WO2013128829A1 - Matériau d'électrode négative pour batterie secondaire au lithium-ion, électrode négative pour batterie secondaire au lithium-ion, et batterie secondaire au lithium-ion - Google Patents

Matériau d'électrode négative pour batterie secondaire au lithium-ion, électrode négative pour batterie secondaire au lithium-ion, et batterie secondaire au lithium-ion Download PDF

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WO2013128829A1
WO2013128829A1 PCT/JP2013/000831 JP2013000831W WO2013128829A1 WO 2013128829 A1 WO2013128829 A1 WO 2013128829A1 JP 2013000831 W JP2013000831 W JP 2013000831W WO 2013128829 A1 WO2013128829 A1 WO 2013128829A1
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negative electrode
graphite
lithium ion
ion secondary
secondary battery
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Japanese (ja)
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江口　邦彦
裕香里 美野
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JFE Chemical Corp
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JFE Chemical Corp
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Priority to KR1020147023049A priority patent/KR101633206B1/ko
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—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
    • 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
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of 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
    • H01M4/362—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
    • 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 negative electrode material for a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, and a lithium ion secondary battery.
  • lithium ion secondary batteries are attracting attention because they can achieve higher voltages than other secondary batteries, and can achieve high energy density.
  • the lithium ion secondary battery has a negative electrode, a positive electrode, and an electrolytic solution (nonaqueous electrolyte) as main components. Lithium ions move between the negative electrode and the positive electrode through the electrolytic solution during the discharging process and the charging process to form a secondary battery.
  • the negative electrode is generally composed of a current collector made of copper foil and a negative electrode material (active material: active material) 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 (see Patent Document 1).
  • Lithium ion secondary batteries installed in recent portable electronic devices are required to have excellent rapid chargeability and rapid discharge characteristics, and the initial discharge capacity does not deteriorate even after repeated charge and discharge (high cycle) Characteristics: cycle performance) is required.
  • Typical examples of conventional graphite negative electrode materials include the following.
  • Graphite particles obtained by collecting or combining a plurality of flat particles so that their orientation surfaces are non-parallel, and having fine pores (Patent Document 2).
  • Graphite of mesocarbon spherules made of Brooks-Taylor type single crystals in which basal surfaces of graphite are arranged in layers in a direction perpendicular to the diameter direction Patent Document 3).
  • the density of the active material layer (coated active material) is increased and the discharge capacity per volume is set higher.
  • the active material layer is densified after being applied to the current collector and then pressed at a high pressure, various problems arise with these conventional negative electrode materials.
  • the negative electrode material using the massive graphite particles described in Patent Document 5 can suppress the orientation of the basal plane of graphite 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, due to the oxidation, the crystallinity of the graphite particle surface is lowered, so that there is a problem that the discharge capacity is low.
  • a negative electrode material that maintains excellent rapid chargeability, rapid discharge performance, and cycle characteristics even at high density, is soft, and can be easily densified even at low press pressure is desired.
  • Secondary battery Patent Document 6
  • Patent Document 7 A negative electrode for a lithium ion secondary battery using a negative electrode material in which a mesophase small sphere graphitized product and non-flaky graphite particles having a smaller average particle diameter than the graphitized product (graphitized product of mesophase small spheres) are mixed.
  • a negative electrode material for a lithium secondary battery in which a hydrophilized product of graphitized particles of mesophase microspheres and a composite graphitic carbon material coated with a low crystalline carbon material are mixed (Patent Document 8).
  • the negative electrode for lithium secondary batteries used (Patent Document 9).
  • a non-aqueous secondary battery using a mixture of pitch graphitized material and graphitized mesocarbon microbeads as a negative electrode material Patent Document 10
  • a non-aqueous electrolyte secondary battery using a negative electrode material obtained by mixing a graphite material coated with a non-graphitic carbon material and a natural graphite material Patent Document 11
  • Lithium secondary battery using negative electrode material comprising mesophase spherical graphite having an average particle size of 8 ⁇ m or more and mesophase microspherical graphite having an average particle size of 3 ⁇ m or less so as to fill the gap (7.5% by weight or less) Patent Document 12).
  • Patent Document 13 A non-aqueous electrolyte secondary battery using a mixture of graphite, a first non-graphite carbon material, and acetylene black having a smaller particle diameter as a negative electrode material.
  • Patent Document 14 A nonaqueous electrolyte secondary battery using a negative electrode material obtained by mixing graphitized mesocarbon microbeads and artificial graphite powder having an average particle size smaller than that of the graphitized material.
  • Patent Document 15 The applicant of the present application has proposed Patent Document 15 so far.
  • Japanese Patent Publication No.62-23433 Japanese Patent Laid-Open No. 10-158005 JP 2000-323127 A JP 2004-63321 A JP-A-10-139410 JP 2008-171809 A JP 2007-134276 A JP 2004-253379 A JP 2005-44775 A JP 2005-19096 A JP 2001-185147 A Japanese Patent Laid-Open No. 11-3706 JP-A-10-270019 Japanese Patent Laid-Open No. 7-37618 JP 2011-9051 A
  • the object of the present invention is that when used as a negative electrode material of a lithium ion secondary battery, it reaches a high density at a low pressing pressure, has a high discharge capacity per volume and a high density, while the graphite is crushed.
  • An object of the present invention is to provide a negative electrode material that has excellent rapid chargeability, rapid discharge property, and cycle characteristics without being impaired in the orientation and without impairing the permeability and retention of the electrolyte. 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.
  • the present invention provides the following 1 to 9.
  • A Spherical or ellipsoidal natural graphite having an average particle diameter of 5 to 35 ⁇ m and an average aspect ratio of less than 2.0
  • B a bulk mesophase graphitized product having an average particle size of 2 to 25 ⁇ m and an average aspect ratio of less than 2.0
  • C an average particle size of 1 to 15 ⁇ m and the bulk mesophase graphitized product
  • a, b, and c represent the masses of the components (A), (B), and (C).
  • the spheroidized or ellipsoidal natural graphite (A) comprises spheroidized or ellipsoidal natural graphite having a carbonaceous material or a graphite material attached to at least a part of the surface thereof.
  • Negative electrode material for ion secondary battery. 3.
  • At least one or all of the spheroidized or ellipsoidized natural graphite (A), the bulk mesophase graphitized product (B), and the flaky graphite (C) have a metal oxide embedded on the surface thereof. 6.
  • a lithium ion secondary battery comprising the lithium ion secondary battery negative electrode according to 7 or 8 above.
  • the lithium ion secondary battery negative electrode of the present invention is formed of the negative electrode material of the present invention containing the three types of graphite specified in the above (A) to (C) in a specific amount ratio, whereby an active material layer Even when the density is increased, the current collector is not deformed or broken, and each graphite is prevented from being crushed and oriented, and the electrolyte has excellent permeability. And since each electrolyte tends to exist around each graphite, the diffusibility of lithium ions is improved. Therefore, the lithium ion secondary battery using the negative electrode of the present invention (lithium ion secondary battery of the present invention) has a high discharge capacity per volume and good battery performance such as rapid chargeability, rapid discharge performance, and cycle characteristics. It is. Therefore, the lithium ion secondary battery of the present invention satisfies the recent demand for higher energy density of batteries, and is useful for downsizing and higher performance of equipment to be mounted.
  • a lithium ion secondary battery (hereinafter also simply referred to as a secondary battery) usually has an electrolyte solution (non-aqueous electrolyte), a negative electrode, and a positive electrode as main battery components, and these elements are, for example, in a secondary battery can. It is enclosed.
  • the negative electrode and the positive electrode each act as a lithium ion carrier.
  • the battery mechanism is such that lithium ions are occluded in the negative electrode during charging and lithium ions are released from the negative electrode during discharging.
  • the secondary battery of the present invention is not particularly limited except that the negative electrode material of the present invention is used as the negative electrode material, and other battery components such as a non-aqueous electrolyte, a positive electrode, and a separator are general secondary battery elements.
  • the negative electrode material for a lithium ion secondary battery of the present invention (the negative electrode material of the present invention) (A) Spherical or ellipsoidal natural graphite having an average particle diameter of 5 to 35 ⁇ m and an average aspect ratio of less than 2.0, (B) a bulk mesophase graphitized product having an average particle size of 2 to 25 ⁇ m and an average aspect ratio of less than 2.0, and (C) an average particle size of 1 to 15 ⁇ m and the bulk mesophase graphitized product (B) A negative electrode material for a lithium ion secondary battery containing scaly graphite having an average particle size smaller than an average particle diameter and an average aspect ratio of 5.0 or more in a mass ratio satisfying the following formula (1) and the following formula (2):
  • the negative electrode material of the present invention contains specific spheroidized or ellipsoidal natural graphite (A) and two types of graphite (B) and (C) in a specific amount ratio.
  • the spheroidized or ellipsoidized natural graphite (A), the bulk mesophase graphitized product (B), and the scaly graphite (C) are embedded with a metal oxide on the surface thereof. It is preferable from the standpoint of quick chargeability and excellent cycle characteristics.
  • the metal oxide is embedded, for example, the metal oxide is embedded in the spheroidized or ellipsoidal natural graphite (A), the bulk mesophase graphitized product (B), or the scaly graphite (C) itself.
  • a metal oxide is embedded in or on the surface of the carbonaceous material or the graphite material; a combination thereof may be mentioned.
  • the metal oxide include silica, alumina, titania, zirconia, and iron oxide.
  • One preferred embodiment of the metal oxide is fine particles.
  • the size of the metal oxide can be smaller than graphite (A), (B), and (C), the carbonaceous material that can adhere to these, and the graphite material.
  • Examples of the method of embedding the metal oxide include a method of applying a mechanochemical treatment by repeatedly applying a compressive force and a shearing force to a mixture of the raw material and the metal oxide. Graphite (A) to (C) will be described in detail below.
  • the spheroidized or ellipsoidized natural graphite (hereinafter also referred to as “substantially spherical natural graphite”) (A) used in the present invention has an average particle diameter of 5 to 35 ⁇ m and an average aspect ratio of less than 2.0. It is some natural or spheroidized natural graphite.
  • the shape of the substantially spherical natural graphite (A) is not particularly limited as long as it is spherical or ellipsoidal.
  • the production of the substantially spherical natural graphite (A) is not particularly limited as long as the natural graphite is spheroidized or made into an ellipsoid.
  • a flat or scaly natural graphite that is bent or folded into a substantially spherical shape, or a plurality of scaly natural graphites that are granulated in a concentric or cabbage shape, is preferably spheroidized.
  • the average particle diameter (average particle diameter in terms of volume) of the substantially spherical natural graphite (A) is 5 to 35 ⁇ m, particularly preferably 10 to 30 ⁇ m. If it is 5 micrometers or more, the density of an active material layer can be raised and the discharge capacity per volume will improve. And if it is 35 micrometers or less, quick charge property and cycling characteristics will improve.
  • the average aspect ratio of the substantially spherical natural graphite (A) is less than 2.0, preferably less than 1.5, and more preferably 1.3 or less. The closer the shape to a true sphere, the more the crystal structure of the substantially spherical natural graphite (A) is not oriented in one direction in the particle or on the negative electrode, and the higher the diffusibility of lithium ions in the electrolyte, Dischargeability and cycle characteristics can be improved.
  • the substantially spherical natural graphite (A) has high crystallinity. Since it has high crystallinity, it is soft and contributes to increasing the density of the active material layer. It is preferable that the average lattice spacing d 002 as an index of crystallinity is less than 0.3360 nm, particularly 0.3358 mm or less. Moreover, since substantially spherical natural graphite (A) has high crystallinity, when used for the negative electrode active material of a secondary battery, it can show a high discharge capacity.
  • the discharge capacity when substantially spherical natural graphite (A) alone is used as the negative electrode material is approximately 350 mAh / g or more, preferably 360 mAh / g or more, although it varies depending on the production conditions of the negative electrode and the evaluation battery.
  • the specific surface area of approximately spherical natural graphite (A), in order to lead to a decrease in the initial charge-discharge efficiency of the secondary battery is too large, preferably not more than 20 m 2 / g in specific surface area, 10 m 2 / g or less is more preferable.
  • the production of the substantially spherical natural graphite (A) contained in the negative electrode material of the present invention is not particularly limited.
  • it can be produced by applying mechanical external force to flat or scale-like natural graphite.
  • it can be spheroidized by applying a high shearing force, bending by applying a rolling operation, or spheroidizing by concentric granulation.
  • 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) Heavy Industries Co., Ltd.), “GRANUREX” (Freund Sangyo Co., Ltd.), “New Gramachine” (Seisin Enterprise Co., Ltd.), “Agromaster” (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” (Nara Machinery Co., Ltd.), Compressive
  • the substantially spherical natural graphite (A) is partly or entirely part of which at least part of the surface thereof has a carbonaceous material (A1) or graphite material (A2). .
  • the adhesion of the carbonaceous material or the graphite material can prevent the natural graphite (A) from being crushed.
  • the carbonaceous material attached to the substantially spherical natural graphite (A1) include, for example, coal-based or petroleum-based heavy oil, tars, pitches, and resins such as phenolic resins, which are finally 500 ° C. or higher and 1500 ° C. Carbide formed by heat treatment with less than the above.
  • the adhesion amount of the carbonaceous material is preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the substantially spherical natural graphite (A).
  • Examples of the graphite material adhering to the substantially spherical natural graphite (A2) include heating coal-based or petroleum-based heavy oil, tars, pitches, and resins such as phenol resins at 1500 ° C. or higher and lower than 3300 ° C. Examples thereof include graphitized products obtained by treatment.
  • the adhering amount of the graphite material is preferably 1 to 30 parts by mass, and particularly preferably 5 to 20 parts by mass with respect to 100 parts by mass of the substantially spherical natural graphite (A).
  • a carbonaceous material or a graphite material to a part or all of the substantially spherical natural graphite (A)
  • a carbonaceous material or a precursor of the graphite material for example, coal
  • Manufactured by attaching or coating heavy or petroleum-based oils, tars, pitches, phenolic resins, etc. by any of the vapor phase method, liquid phase method, and solid phase method, followed by heat treatment can do.
  • a specific example of the vapor phase method is a method in which a vapor of a precursor of a carbonaceous material typified by hydrocarbons such as benzene and toluene is deposited on the surface of substantially spherical natural graphite (A) at 900 to 1200 ° C. It is done.
  • the hydrocarbon precursor is carbonized during vapor deposition, and substantially spherical natural graphite (A1) with a carbonaceous material attached thereto is obtained.
  • liquid phase method examples include coal tar, tar light oil, tar middle oil, tar heavy oil, naphthalene oil, anthracene oil, coal tar pitch, pitch oil, mesophase pitch, oxygen-crosslinked petroleum pitch, etc.
  • thermoplastic resins such as polyvinyl alcohol, thermosetting resins such as phenolic resins and furan resins, sugars and celluloses (hereinafter also referred to as carbonaceous material precursors), substantially spherical natural graphite (A)
  • the carbonaceous material precursor or a solution thereof is attached to the substantially spherical natural graphite (A), and finally heat treated at 500 ° C. or more and less than 1500 ° C.
  • substantially spherical natural graphite (A1) to which the material is attached is mentioned.
  • substantially spherical natural graphite (A2) to which the graphite material is attached can be produced.
  • stirring, a heating, and pressure reduction can be performed.
  • the carbonaceous material precursor powder exemplified in the description of the liquid phase method and the substantially spherical natural graphite (A) are mixed, and mechanical energy such as compression, shear, collision, friction, etc. is mixed.
  • the carbonaceous material precursor powder is pressure-bonded to the surface of the substantially spherical natural graphite (A) by the mechanochemical treatment to be applied.
  • the mechanochemical treatment By the mechanochemical treatment, the carbonaceous material precursor is melted or softened and adhered by being rubbed against the substantially spherical natural graphite (A).
  • the apparatus capable of mechanochemical treatment include the various compression shearing processing apparatuses described above.
  • a substantially spherical natural graphite (A1) to which a carbonaceous material is adhered is produced by finally heat-treating the substantially spherical natural graphite (A) to which the powder of the carbonaceous material precursor is adhered at 500 ° C. or more and less than 1500 ° C. Can do. Similarly, by increasing the heat treatment temperature to 1500 ° C. or more and less than 3300 ° C., substantially spherical natural graphite (A2) to which the graphite material is attached can be produced.
  • a conductive material such as carbon fiber or carbon black may be used together with the carbonaceous material precursor.
  • an alkali metal such as Na and K
  • an alkaline earth metal such as Mg and Ca
  • Ti and V Transition metals such as Cr, Mn, Fe, Co, Ni, Zr, Nb, Mn, Mo, Tc, Ru, Rh, Pd, Hf, Ta, W, Re, Os, Ir, Pt, Al, Ge, etc.
  • Metals, metalloids such as B and Si, and metal compounds thereof, for example, hydroxides, oxides, nitrides, chlorides, sulfides and the like may be used alone or in combination.
  • the substantially spherical natural graphite (A) includes at least a part of its surface (A1) having a carbonaceous material attached thereto or (A2) having a graphite material attached thereto (A2) (A) in the total amount (A1)
  • the amount of (A2) is preferably 30 to 100% by mass from the viewpoint of maintaining the shape of the substantially spherical natural graphite (A), that is, excellent initial charge / discharge efficiency even when the density of the negative electrode is increased. .
  • the substantially spherical natural graphite (A1) to which the carbonaceous material is attached or the substantially spherical natural graphite (A2) to which the graphite material is attached is composed of carbon fibers or It may have a conductive material such as carbon black, or may have a metal oxide such as silica, aluminum oxide (alumina), titanium oxide (titania) attached or embedded (for example, in fine particles), A metal or a metal compound such as silicon, tin, cobalt, nickel, copper, silicon oxide, tin oxide, or lithium titanate may be attached or embedded.
  • the carbonaceous material or graphite material that adheres to the substantially spherical natural graphite (A) preferably has the above metal oxide (for example, as fine particles of the metal oxide) inside or on the surface thereof, More preferably, it is buried.
  • a method of applying mechanical external force to the substantially spherical natural graphite (A1) or (A2) in the presence of the metal oxide fine particles is exemplified. It can be manufactured by using a compression shear type processing apparatus.
  • the amount of the metal oxide is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of the substantially spherical natural graphite (A1) or (A2).
  • the substantially spherical natural graphite (A) includes a carbonaceous material (A1) or a graphite material (A2) attached to at least a part of its surface, and the carbonaceous material or graphite material is contained therein.
  • the surface has a metal oxide (such a graphite material is referred to as natural graphite (A3))
  • the amount of natural graphite (A3) is 30% in the total amount of (A) from the viewpoint of excellent quick chargeability. It is preferably from ⁇ 100% by mass.
  • spherical natural graphite (A1) with carbonaceous material attached approximately spherical natural graphite (A2) with attached graphite material, average particle diameter, average aspect ratio, average lattice of natural graphite after metal oxide is embedded
  • the preferable range of the interplanar spacing d 002 and the specific surface area is the same as in the case of the substantially spherical natural graphite (A) having no adhesion of the carbonaceous material or the graphite material.
  • the substantially spherical natural graphite (A) can be used alone or in combination of two or more.
  • the bulk mesophase graphitized product (B) used in the present invention is artificial graphite particles having a dense particle interior.
  • the average particle diameter (in terms of volume) of the bulk mesophase graphitized product (B) is 2 to 25 ⁇ m, and particularly preferably 3 to 20 ⁇ m. If it is less than 2 ⁇ m, the initial charge / discharge efficiency may be lowered. When the thickness exceeds 25 ⁇ m, a high pressure is required to increase the density of the active material layer, which may cause problems such as deformation, elongation, and breakage of the copper foil as the current collector.
  • the active material layer can be made dense at a low pressure. This is desirable.
  • the average aspect ratio of the bulk mesophase graphitized product (B) is less than 2.0, preferably less than 1.5, and more preferably less than 1.3. The closer the shape is to a perfect sphere, the more the crystal structure of the bulk mesophase graphitized product (B) is not oriented in one direction in the particles or on the negative electrode, and the higher the diffusibility of lithium ions in the electrolyte, Dischargeability and cycle characteristics are improved.
  • Bulk mesophase graphite product (B) is preferably has a high crystallinity, average lattice spacing d 002 of less than 0.3370 nm, it is preferable that particularly 0.3365nm or less.
  • the discharge capacity when the bulk mesophase graphitized material (B) alone is used as the negative electrode active material of the secondary battery is 320 mAh / g or more, preferably 330 mAh / g or more, although it varies depending on the preparation conditions of the negative electrode and the evaluation battery. .
  • the specific surface area of the bulk mesophase graphite product (B), in order to lead to a decrease in the initial charge-discharge efficiency of the secondary battery is too large, preferably 20 m 2 / g or less in specific surface area, 10 m 2 / g or less is more preferable.
  • the bulk mesophase graphitized product (B) preferably includes a bulk mesophase graphitized product obtained by heat-treating tars and / or pitches to be pulverized, oxidized, carbonized, and graphitized.
  • Mesophase calcined carbon (bulk mesophase) obtained by heating coal-based tar and / or pitch to bring the aspect ratio of the bulk mesophase graphitized product (B) as close to 1.0 as possible, that is, close to a true sphere.
  • a bulk mesophase graphitized product obtained by pulverizing, oxidizing, carbonizing, and graphitizing this material is particularly preferable.
  • coal-based tars and pitches are heat-treated at 250 to 400 ° C.
  • the bulk mesophase graphitized product (B) is preferably a part or all of the bulk mesophase graphitized material (B1) having a carbonaceous material attached to at least a part of its surface (B2) or a material having a graphite material attached (B2). One of them.
  • the adhesion of the carbonaceous material or the graphite material can prevent the bulk mesophase graphitized product (B) from being crushed.
  • the carbonaceous material that can be used is the same as described above.
  • the adhesion amount of the carbonaceous material is preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the bulk mesophase graphitized product (B).
  • the graphite material that can be used is the same as described above.
  • the adhesion amount of the graphite material is preferably 1 to 30 parts by mass, particularly preferably 5 to 20 parts by mass with respect to 100 parts by mass of the bulk mesophase graphitized product (B).
  • the method of attaching the carbonaceous material or the graphite material to a part or all of the bulk mesophase graphitized product (B) is the same as described above.
  • the amount of (B2) is preferably 30 to 100% by mass from the viewpoint of maintaining the shape of the bulk mesophase graphitized product (B), that is, excellent in initial charge / discharge efficiency even when the density of the negative electrode is increased.
  • the bulk mesophase graphitized material (B1) to which the carbonaceous material is adhered or the bulk mesophase graphitized material (B2) to which the graphite material is adhered is formed of carbon fiber, carbon black, or the like inside or on the surface of the carbonaceous material or graphite material. It may have a conductive material, or may be one in which a metal oxide such as silica, aluminum oxide (alumina), titanium oxide (titania) is attached or embedded (for example, in fine particles), silicon, tin, A metal or a metal compound such as cobalt, nickel, copper, silicon oxide, tin oxide, or lithium titanate may be attached or embedded.
  • the carbonaceous material or graphite material that adheres to the bulk mesophase graphitized product (B) preferably has the above metal oxide (for example, as fine particles of the metal oxide) inside or on the surface thereof, More preferably, it is buried.
  • the burying method is the same as described above.
  • the amount of the metal oxide is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of the substantially spherical natural graphite (B1) or (B2).
  • the bulk mesophase graphitized material (B) includes at least a part of the surface of which the carbonaceous material is adhered (B1) or the material of the graphite material (B2), and the carbonaceous material or the graphite material is contained therein.
  • the surface has a metal oxide (such a graphite material is referred to as a bulk mesophase graphitized product (B3))
  • the amount of the bulk mesophase graphitized product (B3) is (B) from the viewpoint of excellent quick chargeability. It is preferably 30 to 100% by mass in the total amount.
  • Average particle diameter, average aspect ratio, average of bulk mesophase graphitized material [for example, (B1), (B2), (B3)] after carbonaceous material, graphite material, metal oxide or the like is attached or embedded
  • the preferred range of the lattice spacing d 002 and the specific surface area is the same as that of the bulk mesophase graphitized material (B) not attached or embedded.
  • the bulk mesophase graphitized product (B) can be used alone or in combination of two or more.
  • the flaky graphite (C) used in the present invention is flaky artificial graphite or natural graphite.
  • the scaly graphite (C) may be in a state where a plurality thereof is laminated, a state where it is dispersed as single particles is preferable. It may be in a state where it is bent in the middle of the scale shape or in a state where the end of the particle is rounded.
  • the average particle size of the flake graphite (C) must be smaller than the average particle size of the bulk mesophase graphitized product (B), and the average particle size in terms of volume is 1 to 15 ⁇ m, particularly 3 to 10 ⁇ m. Preferably there is.
  • the reactivity of electrolyte solution can be suppressed and high initial stage charge / discharge efficiency can be obtained. And if it is 15 micrometers or less, rapid discharge property and cycling characteristics will improve.
  • the average particle size of the scale-like graphite (C) is larger than the average particle size of the bulk mesophase graphitized product (B), when the active material layer is densified, sufficient voids are not secured in the negative electrode, and lithium Ion diffusibility decreases, causing rapid chargeability, rapid discharge, and cycle characteristics to deteriorate.
  • the average aspect ratio of the flake graphite (C) is 5.0 or more, and preferably 20 or more. As the aspect ratio is larger and the thickness is thinner, the conductivity of the negative electrode made of each of these graphites can be increased without impeding the contact of other graphites (A) and (B). Improved characteristics. When the average aspect ratio is less than 5, a high pressure is required to increase the density of the active material layer, which may cause problems such as deformation, elongation and breakage of the copper foil as the current collector.
  • Scaly graphite (C) has high crystallinity. Since it has high crystallinity, it is soft and contributes to increasing the density of the active material layer. Less than average lattice spacing d 002 is 0.3360 nm, it is preferable that particularly 0.3358nm or less. In addition, since scaly graphite (C) has high crystallinity, when it is used as a negative electrode active material for a secondary battery, it exhibits a high discharge capacity. The discharge capacity when scaly graphite (C) alone is used as the negative electrode material is approximately 350 mAh / g or more, preferably 360 mAh / g or more, although it varies depending on the production conditions of the negative electrode and the evaluation battery.
  • the specific surface area of the flake graphite (C), in order to lead to a decrease in the initial charge-discharge efficiency of the secondary battery is too large, preferably not more than 20 m 2 / g in specific surface area, 10 m 2 / g or less is more preferable.
  • the scaly graphite (C) is partly or wholly (C1) having a carbonaceous material attached to at least part of its surface.
  • the carbonaceous material attached to the flaky graphite (C1) include those similar to the above-mentioned substantially spherical natural graphite (A1).
  • the amount of the carbonaceous material attached is 100 parts by weight of the flaky graphite (C).
  • the amount is preferably 0.1 to 10 parts by mass, particularly 0.5 to 5 parts by mass.
  • a precursor of a carbonaceous material is added to the above-mentioned natural graphite (A) by a gas phase method, a liquid phase method, or a solid phase method.
  • the same method as the method of heat-treating after applying or covering with either can be applied.
  • the amount of (C1) in the total amount of (C) may increase the density of the negative electrode.
  • the amount of (C1) in the total amount of (C) may increase the density of the negative electrode. From the viewpoint of maintaining the shape of the scaly graphite (C), that is, excellent initial charge / discharge efficiency, it is preferably 30 to 100% by mass.
  • the flaky graphite (C) or the flaky graphite (C1) to which the carbonaceous material is attached may have a conductive material such as carbon fiber or carbon black on its surface or inside the carbonaceous material, and silica.
  • a conductive material such as carbon fiber or carbon black
  • silica Aluminum oxide (alumina), titanium oxide (titania) and other metal oxide fine particles may be attached or embedded, silicon, tin, cobalt, nickel, copper, silicon oxide, tin oxide, lithium titanate
  • a metal or a metal compound such as those attached or embedded may be used.
  • the metal oxide fine particles are preferably embedded.
  • the carbonaceous material adhering to the flaky graphite (C) has the above metal oxide (for example, as fine particles of the metal oxide) inside or on the surface, and it is more preferable to embed it.
  • the burying method include a method of applying mechanical external force to the flaky graphite (C1) or the flaky graphite (C1) to which the carbonaceous material is adhered in the presence of the fine particles of the metal oxide. It can be manufactured by using a compression shear type processing device among the devices capable of processing.
  • the amount of the metal oxide is preferably 0.01 to 10 parts by mass, more preferably 100 parts by mass of the flaky graphite (C) or the flaky graphite (C1) to which the carbonaceous material adheres. 0.05 to 2 parts by mass.
  • the scaly graphite (C) includes at least a part of its surface (C1) having a carbonaceous material attached thereto, and the carbonaceous material has a metal oxide inside or on its surface (such a graphite material)
  • the amount of flaky graphite (C3)) and flaky graphite (C3) is preferably 30 to 100% by mass in the total amount of (C) from the viewpoint of excellent rapid chargeability.
  • the preferred range of the specific surface area is the same as the flaky graphite (C) that is not attached, embedded or the like.
  • Each of the flaky graphites (C) can be used alone or in combination of two or more.
  • the negative electrode material for a lithium ion secondary battery of the present invention (hereinafter also simply referred to as a negative electrode material) essentially consists of the above three components (A), (B) and (C), represented by the following formulas (1) and ( It is included at a specific ratio that satisfies 2).
  • a: b (60 to 95): (40 to 5)
  • a + b): c (85 or more to less than 100): (15 or less to more than 0) (2)
  • a, b, and c show the mass of each component (A), (B), and (C).
  • Exceeding 0 indicates a value exceeding 0.
  • known active materials and conductive materials other than the above (A), (B) and (C) can be mixed into the negative electrode material of the present invention.
  • carbon particles such as soft carbon and hard carbon obtained by heat-treating the above carbonaceous material precursor at 500 to 1500 ° C.
  • carbon blacks such as ketjen black and acetylene black
  • vapor grown carbon fiber carbon nanofiber
  • Conductive materials such as carbon nanotubes, metals such as silicon, tin, or oxides thereof that form an alloy with lithium, and metalloids such as metal oxides.
  • the discharge capacity of the negative electrode material of the present invention comprising the above three components (A), (B) and (C) varies depending on the production conditions of the negative electrode and the evaluation battery, it is approximately 355 mAh / g or more, preferably 360 mAh / g That's it.
  • 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 performing the above.
  • 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. When this is applied to the current collector and dried, the negative electrode mixture layer adheres uniformly and firmly to the current collector.
  • 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.
  • 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.
  • the density of the negative electrode mixture layer is preferably 1.70 g / cm 3 or more, particularly preferably 1.75 g / cm 3 or more in order to increase the volume capacity of the negative electrode.
  • 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 negative electrode material of the present invention has a high density, the collapse and orientation of graphite are suppressed.
  • the degree of orientation of the negative electrode can be quantitatively evaluated by X-ray diffraction, and the measurement method will be described below.
  • a negative electrode whose density of the negative electrode mixture layer is adjusted to 1.70 to 1.75 g / cm 3 is punched into a 2 cm 2 disk shape, and this is stuck on the glass plate so that the negative electrode mixture layer faces upward.
  • this sample is irradiated with X-rays and diffracted, a diffraction peak corresponding to the crystal plane of graphite appears.
  • the degree of orientation (I004 / I110) of the negative electrode of the present invention is 20 or less, preferably 15 or less, more preferably 12 or less, when the density of the negative electrode mixture layer is 1.70 to 1.75 g / cm 3 .
  • 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 LiM 1 1-X M 2 X O 2 (wherein X is a numerical value in the range of 0 ⁇ X ⁇ 1, and M 1 and M 2 are at least one kind) Is a transition metal element) or LiM 1 1-Y M 2 Y O 4 (wherein Y is a numerical value in the range of 0 ⁇ Y ⁇ 1, and M 1 and M 2 are at least one transition metal element) Indicated.
  • the transition metal elements represented by M 1 and M 2 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 may be formed by dispersing the positive electrode mixture in a solvent and applying the paste-like positive electrode mixture to a current collector and drying to form a positive electrode mixture layer. After that, 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, t
  • 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 polymer solid electrolyte or polymer gel electrolyte is mixed with a plasticizer, and the electrolyte salt or non-aqueous solvent can be used as the plasticizer.
  • 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.
  • the polymer compound constituting the matrix, the lithium salt, and the nonaqueous solvent (plasticizer) are mixed and heated to melt the polymer compound.
  • Method of evaporating organic solvent for mixing after dissolving polymer compound, lithium salt, and non-aqueous solvent (plasticizer) in organic solvent, mixing polymerizable monomer, lithium salt and non-aqueous solvent (plasticizer) In addition, a method of obtaining a polymer compound by irradiating the mixture with ultraviolet rays, an electron beam, a molecular beam or the like to polymerize a polymerizable monomer can be exemplified.
  • 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.
  • the negative or spherical material was prepared by mixing 75 parts by mass of the spheroidized or ellipsoidal natural graphite (A), 20 parts by mass of the bulk mesophase graphitized product (B) and 5 parts by mass of the flake graphite (C).
  • 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 positive electrode
  • LiPF 6 was dissolved at a concentration of 1 mol / L in a mixed solvent of ethylene carbonate 33 vol% and 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.
  • a current collector 7 a made of nickel net 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 (positive electrode) 4 made of lithium foil, a separator 5 impregnated with an electrolyte, and a disk-like action made of a negative electrode mixture
  • 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.
  • 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
  • the evaluation battery obtained by using the negative electrode material of Example 1 as the working electrode can increase the density of the active material layer and exhibits a high discharge capacity per mass. 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 [Preparation of Spherical or Ellipsoidal Natural Graphite (A1-1) with Carbonaceous Material Adhered]
  • A spheroidized or ellipsoidal natural graphite
  • A spheroidized or ellipsoidal natural graphite
  • 3 parts by mass of pitch powder (average particle size 2 ⁇ m) having a softening point of 120 ° C. and Ketjen Black (average particle size 30 nm) 0.1 Mass parts were mixed and put into a “mechanofusion system”, and mechanochemical treatment was performed by repeatedly applying compressive force and shearing force under conditions of a peripheral speed of the rotating drum of 20 m / second and a treatment time of 30 minutes.
  • the obtained sample was filled in a graphite crucible and fired at 1000 ° C. for 3 hours in a non-oxidizing atmosphere.
  • the obtained spheroidized or ellipsoidal natural graphite had a carbide deposited in the form of a film on most of its surface.
  • Example 1 Except that the spheroidized or ellipsoidized natural graphite (A) and the scaly graphite (C) in Example 1 were replaced with these (A1-1) and (C1), the same procedure as in Example 1 was performed.
  • a working electrode was prepared by adjusting the density of the negative electrode mixture layer 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.
  • Example 2 the mass of spheroidized or ellipsoidal natural graphite (A1-1) to which a carbonaceous material was adhered, bulk mesophase graphitized product (B), and scale-like graphite (C1) to which a carbonaceous material was adhered.
  • a working electrode was prepared by adjusting the density of the negative electrode mixture layer to 1.75 g / cm 3 in the same manner as in Example 2 except that the ratio was changed as shown in Table 1, and an evaluation battery was prepared. The same charge / discharge test as in Example 1 was performed, and the evaluation results of the battery characteristics are shown in Table 1.
  • the density of the negative electrode mixture layer can be increased, and the discharge capacity, initial charge / discharge efficiency, rapid charge rate, rapid discharge rate, cycle characteristics None of them were excellent.
  • Example 1 The density of the negative electrode mixture layer was adjusted to 1.75 g / cm 3 in the same manner as in Example 1 except that the spheroidized or ellipsoidal natural graphite (A) used in Example 1 was used alone as the negative electrode material. Thus, a working electrode was produced, 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.
  • Example 2 The density of the negative electrode mixture layer was the same as in Example 1 except that the spheroidized or ellipsoidal natural graphite (A1-1) to which the carbonaceous material used in Example 2 was attached was used alone as the negative electrode material. was adjusted to 1.75 g / cm 3 to produce a working electrode, 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.
  • Example 3 A working electrode was prepared by adjusting the density of the negative electrode mixture layer to 1.75 g / cm 3 in the same manner as in Example 1 except that the bulk mesophase graphitized product (B) used in Example 1 was used alone as the negative electrode material. Then, 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.
  • Example 4 A working electrode was prepared by adjusting the density of the negative electrode mixture layer to 1.75 g / cm 3 in the same manner as in Example 1 except that the scaly graphite (C) used in Example 1 was used alone as the negative electrode material. 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.
  • Example 5 The density of the negative electrode mixture layer was adjusted to 1.75 g / cm 3 in the same manner as in Example 1 except that the scaly graphite (C1) to which the carbonaceous material used in Example 2 was attached was used alone as the negative electrode material. Thus, a working electrode was produced, 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.
  • Example 2 the mass of spheroidized or ellipsoidal natural graphite (A1-1) to which a carbonaceous material was adhered, bulk mesophase graphitized product (B), and scale-like graphite (C1) to which a carbonaceous material was adhered.
  • a working electrode was prepared by adjusting the density of the negative electrode mixture layer to 1.75 g / cm 3 in the same manner as in Example 2 except that the ratio was changed as shown in Table 1, and an evaluation battery was prepared. The same charge / discharge test as in Example 1 was performed, and the evaluation results of the battery characteristics are shown in Table 1.
  • the working electrode was made of a negative electrode material that deviated from the mass ratio defined by the present invention, any of discharge capacity, initial charge / discharge efficiency, rapid charge rate, rapid discharge rate, and cycle characteristics was insufficient.
  • Example 6 [Preparation of Spheroidized or Ellipsoidized Natural Graphite (A2-1) with Graphite Material Adhered] 25 parts by mass of pitch powder (average particle diameter 2 ⁇ m) having a softening point of 120 ° C. was mixed with 100 parts by mass of the spheroidized or ellipsoidized natural graphite (A) used in Example 1, and put into the “mechanofusion system”. Then, a mechanochemical treatment was performed by repeatedly applying a compressive force and a shearing force under the conditions of a peripheral speed of the rotating drum of 20 m / second and a treatment time of 30 minutes.
  • the obtained sample was filled in a graphite crucible and fired at 1000 ° C. for 3 hours in a non-oxidizing atmosphere. Next, graphitization was performed for 5 hours at 3000 ° C. in a non-oxidizing atmosphere to prepare spheroidized or ellipsoidal natural graphite (A2-1) to which a graphite material was adhered.
  • the obtained spheroidized or ellipsoidal natural graphite had a graphitized substance attached to the most part of its surface in the form of a film.
  • the average particle diameter of the spheroidized or ellipsoidized natural graphite (A2-1) to which the obtained graphite material is attached is 19 ⁇ m
  • the average lattice spacing d 002 is 0.3357 nm
  • the specific surface area is 1.2 m 2 / g. there were.
  • (A2-1) was adjusted to 1.75 g / cm 3 to produce a working electrode, 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.
  • Example 7 [Preparation of spherical or ellipsoidal natural graphite (A3) embedded with metal oxide fine particles]
  • the silica powder (average particle diameter of 50 nm) 0.5 part by mass was mixed with 100 parts by mass of the spherical or ellipsoidal natural graphite (A1-1) to which the carbonaceous material used in Example 2 was attached.
  • the mechanochemical treatment was performed by repeatedly applying a compressive force and a shearing force under the conditions of a peripheral speed of the rotating drum of 20 m / sec and a treatment time of 30 minutes.
  • the obtained spheroidized or ellipsoidal natural graphite (A3) had silica powder uniformly embedded in a carbide coating on the surface.
  • Example 2 the spheroidized or ellipsoidal natural graphite (A1-1) to which the carbonaceous matter was attached and the flaky graphite (C1) to which the carbonaceous matter was attached were obtained as (A3) and (C1 ′).
  • a working electrode was prepared by adjusting the density of the negative electrode mixture layer to 1.75 g / cm 3 in the same manner as in Example 2 except that the evaluation battery was prepared. 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 7 is the same as Example 7 except that the combination of (A1-1) or (A3), bulk mesophase graphitized product (B), and (C1) or (C1 ′) is changed as shown in Table 1. Similarly, the working electrode was prepared by adjusting the density of the negative electrode mixture layer 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.
  • Example 7 spheroidized or ellipsoidal natural graphite (A3) embedded with metal oxide fine particles, bulk mesophase graphitized product (B), and / or flaky graphite (C1 ′) embedded with metal oxide fine particles ) was changed as shown in Table 1 and the density of the negative electrode mixture layer was adjusted to 1.75 g / cm 3 in the same manner as in Example 7 to produce a working electrode, 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.
  • the density of the negative electrode mixture layer can be increased, and the discharge capacity, initial charge / discharge efficiency, rapid charge rate, rapid discharge rate, All of the cycle characteristics were excellent.
  • Example 7 the density of the negative electrode mixture layer was changed in the same manner as in Example 7 except that the average particle sizes of (A3), bulk mesophase graphitized products (B) and (C1 ′) were changed as shown in Table 1.
  • 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.
  • any of discharge capacity, initial charge / discharge efficiency, rapid charge rate, rapid discharge rate, and cycle characteristics is insufficient. It was.
  • Example 2 a non-granulated graphite having a small average aspect ratio described below was prototyped and used instead of scaly graphite (C1).
  • the coal tar pitch was heat-treated at 450 ° C. for 90 minutes in an inert atmosphere to produce 35% by mass of mesophase spherules in the pitch matrix. Thereafter, mesophase spherules were dissolved and extracted using tar oil, separated by filtration, and dried at 120 ° C. in a nitrogen atmosphere. This was heat-treated at 600 ° C. for 3 hours in a nitrogen atmosphere to prepare a mesophase microsphere fired product.
  • the fired product was pulverized, filled into a graphite crucible, and graphitized at 3150 ° C. for 5 hours in a non-oxidizing atmosphere.
  • 100 parts by mass of the graphitized material was mixed with 0.5 parts by mass of silica powder (average particle size: 50 nm) and put into a “mechanofusion system”.
  • the peripheral speed of the rotating drum was 20 m / sec and the processing time was 30 minutes. Under the conditions, compressive force and shear force were repeatedly applied to perform mechanochemical treatment.
  • Silica powder was uniformly embedded in the surface of the obtained graphite.
  • the obtained non-granulated mesophase microsphere graphitized product is a lump with an average aspect ratio of 1.2, an average particle diameter of 5 ⁇ m, an average lattice spacing d 002 of 0.3360 nm, and a specific surface area of 4.2. m 2 / g.
  • a working electrode was prepared by adjusting the density of the negative electrode mixture layer to 1.75 g / cm 3 in the same manner as in Example 2 except that the scaly graphite (C1) was changed to the non-granulated graphite. Was made.
  • the same charge / discharge test as in Example 1 was performed, and the evaluation results of the battery characteristics are shown in Table 1.
  • the working electrode was made of a negative electrode material that deviated from the average aspect ratio range of the flaky graphite defined by the present invention, the rapid charge rate and cycle characteristics were insufficient.
  • Example 14 a granulated graphite having a small average aspect ratio described below was prototyped and used instead of scaly graphite (C1).
  • Coke particles (average particle size 5 ⁇ m) 80 parts by mass and coal tar pitch 20 parts by mass were kneaded at 200 ° C. for 1 hour using a biaxial kneader. The kneaded product was molded into a box shape at 200 ° C., and then graphitized at 3150 ° C. for 5 hours in a non-oxidizing atmosphere. The obtained graphitized material was pulverized to prepare granulated graphite.
  • the obtained granulated graphite was a massive aggregate having an average aspect ratio of 1.7, an average particle diameter of 15 ⁇ m, an average lattice spacing d 002 of 0.3358 nm, and a specific surface area of 3.2 m 2 / g. .
  • a working electrode was prepared by adjusting the density of the negative electrode mixture layer to 1.75 g / cm 3 in the same manner as in Example 2 except that the scaly graphite (C1) was changed to the granulated graphite, and an evaluation battery was prepared. 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.
  • the working electrode was made of a negative electrode material that deviated from the average aspect ratio range of the flaky graphite defined by the present invention, the rapid charge rate and cycle characteristics were insufficient.
  • Example 14 and 15 The density of the negative electrode mixture layer was adjusted to 1.75 g / cm 3 in the same manner as in Example 2 except that the combination of (A1-1) and (C1) was changed as shown in Table 1 in Example 2. Thus, a working electrode was produced, 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.
  • Example 16 [Preparation of bulk mesophase graphitized material (B1 ') embedded with metal oxide fine particles]
  • carbide was adhered in the same manner as A1-1 used in Example 2.
  • silica powder was uniformly embedded in the bulk mesophase graphitized product (B1) to which the obtained carbonaceous material was adhered in the same manner as the spheroidized or ellipsoidized natural graphite (A3) used in Example 7.
  • a bulk mesophase graphitized material (B1 ′) in which metal oxide fine particles were embedded was prepared.
  • a working electrode was prepared by adjusting the density of the negative electrode mixture layer to 1.75 g / cm 3 in the same manner as in Example 2 except that the bulk mesophase graphitized product (B) was changed to (B1 ′) in Example 2. Then, 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.
  • Example 17 In Example 2, when preparing the bulk mesophase graphitized product (B), the negative electrode mixture layer was changed in the same manner as in Example 2 except that the pulverization method of the bulk mesophase was changed to change the average aspect ratio and the average particle size. was adjusted to 1.75 g / cm 3 to produce a working electrode, 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.
  • Example 18 Spherical or ellipsoidal natural graphite (A3) embedded with metal oxide fine particles prepared in Example 7, bulk mesophase graphitized material (B1 ′) embedded with metal oxide fine particles prepared in Example 16, and Using the scale-like graphite (C1 ′) embedded with the metal oxide fine particles prepared in Example 7, the negative electrode mixture layer density was adjusted to 1.75 g / cm 3 in the same manner as in Example 1 to obtain a working electrode. An evaluation battery was prepared. The same charge / discharge test as in Example 1 was performed, and the evaluation results of the battery characteristics are shown in Table 2.
  • Example 19 [Preparation of spherical or ellipsoidal natural graphite (A3 ′) embedded with metal oxide fine particles]
  • Spherical or ellipsoidal natural graphite (A3 ′) embedded with alumina was prepared in the same manner as in Example 7 except that alumina was used instead of silica as the metal oxide.
  • the negative electrode mixture layer was formed in the same manner as in Example 2 except that the spheroidized or ellipsoidized natural graphite (A1-1) to which the carbonaceous material was adhered was changed to the above (A3 ′).
  • a working electrode was prepared by adjusting the density 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 2.
  • Example 20 [Preparation of bulk mesophase graphitized material (B1 '') embedded with metal oxide fine particles]
  • Bulk mesophase graphitized material (B1 ′′) in which titanium oxide was embedded was prepared in the same manner as in Example 16 except that titanium oxide was used instead of silica as the metal oxide in Example 16.
  • the density of the negative electrode mixture layer was adjusted to 1.75 g / cm 3 in the same manner as in Example 2 except that the bulk mesophase graphitized product (B) was changed to (B1 ′′).
  • An evaluation battery was prepared. The same charge / discharge test as in Example 1 was performed, and the evaluation results of the battery characteristics are shown in Table 2.
  • Example 21 [Preparation of flake graphite (C1 ′′) with metal oxide fine particles embedded] Scale-like graphite (C1 ′′) in which alumina was embedded was prepared in the same manner as in Example 7 except that alumina was used instead of silica as the metal oxide.
  • the density of the negative electrode mixture layer was changed to 1.75 g / cm 3 in the same manner as in Example 2 except that the scaly graphite (C1) to which the carbonaceous material was adhered was changed to (C1 ′′).
  • a working electrode was prepared by adjusting, and an evaluation battery was prepared. The same charge / discharge test as in Example 1 was performed, and the evaluation results of the battery characteristics are shown in Table 2.
  • Example 2 the density of the negative electrode mixture layer was adjusted to 1.75 g / cm 3 in the same manner as in Example 1 except that the bulk mesophase graphite compound (B) was changed to the mesophase microsphere graphitized material prepared as described above. Thus, a working electrode was produced, 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 2.
  • Example 16 In Example 2, the density of the negative electrode mixture layer was adjusted to 1.75 g / cm 3 in the same manner as in Example 2 except that the bulk mesophase graphite compound (B) was changed to the mesophase microsphere graphitized material prepared in Comparative Example 15. Thus, a working electrode was produced, 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 2.
  • 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.

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Abstract

L'invention concerne un matériau d'électrode négative pour batterie secondaire au lithium-ion, une électrode négative pour batterie secondaire au lithium-ion ainsi qu'une batterie secondaire au lithium-ion mettant en œuvre celui-ci. Le matériau d'électrode négative pour batterie secondaire au lithium-ion contient en proportion en masse : (A) un graphite naturel sphéroïdisé ou ellipsoïdisé de diamètre moyen de particule de 5 à 35µm, et de rapport d'aspect moyen inférieur à 2,0 ; (B) un produit de graphitisation en mésophase en volume de diamètre moyen de particule de 2 à 25µm, et de rapport d'aspect moyen inférieur à 2,0 ; et (C) un graphite en forme d'écaille de diamètre moyen de particule de 5 à 15µm et plus petit que celui dudit (B) produit de graphitisation en mésophase en volume, et de rapport d'aspect moyen supérieur ou égal à 5,0.
PCT/JP2013/000831 2012-03-02 2013-02-15 Matériau d'électrode négative pour batterie secondaire au lithium-ion, électrode négative pour batterie secondaire au lithium-ion, et batterie secondaire au lithium-ion Ceased WO2013128829A1 (fr)

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KR1020147023049A KR101633206B1 (ko) 2012-03-02 2013-02-15 리튬 이온 이차 전지용 부극 재료, 리튬 이온 이차 전지용 부극 및 리튬 이온 이차 전지

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CN104145358A (zh) 2014-11-12
TW201345031A (zh) 2013-11-01
KR20140121445A (ko) 2014-10-15
CN104145358B (zh) 2017-03-08

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