act as a lithium ion carrier, and lithium ions are released from the negative electrode during charging.
  • the positive electrode used in the secondary battery of the present invention is formed, for example, by applying a positive electrode mixture composed of a positive electrode material, a binder and a conductive material to the surface of the current collector.
  • a lithium compound is used, but it is preferable to select a material that can occlude / desorb a sufficient amount of lithium.
  • lithium-containing transition metal oxide, transition metal chalcogenide, vanadium oxide, other lithium compounds, chemical formula M X Mo 6 OS 8-Y (where X is 0 ⁇ X ⁇ 4, Y is 0 ⁇ Y ⁇ 1) And the like, and M is at least one kind of transition metal element), and the like can be used.
  • the vanadium oxide is V 2 O 5 , V 6 O 13 , V 2 O 4 , V 3 O 8 or the like.
  • the lithium-containing transition metal composite oxide is a composite oxide of lithium and a transition metal, and may be a solid solution of lithium and two or more transition metals. Complex oxides may be used alone or in combination of two or more.
  • the lithium-containing transition metal compound oxide is LiM1 1-X M2 X O 2 (wherein X is a numerical value in the range of 0 ⁇ X ⁇ 1, and M1 and M2 are at least one kind of transition metal element.
  • LiM1 1-Y M2 Y O 4 wherein Y is a numerical value in the range of 0 ⁇ Y ⁇ 1, and M1 and M2 are at least one transition metal element).
  • the transition metal elements represented by M1 and M2 are Co, Ni, Mn, Cr, Ti, V, Fe, Zn, Al, In, Sn, etc., preferably Co, Mn, Cr, Ti, V, Fe , Al and the like.
  • Preferred examples are LiCoO 2 , LiNiO 2 , LiMnO 2 , LiNi 0.9 Co 0.1 O 2 , LiNi 0.5 Co 0.5 O 2, and the like.
  • the lithium-containing transition metal oxide include lithium, transition metal oxides, hydroxides, salts, and the like as starting materials, and these starting materials are mixed in accordance with the composition of the desired metal oxide, and are mixed under an oxygen atmosphere. It can be obtained by firing at a temperature of ⁇ 1000 ° C.
  • the lithium compound may be used alone or in combination of two or more.
  • alkali carbonates such as lithium carbonate
  • the positive electrode is formed by, for example, applying a positive electrode mixture composed of the lithium compound, the binder, and a conductive material for imparting conductivity to the positive electrode on one or both sides of the current collector to form a positive electrode mixture layer.
  • the binder the same one as that used for producing the negative electrode can be used. Carbon materials such as graphite and carbon black are used as the conductive material.
  • the positive electrode mixture (composite cathode material) may be dispersed in a solvent, and the paste-formed positive electrode mixture may be applied to a current collector and dried to form a positive electrode mixture layer. After the mixture layer is formed, pressure bonding such as press pressing may be further performed. As a result, the positive electrode mixture layer is uniformly and firmly bonded to the current collector.
  • the shape of the current collector is not particularly limited, but is preferably a foil shape, a mesh shape, a net shape such as expanded metal, or the like.
  • the material of the current collector is aluminum, stainless steel, nickel or the like. In the case of a foil, the thickness is preferably 10 to 40 ⁇ m.
  • the nonaqueous electrolyte (electrolytic solution) used for the secondary battery of the present invention is an electrolyte salt used for a normal nonaqueous electrolytic solution.
  • the electrolyte salt include LiPF 6 , LiBF 4 , LiAsF 6 , LiClO 4 , LiB (C 6 H 5 ) 4 , LiCl, LiBr, LiCF 3 SO 3 , LiCH 3 SO 3 , LiN (CF 3 SO 2 ) 2.
  • LiC (CF 3 SO 2 ) 3 LiN (CF 3 CH 2 OSO 2 ) 2 , LiN (CF 3 CF 2 OSO 2 ) 2 , LiN (HCF 2 CF 2 CH 2 OSO 2 ) 2 , LiN [(CF 3 ) 2 CHOSO 2 ] 2 , LiB [C 6 H 3 (CF 3 ) 2 ] 4 , LiAlCl 4 , LiSiF 5 and other lithium salts can be used.
  • LiPF 6 and LiBF 4 are preferable from the viewpoint of oxidation stability.
  • the electrolyte salt concentration of the electrolytic solution is preferably 0.1 to 5 mol / L, and more preferably 0.5 to 3 mol / L.
  • the non-aqueous electrolyte may be liquid, or may be a solid or gel polymer electrolyte.
  • the nonaqueous electrolyte battery is configured as a so-called lithium ion secondary battery
  • the nonaqueous electrolyte battery is configured as a polymer electrolyte battery such as a polymer solid electrolyte battery or a polymer gel electrolyte battery.
  • Examples of the solvent constituting the nonaqueous electrolyte include carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, and diethyl carbonate, 1,1- or 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 2- Methyltetrahydrofuran, ⁇ -butyrolactone, 1,3-dioxolane, 4-methyl-1,3-dioxolane, ethers such as anisole and diethyl ether, thioethers such as sulfolane and methylsulfolane, nitriles such as acetonitrile, chloronitrile and propionitrile , Trimethyl borate, tetramethyl silicate, nitromethane, dimethylformamide, N-methylpyrrolidone, ethyl acetate, trimethyl orthoformate, nitrobenzene, benzoyl chloride, benzoyl bromide, La
  • a polymer compound gelled with a plasticizer non-aqueous electrolyte
  • the polymer compound constituting the matrix include ether polymer compounds such as polyethylene oxide and its cross-linked products, polymethacrylate polymer compounds, polyacrylate polymer compounds, polyvinylidene fluoride, and vinylidene fluoride-hexafluoropropylene.
  • Fluorine polymer compounds such as copolymers can be used alone or in combination. It is particularly preferable to use a fluorine-based polymer compound such as polyvinylidene fluoride or vinylidene fluoride-hexafluoropropylene copolymer.
  • the plastic solid electrolyte or polymer gel electrolyte is mixed with a plasticizer.
  • a plasticizer the above electrolyte salts and non-aqueous solvents can be used.
  • the electrolyte salt concentration in the non-aqueous electrolyte as a plasticizer is preferably 0.1 to 5 mol / L, more preferably 0.5 to 2 mol / L.
  • the method for producing the polymer solid electrolyte is not particularly limited.
  • a method of mixing a polymer compound constituting a matrix, a lithium salt, and a non-aqueous solvent (plasticizer) and heating to melt the polymer compound, a polymer compound, a lithium salt, and non-water as an organic solvent for mixing Method of evaporating organic solvent for mixing after dissolving solvent (plasticizer), mixing polymerizable monomer, lithium salt and non-aqueous solvent (plasticizer), and irradiating the mixture with ultraviolet rays, electron beam, molecular beam, etc.
  • a method of polymerizing a polymerizable monomer to obtain a polymer compound is not particularly limited.
  • a method of mixing a polymer compound constituting a matrix, a lithium salt, and a non-aqueous solvent (plasticizer) and heating to melt the polymer compound, a polymer compound, a lithium salt, and non-water as an organic solvent for mixing Method of evaporating organic solvent for mixing after dis
  • the proportion of the nonaqueous solvent (plasticizer) in the polymer solid electrolyte is preferably 10 to 90% by mass, more preferably 30 to 80% by mass. If it is less than 10% by mass, the electrical conductivity will be low, and if it exceeds 90% by mass, the mechanical strength will be weak and film formation will be difficult.
  • a separator can also be used.
  • the material of a separator is not specifically limited, For example, a woven fabric, a nonwoven fabric, a synthetic resin microporous film, etc. are mentioned.
  • a synthetic resin microporous membrane is preferred, and among them, a polyolefin microporous membrane is preferred in terms of thickness, membrane strength, and membrane resistance. Specifically, it is a microporous membrane made of polyethylene and polypropylene, or a microporous membrane that combines these.
  • the secondary battery of the present invention is produced by laminating the negative electrode, the positive electrode, and the nonaqueous electrolyte in the order of, for example, the negative electrode, the nonaqueous electrolyte, and the positive electrode, and accommodating the laminate in the battery exterior material. Further, a non-aqueous electrolyte may be disposed outside the negative electrode and the positive electrode.
  • the structure of the secondary battery of the present invention is not particularly limited, and the shape and form thereof are not particularly limited, and may be cylindrical, rectangular, depending on the application, mounted equipment, required charge / discharge capacity, and the like.
  • a coin type, a button type, or the like can be arbitrarily selected.
  • a structure enclosed in a laminate film can also be used.
  • buttons-type secondary batteries for evaluation having a configuration as shown in FIG. 1 were produced and evaluated.
  • the battery can be produced according to a known method based on the object of the present invention.
  • Example 1 [Preparation of spheroidized graphite particles (A)] While pulverizing and rolling the flaky natural graphite having an average particle diameter of 55 ⁇ m, it is shaped into a spherical shape with an average particle diameter of 12 ⁇ m, an average aspect ratio of 1.4, and (d 002 ) of 0. .3357 nm, specific surface area was 7.0 m ⁇ 2> / g, and pore volume with a pore diameter of 0.5 [mu] m or less by a mercury porosimeter was adjusted to 0.12 ml / g.
  • the spherical graphite particles were compressed by a mold press at a pressure of 0.5 ton / cm 2 , the average particle diameter was 12 ⁇ m, the average aspect ratio was 1.8, (d 002 ) was 0.3357 nm, the specific surface area was 6.5 m 2 / g, and the pore volume with a pore diameter of 0.5 ⁇ m or less by a mercury porosimeter was adjusted to 0.08 ml / g.
  • composite graphite particles (C1) composed of a porous material (B1) and spheroidized graphite particles (A) were obtained.
  • the obtained composite graphite particles (C1) had a high sieve yield of 99.8% by sieving with a mesh size of 53 ⁇ m, and were substantially unfused.
  • the average particle diameter is 13 ⁇ m
  • the average aspect ratio is 1.8
  • (d 002 ) is 0.3357 nm
  • the specific surface area is 3.6 m 2 / g
  • the pore diameter is 0.5 ⁇ m or less by a mercury porosimeter.
  • the pore volume was 0.06 ml / g.
  • the composite graphite particles (C1) were observed with a scanning electron microscope, they were smooth ellipsoidal coated graphite particles with scaly natural graphite attached to the surface. No particles of calcined carbon alone derived from coal tar pitch were observed, and no crushed fracture surface derived from crushing of the fused portion was observed.
  • the obtained composite graphite particles (C2) had a high sieve yield of 99.5% by sieving with a mesh size of 53 ⁇ m and were substantially unfused.
  • the average particle size is 14 ⁇ m
  • the average aspect ratio is 1.8
  • (d 002 ) is 0.3358 nm
  • the specific surface area is 0.6 m 2 / g
  • the pore diameter is 0.5 ⁇ m or less by a mercury porosimeter.
  • the pore volume was 0.04 ml / g.
  • the mixture has an average particle diameter of 14 ⁇ m, an average aspect ratio of 1.8, a (d 002 ) of 0.3358 nm, a specific surface area of 2.1 m 2 / g, and a pore volume of not more than 0.5 ⁇ m by a mercury porosimeter.
  • the mixture the intensity ratio of 1580 cm -1 near the peak intensity and 1360 cm -1 near peak intensity of a Raman spectrum (I 1360) at any 200 point (I 1580) (I 1360 / I 1580) results of measuring the distribution Is shown in FIG.
  • the intensity ratio (I 1360 / I 1580 ) showed maximum peaks in the vicinity of 0.04 and 0.172.
  • the negative electrode mixture paste was applied on a copper foil having a thickness of 16 ⁇ m to a uniform thickness, and further, water in a dispersion medium was evaporated at 90 ° C. in a vacuum to dry the paste.
  • the negative electrode mixture applied onto the copper foil was pressed with a hand press at 12 kN / cm 2 (120 MPa), and further punched into a circular shape with a diameter of 15.5 mm.
  • a working electrode having an agent layer (thickness 60 ⁇ m) was prepared.
  • the density of the negative electrode mixture layer was 1.75 g / cm 3 .
  • the working electrode was stretched and not deformed, and the current collector viewed from the cross section had no dent.
  • a lithium metal foil is pressed onto a nickel net and punched into a circular shape with a diameter of 15.5 mm, and consists of a current collector made of nickel net and a lithium metal foil (thickness 0.5 mm) in close contact with the current collector.
  • a counter electrode was produced.
  • LiPF 6 was dissolved at a concentration of 1 mol / L in a mixed solvent of ethylene carbonate 33 vol% -methyl ethyl carbonate 67 vol% to prepare a non-aqueous electrolyte.
  • the obtained nonaqueous electrolytic solution was impregnated into a polypropylene porous body (thickness: 20 ⁇ m) to produce a separator impregnated with the electrolytic solution.
  • a button-type secondary battery shown in FIG. 1 was prepared as an evaluation battery.
  • the exterior cup 1 and the exterior can 3 were sealed by interposing an insulating gasket 6 at the peripheral portion thereof and caulking both peripheral portions.
  • an insulating gasket 6 Inside, in order from the inner surface of the outer can 3, a current collector 7 a made of nickel net, a cylindrical counter electrode 4 made of lithium foil, a separator 5 impregnated with an electrolyte, a disk-shaped working electrode 2 made of a negative electrode mixture, and A battery in which current collectors 7b made of copper foil are laminated.
  • the evaluation battery is a battery composed of a working electrode 2 containing graphite particles that can be used as a negative electrode active material and a counter electrode 4 made of a lithium metal foil in an actual battery.
  • the evaluation battery produced as described above was subjected to the following charge / discharge test at a temperature of 25 ° C., discharge capacity per mass, discharge capacity per volume, initial charge / discharge efficiency, rapid charge rate, rapid discharge. Rate and cycle characteristics were evaluated. The evaluation results are shown in Table 1 (shown in Table 1-1 and Table 1-2, the same shall apply hereinafter).
  • Rapid charge rate (%) (constant current charge capacity in the second cycle / discharge capacity in the first cycle) ⁇ 100
  • Rapid discharge rate (discharge capacity in the second cycle / discharge capacity in the first cycle) ⁇ 100
  • Cycle characteristics (%) (discharge capacity in the 100th cycle / discharge capacity in the first cycle) ⁇ 100
  • the evaluation battery obtained using the negative electrode material of Example 1 as the working electrode can increase the density of the active material to 1.75 g / cm 3 and has a high mass per mass. It shows discharge capacity and high initial charge / discharge efficiency. For this reason, the discharge capacity per volume can be improved significantly. Even at its high density, the rapid charge rate, rapid discharge rate, and cycle characteristics maintain excellent results.
  • Example 2 Example 5
  • the density of the negative electrode mixture layer was changed to 1.75 g by changing the pressing pressure in the same manner as in Example 1.
  • a working electrode was prepared by adjusting to / cm 3 to prepare an evaluation battery. The same charge / discharge test as in Example 1 was performed, and the evaluation results of the battery characteristics are shown in Table 1.
  • Example 1 the density of the negative electrode mixture layer was changed in the same manner as in Example 1 except that the composite graphite particles (C1) and the composite graphite particles (C2) were not mixed and each was used alone as a negative electrode material.
  • a working electrode was prepared by adjusting to 1.75 g / cm 3 to prepare an evaluation battery. The same charge / discharge test as in Example 1 was performed, and the evaluation results of the battery characteristics are shown in Table 1.
  • Table 1 In addition to Examples 1 to 5, the relationship between the mixing ratio of the composite graphite particles (C1) and the composite graphite particles (C2) and the battery characteristics is shown in FIGS.
  • the mixed graphite particles of the present invention have a high charge rate shown in FIG. 3, a rapid discharge rate shown in FIG. 4, and a cycle characteristic shown in FIG.
  • the composite graphite particles (C1) and the composite graphite particles (C2) are not mixed and each of them is used alone as a negative electrode material, either of the characteristics of the rapid charge rate and the rapid discharge rate is insufficient. Due to the influence, the cycle characteristics are inferior.
  • Example 6 A working electrode was produced in the same manner as in Example 1 except that the density of the negative electrode mixture layer in Example 1 was changed to 1.80 g / cm 3 (Example 6), and an evaluation battery was produced. The same charge / discharge test as in Example 1 was performed, and the evaluation results of the battery characteristics are shown in Table 1. As the density of the negative electrode mixture layer increases, the battery characteristics tend to decrease, but at a density of 1.80 g / cm 3 , a sufficiently high level is maintained. On the other hand, when the density is too high, deformation of the copper foil as a current collector and deterioration of battery characteristics become remarkable.
  • Example 1 the average particle diameter, average aspect ratio, compression treatment presence / absence of the spheroidized graphite particles (A), the ratio of the carbonaceous material (B1) and the graphite material (B2), to the composite graphite particles (C1) Other than the addition of 2 parts by mass of 120 nm ⁇ 5 ⁇ m long graphitized carbon fiber together with the precursor of the graphite material (B2) when producing composite graphite particles (C2) Produced a working electrode in the same manner as in Example 1 to produce an evaluation battery.
  • the same charge / discharge test as in Example 1 was performed, and the evaluation results of the battery characteristics are shown in Table 1.
  • Table 1 shows various physical properties of the mixed graphite particles.
  • the discharge capacity is low.
  • the tap density is less than 1.0 g / cm 3 or when the average aspect ratio is 4 or more, the rapid discharge rate and cycle characteristics are insufficient.
  • the average particle diameter is less than 5 ⁇ m, the initial charge / discharge efficiency is low, and when it exceeds 25 ⁇ m, the rapid charge rate and cycle characteristics are insufficient.
  • the pore volume with a pore diameter of 0.5 ⁇ m or less by a mercury porosimeter exceeds 0.08 ml / g, the cycle characteristics are relatively inferior.
  • Example 10 A working electrode was prepared in the same manner as in Example 1 except that 85 parts by mass of the mixed graphite particles of Example 9 and 15 parts by mass of the bulk mesophase graphitized material shown below were mixed as other negative electrode materials. Produced. The same charge / discharge test as in Example 1 was performed, and the evaluation results of the battery characteristics are shown in Table 1. Table 1 shows various physical properties of the mixed graphite particles.
  • Example 11 80 parts by mass of the mixed graphite particles of Example 9, 10 parts by mass of the bulk mesophase graphitized material shown in Example 10 and 5 parts of scaly graphite coated with the carbonaceous material shown below as another negative electrode material
  • a working electrode was produced in the same manner as in Example 1 except that the parts were mixed, and an evaluation battery was produced.
  • the same charge / discharge test as in Example 1 was performed, and the evaluation results of the battery characteristics are shown in Table 1.
  • Table 1 shows various physical properties of the mixed graphite particles.
  • the scaly natural graphite coated with the obtained carbonaceous material had an average particle diameter of 5 ⁇ m, an average aspect ratio of 34, (d 002 ) of 0.3357 nm, and a specific surface area of 7.0 m 2 / g.
  • the density of the negative electrode mixture layer can be increased, and the discharge capacity, initial charge / discharge efficiency, rapid charge rate, rapid discharge Both rate and cycle characteristics were excellent.
  • the working electrode was made of a negative electrode material that does not meet the provisions of the present invention, any of discharge capacity, initial charge / discharge efficiency, rapid charge rate, rapid discharge rate, and cycle characteristics was insufficient. .
  • the negative electrode material of the present invention can be used as a negative electrode material for a lithium ion secondary battery that contributes effectively to downsizing and high performance of equipment to be mounted.

Abstract

La présente invention concerne : un matériau d'électrode négative qui présente une excellente efficacité de charge/décharge initiale et/ou d'excellentes caractéristiques de charge à haut débit et/ou d'excellentes caractéristiques de décharge à haut débit et/ou d'excellentes caractéristiques de cycle à long terme; une électrode négative qui utilise ce matériau d'électrode négative; et une batterie secondaire au lithium. Des particules de graphite pour matériaux d'électrode négative de batterie secondaire au lithium-ion, qui sont un mélange de particules de graphite composites (C1) – qui comprennent une matière carbonée (B1) à l'intérieur de particules de graphite sphéroïdal (A) ayant des formes sphériques ou généralement sphériques et/ou sur au moins une partie des surfaces des particules de graphite sphéroïdal (A) – et de particules de graphite composites (C2) qui ont un matériau à base de graphite (B2) à l'intérieur des particules de graphite sphéroïdal (A) ayant des formes sphériques ou généralement sphériques et/ou sur au moins une partie des surfaces des particules de graphite sphéroïdal (A). À cet égard, le mélange satisfait aux exigences (1) à (5) suivantes. (1) La distance inter-planaire (d002) d'une couche superficielle de réseau de carbone est inférieure ou égale à 0,3360 nm. (2) La masse volumique après tassement est égale ou supérieure à 1,0 g/cm3. (3) Le diamètre moyen des particules est compris entre 5 et 25 μm. (4) Le rapport d'aspect moyen est égal ou supérieur à 1,2 mais inférieur à 4,0. (5) Le volume de pores des pores ayant un diamètre inférieur ou égal à 0,5 µm, tel que déterminé au moyen d'un porosimètre à mercure, est inférieur ou égal à 0,08 ml/g.
PCT/JP2015/005207 2014-10-28 2015-10-15 Particules de graphite pour matériaux d'électrode négative de batterie secondaire au lithium-ion, électrode négative de batterie secondaire au lithium-ion et batterie secondaire au lithium-ion WO2016067539A1 (fr)

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CN201580058234.4A CN107078288B (zh) 2014-10-28 2015-10-15 锂离子二次电池负极材料用石墨质粒子、锂离子二次电池负极和锂离子二次电池

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3683871B1 (fr) 2017-10-27 2021-12-01 LG Chem, Ltd. Matériau actif d'électrode négative pour batterie rechargeable au lithium et batterie rechargeable au lithium le comprenant
CN114242966A (zh) * 2021-11-12 2022-03-25 惠州锂威新能源科技有限公司 一种负极复合材料及其制备方法、负极片以及二次电池
EP3869586A4 (fr) * 2018-10-17 2022-07-13 Murata Manufacturing Co., Ltd. Électrode négative pour batterie secondaire au lithium-ion et batterie secondaire au lithium-ion
CN114765253A (zh) * 2021-01-14 2022-07-19 泰星能源解决方案有限公司 石墨系负极活性物质
CN114804095A (zh) * 2022-04-27 2022-07-29 中南大学 一种球化石墨微粉废料制得的石墨负极活性材料及制备方法和应用

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* Cited by examiner, † Cited by third party
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JP6858691B2 (ja) * 2016-11-28 2021-04-14 Ｊｆｅケミカル株式会社 リチウムイオン二次電池負極材料用炭素質被覆黒鉛質粒子の製造方法
JP2019019048A (ja) * 2017-07-13 2019-02-07 Ｊｆｅケミカル株式会社 炭素質被覆黒鉛粒子の製造方法、炭素質被覆黒鉛粒子、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
CN108711623A (zh) * 2018-05-30 2018-10-26 欣旺达电子股份有限公司 锂离子电池、负极片、复合石墨负极材料及其制备方法
US20210218025A1 (en) * 2018-06-15 2021-07-15 Panasonic Intellectual Property Management Co., Ltd. Non-aqueous electrolyte secondary battery
JP7251069B2 (ja) * 2018-08-02 2023-04-04 トヨタ自動車株式会社 全固体電池およびその製造方法
CN113226986B (zh) * 2018-12-19 2023-11-17 浦项控股股份有限公司 锂二次电池负极活性材料的制备方法
JP7293901B2 (ja) * 2019-06-20 2023-06-20 株式会社豊田中央研究所 造粒体、並びに、撥水層及びその製造方法
KR102527750B1 (ko) * 2019-09-17 2023-04-28 제이에프이 케미칼 가부시키가이샤 흑연 재료의 제조 방법
CN114171738B (zh) * 2020-09-10 2023-11-17 贝特瑞新材料集团股份有限公司 石墨负极材料及其制备方法和锂离子电池
CN115279694A (zh) * 2021-03-01 2022-11-01 杰富意化学株式会社 碳质包覆石墨材料的制造方法
CN115472829A (zh) * 2021-06-10 2022-12-13 国家能源投资集团有限责任公司 负极材料及其制备方法与应用、负极片与应用
EP4212479A1 (fr) * 2021-08-17 2023-07-19 JFE Chemical Corporation Graphite sphéroïdal revêtu, électrode négative pour batteries secondaires au lithium-ion et batterie secondaire au lithium-ion
WO2023181705A1 (fr) * 2022-03-24 2023-09-28 三菱ケミカル株式会社 Composition de matériau carboné, procédé de production d'une composition de matériau carboné, électrode négative et batterie secondaire
JP7351438B1 (ja) * 2022-03-24 2023-09-27 三菱ケミカル株式会社 炭素材組成物、炭素材組成物の製造方法、負極及び二次電池

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004111272A (ja) * 2002-09-19 2004-04-08 Sharp Corp リチウムポリマー電池及びその製造方法
JP2008027664A (ja) * 2006-07-19 2008-02-07 Nippon Carbon Co Ltd リチウムイオン二次電池用負極及び負極活物質
WO2010113783A1 (fr) * 2009-03-30 2010-10-07 住友金属工業株式会社 Matériau carbone mixte et électrode négative pour batterie secondaire utilisant un électrolyte non aqueux
JP2010251314A (ja) * 2009-03-27 2010-11-04 Mitsubishi Chemicals Corp 非水電解液二次電池用負極材料及びこれを用いた非水電解液二次電池
JP2014067625A (ja) * 2012-09-26 2014-04-17 Sanyo Electric Co Ltd 非水電解質二次電池
JP2014186956A (ja) * 2013-03-25 2014-10-02 Mitsubishi Chemicals Corp 非水系二次電池負極用炭素材、非水系二次電池用負極及び非水系二次電池

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3236002B2 (ja) 1990-11-22 2001-12-04 大阪瓦斯株式会社 リチウム二次電池
US7829222B2 (en) * 2001-01-25 2010-11-09 Hitachi Chemical Company, Ltd. Artificial graphite particles and method for manufacturing same, nonaqueous electrolyte secondary cell, negative electrode and method for manufacturing same, and lithium secondary cell
JP4666876B2 (ja) 2001-09-26 2011-04-06 Ｊｆｅケミカル株式会社 複合黒鉛質材料およびその製造方法、ならびにリチウムイオン二次電池用負極材料およびリチウムイオン二次電池
JP4040381B2 (ja) 2002-07-30 2008-01-30 Ｊｆｅケミカル株式会社 複合黒鉛質粒子およびその製造方法ならびに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
KR100704096B1 (ko) * 2002-12-19 2007-04-06 제이에프이 케미칼 가부시키가이샤 복합 흑연 입자 및 그의 제조방법, 및 이것을 이용한 리튬이온 2차 전지의 음극재 및 리튬 이온 2차 전지
JP5081375B2 (ja) 2004-02-12 2012-11-28 三菱化学株式会社 リチウム二次電池用負極材料及びその製造方法、並びにそれを用いたリチウム二次電池用負極及びリチウム二次電池
CN113594543A (zh) * 2005-10-20 2021-11-02 三菱化学株式会社 锂二次电池以及其中使用的非水电解液
CN104659414B (zh) * 2005-10-20 2019-04-12 三菱化学株式会社 锂二次电池以及其中使用的非水电解液
JP4989114B2 (ja) 2006-06-02 2012-08-01 日本カーボン株式会社 リチウム二次電池用負極及び負極活物質
EP2128916A4 (fr) * 2006-12-26 2016-11-30 Mitsubishi Chem Corp Particules de graphite composites pour des batteries secondaires non aqueuses, matériau d'électrode négative contenant celles-ci, électrodes négatives et batteries secondaires non aqueuses
KR101641750B1 (ko) * 2009-03-27 2016-07-21 미쓰비시 가가꾸 가부시키가이샤 비수 전해액 2 차 전지용 부극 재료 및 이것을 사용한 비수 전해액 2 차 전지
JP5898628B2 (ja) * 2010-12-08 2016-04-06 日本コークス工業株式会社 リチウムイオン二次電池用負極材料及びその製造方法
CN103477476B (zh) * 2011-03-29 2017-09-08 三菱化学株式会社 非水系二次电池用负极碳材料、负极以及非水系二次电池
JP5266428B1 (ja) * 2011-10-21 2013-08-21 昭和電工株式会社 黒鉛材料、電池電極用炭素材料、及び電池
KR101739295B1 (ko) * 2012-11-26 2017-05-24 삼성에스디아이 주식회사 복합음극활물질, 이를 채용한 음극과 리튬전지 및 그 제조방법

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004111272A (ja) * 2002-09-19 2004-04-08 Sharp Corp リチウムポリマー電池及びその製造方法
JP2008027664A (ja) * 2006-07-19 2008-02-07 Nippon Carbon Co Ltd リチウムイオン二次電池用負極及び負極活物質
JP2010251314A (ja) * 2009-03-27 2010-11-04 Mitsubishi Chemicals Corp 非水電解液二次電池用負極材料及びこれを用いた非水電解液二次電池
WO2010113783A1 (fr) * 2009-03-30 2010-10-07 住友金属工業株式会社 Matériau carbone mixte et électrode négative pour batterie secondaire utilisant un électrolyte non aqueux
JP2014067625A (ja) * 2012-09-26 2014-04-17 Sanyo Electric Co Ltd 非水電解質二次電池
JP2014186956A (ja) * 2013-03-25 2014-10-02 Mitsubishi Chemicals Corp 非水系二次電池負極用炭素材、非水系二次電池用負極及び非水系二次電池

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3683871B1 (fr) 2017-10-27 2021-12-01 LG Chem, Ltd. Matériau actif d'électrode négative pour batterie rechargeable au lithium et batterie rechargeable au lithium le comprenant
EP3869586A4 (fr) * 2018-10-17 2022-07-13 Murata Manufacturing Co., Ltd. Électrode négative pour batterie secondaire au lithium-ion et batterie secondaire au lithium-ion
CN114765253A (zh) * 2021-01-14 2022-07-19 泰星能源解决方案有限公司 石墨系负极活性物质
CN114765253B (zh) * 2021-01-14 2024-02-20 泰星能源解决方案有限公司 石墨系负极活性物质
CN114242966A (zh) * 2021-11-12 2022-03-25 惠州锂威新能源科技有限公司 一种负极复合材料及其制备方法、负极片以及二次电池
CN114242966B (zh) * 2021-11-12 2023-06-13 惠州锂威新能源科技有限公司 一种负极复合材料及其制备方法、负极片以及二次电池
CN114804095A (zh) * 2022-04-27 2022-07-29 中南大学 一种球化石墨微粉废料制得的石墨负极活性材料及制备方法和应用
CN114804095B (zh) * 2022-04-27 2023-12-12 中南大学 一种球化石墨微粉废料制得的石墨负极活性材料及制备方法和应用

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