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WO2016194355A1 - Particules de graphite à revêtement carboné pour matériau d'électrode négative de pile rechargeable lithium-ion, électrode négative pour pile rechargeable lithium-ion, et pile rechargeable lithium-ion - Google Patents

Particules de graphite à revêtement carboné pour matériau d'électrode négative de pile rechargeable lithium-ion, électrode négative pour pile rechargeable lithium-ion, et pile rechargeable lithium-ion Download PDF

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Publication number
WO2016194355A1
WO2016194355A1 PCT/JP2016/002602 JP2016002602W WO2016194355A1 WO 2016194355 A1 WO2016194355 A1 WO 2016194355A1 JP 2016002602 W JP2016002602 W JP 2016002602W WO 2016194355 A1 WO2016194355 A1 WO 2016194355A1
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Prior art keywords
graphite particles
negative electrode
ion secondary
carbonaceous
lithium
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PCT/JP2016/002602
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English (en)
Japanese (ja)
Inventor
間所　靖
江口　邦彦
哲夫 塩出
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Ｊｆｅケミカル株式会社
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Priority claimed from JP2016095119A external-priority patent/JP6412520B2/ja
Application filed by Ｊｆｅケミカル株式会社 filed Critical Ｊｆｅケミカル株式会社
Priority to KR1020177029191A priority Critical patent/KR101990723B1/ko
Priority to CN201680025230.0A priority patent/CN107534148B/zh
Publication of WO2016194355A1 publication Critical patent/WO2016194355A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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 carbon-coated graphite particle for 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 using the negative electrode.
  • Lithium ion secondary batteries are widely used in portable electronic devices, and have started to be used in hybrid and electric vehicles. Under such circumstances, lithium ion secondary batteries are required to have higher capacity, faster charge / discharge characteristics, and cycle characteristics.
  • the lithium ion secondary battery has a negative electrode, a positive electrode, and a non-aqueous electrolyte as main components, and acts as a secondary battery by moving lithium ions between the negative electrode and the positive electrode during a discharging process and a charging process.
  • graphite is widely used as the negative electrode material. Graphite is roughly classified into natural graphite and artificial graphite. Natural graphite has the advantage of high crystallinity and high capacity, but due to the scale shape, the particles are oriented in one direction within the electrode, resulting in inferior high-speed charge / discharge characteristics and cycle characteristics.
  • Patent Document 1 discloses a method for producing a negative electrode material for a lithium ion secondary battery, characterized in that spheroidized graphite is isotropically pressurized.
  • Patent Document 2 discloses a lithium ion characterized in that a coating layer made of carbide is formed on the surface of pressurized graphite particles obtained by pressurizing natural graphite spheroidized particles and / or natural graphite agglomerated particles.
  • a graphite material for a secondary battery is disclosed.
  • the present invention has been made in view of the above circumstances. That is, it aims at providing the negative electrode material which can acquire the outstanding battery characteristic, when it uses for a lithium ion secondary battery negative electrode material. Moreover, it aims at providing the manufacturing method of the negative electrode material, the negative electrode containing the negative electrode material, and the lithium ion secondary battery using the negative electrode.
  • the excellent battery characteristics are high discharge capacity, high initial charge / discharge efficiency, high high-speed charge / discharge characteristics, and excellent cycle characteristics.
  • the present invention relates to a graphite core material in which spherical or ellipsoidal graphite particles are used as a core material, and the core material is anisotropically pressed, and at least a part of the surface of the core material is coated with carbonaceous material.
  • It is carbonaceous covering graphite particle for lithium ion secondary battery negative electrode materials characterized by being carbonaceous covering graphite particle which has a layer.
  • the negative electrode of the lithium ion secondary battery is press-molded in the manufacturing process in order to realize the designed electrode density. Usually, a roll press is used for the press molding, and an anisotropic pressure is applied to the negative electrode material constituting the electrode.
  • the present invention has been made paying attention to this point, that is, by subjecting the negative electrode material to anisotropic pressure treatment in advance, deformation of the particles due to press molding at the time of producing the negative electrode, and accompanying it Damage to the coating layer can be suppressed, and high initial charge / discharge efficiency, high-speed charge / discharge characteristics, and cycle characteristics can be maintained even when the electrode density is increased.
  • the carbon-coated graphite particles of the present invention simultaneously satisfy good discharge capacity, initial charge / discharge efficiency, high-speed charge / discharge characteristics, and cycle characteristics as a lithium ion secondary battery negative electrode material. Therefore, the lithium ion secondary battery using the negative electrode material of the present invention satisfies the recent demand for higher energy density of the battery, and is useful for downsizing and higher performance of the mounted device.
  • FIG. 1 is a cross-sectional view of an evaluation battery for evaluating the battery characteristics of the negative electrode of the present invention.
  • Graphite particles (spherical and / or ellipsoidal graphite)
  • graphite particles having a spherical or ellipsoidal average particle diameter of 1 to 50 ⁇ m, preferably an average aspect ratio of 5 or less and an average particle diameter of 5 to 30 ⁇ m are used.
  • the average aspect ratio is 2 or less and the average specific surface area is more preferably 10 m 2 / g or less, and particularly preferably 8 m 2 / g or less.
  • natural graphite particles processed into a spherical or ellipsoidal shape can also be used.
  • natural graphite having a shape other than spherical or ellipsoidal shape for example, flaky graphite particles
  • natural flaky graphite is granulated by mechanical external force to obtain spherical graphite particles.
  • the method of processing into a spherical or ellipsoidal shape is, for example, a method of mixing a plurality of scaly graphites in the presence of a granulating aid such as an adhesive or a resin, without using an adhesive for a plurality of scaly graphites.
  • the method of applying mechanical external force, the combined use of both, etc. are mentioned.
  • the most preferable method is to apply a mechanical external force to granulate into a spherical shape without using a granulating aid.
  • the mechanical external force is mechanically pulverizing and granulating, and scaly graphite can be granulated and spheroidized.
  • the flaky graphite crusher include a pressure kneader, a kneader such as a two-roll mill, a rotating ball mill, a counter jet mill (manufactured by Hosokawa Micron Corporation), a current jet (manufactured by Nisshin Engineering Co., Ltd.), and the like.
  • a grinding device can be used.
  • the pulverized product may be granulated and used.
  • granulated spheroidizers for pulverized products include granulators such as GRANUREX (manufactured by Freund Sangyo Co., Ltd.), Newgra Machine (manufactured by Seisin Co., Ltd.), Agromaster (manufactured by Hosokawa Micron Co., Ltd.), and hybridization.
  • Shear compression processing apparatuses such as (manufactured by Nara Machinery Co., Ltd.), mechanomicros (manufactured by Nara Machinery Co., Ltd.), and mechanofusion system (manufactured by Hosokawa Micron Co., Ltd.) can be used.
  • Lc which is a measured value of X-ray diffraction of the graphite particles of the present invention, is preferably 40 nm or more, and La is preferably 40 nm or more.
  • Lc is the crystallite size Lc (002) in the c-axis direction of the graphite structure
  • La is the crystallite size La (110) in the a-axis direction.
  • d002 is 0.337 nm or less
  • the ratio I 1360 / I 1580 (R value) of 1360 cm ⁇ 1 peak intensity (I 1360 ) and 1580 cm ⁇ 1 peak intensity (I 1580 ) measured by Raman spectroscopy using an argon laser is 0.
  • the full width at half maximum of the 0.06 to 0.30 and 1580 cm ⁇ 1 bands is preferably 10 to 60.
  • the graphite particles of the present invention are formed by anisotropically pressing the spherical or ellipsoidal graphite. As a result, the graphite particles of the present invention have an orientation in which the density is high in the anisotropically pressed direction and the density is low in the perpendicular direction.
  • the graphite particles of the present invention preferably have a pore volume of 500 nm or less as measured by the mercury intrusion method of 0.100 mL / g or less, or a pore volume of 100 to 200 nm as measured by the mercury intrusion method. Is preferably 0.02 mL / g or less. If this range is exceeded, the binder used to produce the negative electrode may permeate into the pores, which may reduce the electrode peel strength.
  • Carbonaceous coated graphite particles The carbonaceous coated graphite particles for a negative electrode material of a lithium ion secondary battery of the present invention have a carbonaceous material on at least a part of the surface of the above-mentioned anisotropically pressed graphite particles. That is, at least a part of the surface of the graphite particles is covered with the carbonaceous material.
  • the manufacturing method is not limited, Preferably, at least a part of the surface of the graphite particles is coated with a carbonaceous material by a manufacturing method described later using a carbonaceous precursor as a raw material. Examples of the precursor of the carbonaceous material used include tar pitches and / or resins.
  • heavy oils particularly tar pitches
  • heavy Examples include oil.
  • the resins include thermoplastic resins such as polyvinyl alcohol and polyacrylic acid, and thermosetting resins such as phenol resins and furan resins. It is advantageous in terms of cost if only tar pitches are used without containing resins. Any of the carbonaceous material precursors exemplified above may be used, but the coal tar pitch is particularly preferably 80% by mass or more.
  • the content of the carbonaceous material is 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the graphite particles in the carbonaceous coated graphite particles.
  • the content of the carbonaceous material is less than 0.1 parts by mass, it is difficult to completely cover the active graphite edge surface, and the initial charge / discharge efficiency may be lowered.
  • it exceeds 3.0 parts by mass the proportion of the carbon material having a relatively low discharge capacity is too high, and the discharge capacity of the carbonaceous coated graphite particles is reduced.
  • the carbonaceous material layer of the carbon-coated graphite particles may be cracked or peeled off, resulting in a decrease in initial charge / discharge efficiency.
  • the content of the carbonaceous material is 0.3 to 3.0 parts by mass, more preferably 1.0 to 3.0 parts by mass with respect to 100 parts by mass of the graphite particles in the carbonaceous coated graphite particles. preferable.
  • the content of the carbonaceous material may be in the above range as an average of the entire carbonaceous coated graphite particles. It is not necessary that all the individual particles are within the above range, and some particles outside the above range may be included.
  • the carbon-coated graphite particles of the present invention have a pore volume of not more than 0.100 mL / g and a pore diameter of not more than 0.54 ⁇ m with respect to the pore volume, as measured with a mercury porosimeter.
  • the ratio of the pore volume is 80% or more.
  • the carbon-coated graphite particles of the present invention preferably have a pore volume of 1.1 ⁇ m or less as measured with a mercury porosimeter of 0.090 mL / g or less, and more preferably 0.085 mL / g or less. preferable.
  • the ratio of the pore volume having a pore diameter of 0.54 ⁇ m or less to the pore volume (pore volume having a pore diameter of 1.1 ⁇ m or less) is preferably 81% or more, More preferably, it is 82% or more.
  • the carbon-coated graphite particles of the present invention have a dibutyl phthalate (DBP) oil absorption of 40.0 mL / 100 g or less. When this numerical value is exceeded, the binder used in the production of the negative electrode penetrates into the pores, so that the electrode peel strength is lowered and the cycle characteristics may be lowered.
  • the graphitic particles of the present invention preferably have a dibutyl phthalate (DBP) oil absorption of 38.0 mL / 100 g or less, more preferably 37.0 mL / 100 g or less.
  • the average particle size of the carbon-coated graphite particles as the final product is preferably in the range of 1 to 50 ⁇ m, and more preferably in the range of 5 to 30 ⁇ m.
  • the specific surface area measured by the BET method is preferably 6.0 m 2 / g or less, and more preferably 4.0 m 2 / g or less.
  • the carbon-coated graphite particles had a ratio I 1360 / I 1580 (R value) of 1360 cm ⁇ 1 peak intensity (I 1360 ) and 1580 cm ⁇ 1 peak intensity (I 1580 ) measured by Raman spectroscopy using an argon laser. ) Is larger than the R value of graphite and is preferably 0.05 to 0.80.
  • the method for producing the carbonaceous coated graphite particles of the present invention is not limited, but preferably, the above-mentioned spherical and / or ellipsoidal graphite is first subjected to anisotropic pressure treatment.
  • Anisotropic pressurization means applying a pressure in a specific direction, not an isotropic pressurization.
  • Isotropic pressurization is, for example, a method of isotropic pressurization using a pressurizing medium such as gas or liquid. In Comparative Examples 2 and 3 described later, a cold isostatic press was used.
  • the anisotropic pressurization is preferably pressurization from one direction or two directions.
  • the method of anisotropic pressurization is not particularly limited, and examples thereof include a mold press, a roll press, and extrusion molding.
  • the applied pressure and the anisotropic direction are not limited, but are performed to the extent corresponding to the applied pressure in the negative electrode forming step when the carbonaceous coated graphite particles are used for the negative electrode material of the lithium ion secondary battery and the anisotropic pressure direction. Is preferred.
  • a mold having an internal volume of 2000 to 3000 cm 3 is filled at a height of 5 to 10 cm and pressurized at a pressure of 40 to 300 MPa.
  • a crushing step may be introduced after the pressure treatment, if necessary.
  • carbonaceous or graphite fibers, carbonaceous precursor materials such as amorphous hard carbon, organic materials, inorganic materials, and metal materials may or may not be added.
  • the combination of the pressurizing direction and the non-pressurizing direction becomes complicated, so that the pressurization result becomes closer to isotropic pressurization.
  • the pressing result becomes simpler and the difference in orientation between the pressing direction and the non-pressing direction becomes larger than when other materials are added during the pressing process.
  • the obtained pressure-treated product is mixed with a carbonaceous precursor.
  • a mixing process will not be specifically limited if it can mix uniformly, A well-known mixing method can be used.
  • solid graphite particles and a solid or semi-solid (including viscous liquid) carbonaceous precursor are mixed.
  • Heavy oil is solid at room temperature.
  • a liquid carbonaceous precursor such as tar light oil or tar medium oil
  • volatilize the solvent in advance at a temperature of about 200 ° C. or lower to perform the next firing step.
  • the raw materials are mixed so that the mixing ratio is 0.1 to 3.0 parts by mass of the carbonaceous material with respect to 100 parts by mass of the graphite particles as the final product.
  • the heating and mixing method is not particularly limited, and examples thereof include a biaxial kneader having a heating mechanism such as a heater and a heat medium.
  • a biaxial kneader having a heating mechanism such as a heater and a heat medium.
  • carbonaceous or graphite fibers, carbonaceous precursor materials such as amorphous hard carbon, organic materials, inorganic materials, and metal materials may be added.
  • the mixing step may be performed simultaneously with the baking step described later or may be performed after mixing.
  • the resulting mixture is fired at 700-2200 ° C.
  • the method for the baking treatment is not particularly limited, but baking is preferably performed while stirring, and the use of a rotary kiln is preferable because homogeneous baking can be performed.
  • the heat treatment may be performed in a plurality of stages.
  • the atmosphere may be oxidizing or non-oxidizing, and both may be used properly at each stage. Examples of the non-oxidizing atmosphere include argon, helium, and nitrogen.
  • the firing time is preferably 5 minutes to 30 hours. Further, the temperature profile at the time of temperature rise and firing can take various forms such as a linear temperature rise and a stepwise temperature rise in which the temperature is held at a constant interval.
  • the method for producing carbonaceous coated graphite particles of the present invention preferably does not include a pulverization step after firing. Further, different types of graphite materials may be attached, embedded, or combined before firing. Carbonaceous or graphite fibers, carbonaceous precursor materials such as amorphous hard carbon, organic materials, inorganic materials, and metal materials may be attached to, embedded in, or combined with the graphite particles of the core material.
  • Negative electrode The present invention is also a negative electrode for a lithium ion secondary battery containing the above-mentioned carbonaceous coated graphite particles, and a lithium ion secondary battery using the negative electrode.
  • the negative electrode for a lithium ion secondary battery of the present invention is produced according to a normal negative electrode molding method, but is not limited as long as it is a method capable of obtaining a chemically and electrochemically stable negative electrode.
  • the binder those showing chemical and electrochemical stability with respect to the electrolyte are preferable.
  • fluorine-based resin powders such as polytetrafluoroethylene and polyvinylidene fluoride, and resin powders such as polyethylene and polyvinyl alcohol Carboxymethyl cellulose and the like are used. These can also be used together.
  • the binder is usually used at a ratio of about 1 to 20% by mass in the total amount (dry basis) of the negative electrode mixture. Therefore, the carbonaceous coated graphite particles of the present invention are usually used at a ratio of 99 to 80% by mass (dry basis).
  • the negative electrode material of the present invention is adjusted to a desired particle size by classification or the like, and a mixture obtained by mixing with a binder is dispersed in a solvent to prepare a negative electrode mixture in a paste form. That is, a slurry obtained by mixing the negative electrode material of the present invention and a binder with a solvent such as water, isopropyl alcohol, N-methylpyrrolidone, dimethylformamide, and the like, using a known stirrer, mixer, kneader, kneader, etc. Use to stir and mix to prepare paste. When the paste is applied to one or both sides of the current collector and dried, a negative electrode in which the negative electrode mixture layer is uniformly and firmly bonded is obtained.
  • the film thickness of the negative electrode mixture layer is 10 to 200 ⁇ m, preferably 20 to 100 ⁇ m.
  • the negative electrode produced from the negative electrode mixture containing carbonaceous coated graphite particles of the present invention is anisotropically pressurized in the state of graphite particles, the negative electrode is prepared after forming the negative electrode mixture layer. Even when press molding is not performed, the electrode density can be made relatively high.
  • the negative electrode of the present invention can also be produced by dry-mixing the negative electrode material of the present invention and resin powders such as polyethylene and polyvinyl alcohol and hot pressing in a mold. 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.
  • the shape of the current collector used for producing the negative electrode is not particularly limited, but may be a foil shape, a mesh shape, a net shape 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 about 5 to 20 ⁇ m in the case of a foil. It should be noted that the negative electrode of the present invention can be included even if different types of graphite materials, carbonaceous materials such as amorphous hard carbon, organic substances, metals, metal compounds, and the like are mixed within a range that does not impair the object of the present invention. Alternatively, it may be coated or laminated.
  • the negative electrode produced from the negative electrode mixture containing carbonaceous coated graphite particles of the present invention is anisotropically pressurized in the state of graphite particles, the negative electrode is prepared after forming the negative electrode mixture layer. This suppresses the deformation of the particles due to press pressurization and damage to the coating layer, and maintains high initial charge / discharge efficiency, high-speed charge / discharge characteristics, and cycle characteristics even when the electrode density is high. .
  • the positive electrode used in the lithium secondary battery of the present invention is formed, for example, by applying a positive electrode mixture comprising a positive electrode material, a binder and a conductive agent to the surface of the current collector.
  • the positive electrode material (positive electrode active material) is preferably selected from materials that can occlude / release a sufficient amount of lithium, and lithium such as lithium-containing transition metal oxides, transition metal chalcogenides, vanadium oxides, and lithium compounds thereof.
  • the vanadium oxide is represented by V 2 O 5 , V 6 O 13 , V 2 O 4 , or V 3 O 8 .
  • the lithium-containing transition metal oxide is a composite oxide of lithium and a transition metal, and may be a solid solution of lithium and two or more transition metals.
  • the composite oxide may be used alone or in combination of two or more.
  • the lithium-containing transition metal oxide is LiM 1 1-X M 2 X O 2 (wherein M 1 and M 2 are at least one transition metal element, and X is in the range of 0 ⁇ X ⁇ 1.
  • LiM 1 1-Y M 2 Y O 4 (wherein M 1 and M 2 are at least one transition metal element, and Y is a value in the range of 0 ⁇ Y ⁇ 1).
  • 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, Fe, Mn, Ti, Cr , V, Al, etc.
  • Preferable specific examples include 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 positive electrode active material may be used alone or in combination of two or more.
  • a carbon salt such as lithium carbonate can be added to the positive electrode.
  • various additives such as a electrically conductive agent and a binder, can be used suitably.
  • the positive electrode is produced by applying a positive electrode mixture comprising the positive electrode material, a binder, and a conductive agent for imparting conductivity to the positive electrode on both sides of the current collector to form a positive electrode mixture layer.
  • a binder the same one as that used for producing the negative electrode can be used.
  • the conductive agent known materials such as graphitized materials and carbon black are used.
  • the shape of the current collector is not particularly limited, but a foil shape or a mesh shape such as a mesh or expanded metal is used.
  • the material of the current collector is aluminum, stainless steel, nickel or the like. The thickness is preferably 10 to 40 ⁇ m.
  • the positive electrode mixture may be formed in a paste by dispersing the positive electrode mixture in a solvent, and the paste-like positive electrode mixture may be applied to a current collector and dried to form a positive electrode mixture layer. After forming the agent layer, 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.
  • Non-aqueous electrolyte used in the lithium ion secondary battery of the present invention, an electrolyte salt used in the conventional non-aqueous electrolyte, LiPF 6, LiBF 4, LiAsF 6, LiClO 4, LiB (C 6 H 5 ), LiCl, LiBr, LiCF 3 SO 3 , LiCH 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiN (CF 3 CH 2 OSO 2 ) 2 , LiN (CF 3 CF 2 OSO 2) 2, LiN ( HCF 2 CF 2 CH 2 OSO 2) 2, LiN ((CF 3) 2 CHOSO 2) 2, LiB [ ⁇ C 6 H 3 (CF 3) 2 ⁇ ] 4, LiAlCl 4, Lithium salts such as LiSiF 6 can be used.
  • the electrolyte salt concentration in the electrolytic solution is preferably from 0.1 to 5.0 mol / L, more preferably from 0.5 to 3.0 mol / L.
  • the non-aqueous electrolyte may be a liquid non-aqueous electrolyte or a polymer electrolyte such as a solid electrolyte or a gel electrolyte.
  • the non-aqueous electrolyte battery is configured as a so-called lithium ion secondary battery
  • the non-aqueous electrolyte battery is configured as a polymer electrolyte battery such as a polymer solid electrolyte or a polymer gel electrolyte battery.
  • Solvents for preparing the non-aqueous 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, acetonitrile, chloronitrile, propionitrile, etc.
  • carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, and diethyl carbonate
  • 1,1- or 1,2-dimethoxyethane 1,2-diethoxyethane
  • tetrahydrofuran 2-methyltetrahydrofuran
  • a graphite negative electrode material when used, a system that does not contain propylene carbonate (PC) is used as the electrolytic solution.
  • PC is not preferable because it tends to cause a decomposition reaction on the graphite surface, increases the internal pressure of the battery due to gas generation, and reduces the battery characteristics because a large amount of decomposition reaction products (SEI coating) are generated on the negative electrode material. It is said that.
  • SEI coating decomposition reaction products
  • SEI coating decomposition reaction products
  • spherical and / or ellipsoidal graphite is anisotropically pressurized and further coated with carbon, so the reactivity between the surface of the carbon-coated graphite particles and propylene carbonate is low. Even if propylene carbonate is contained in the electrolyte, the battery characteristics when used as a negative electrode material for a lithium ion secondary battery are comparable.
  • the non-aqueous electrolyte is a polymer electrolyte such as a polymer solid electrolyte or a polymer gel electrolyte
  • a polymer gelled with a plasticizer non-aqueous electrolyte
  • the polymer constituting the matrix include ether-based polymer compounds such as polyethylene oxide and crosslinked products thereof, polymethacrylate-based polymer compounds, polyacrylate-based polymer compounds, polyvinylidene fluoride, and vinylidene fluoride-hexafluoropropylene.
  • a fluorine-based polymer compound such as a copolymer.
  • the polymer solid electrolyte or polymer gel electrolyte is mixed with a plasticizer, and as the plasticizer, the electrolyte salt and the non-aqueous solvent can be used.
  • the concentration of the electrolyte salt in the non-aqueous electrolyte as a plasticizer is preferably 0.1 to 5.0 mol / L, and more preferably 0.5 to 2.0 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 nonaqueous solvent (plasticizer) and heating to melt the polymer compound, an organic solvent A method in which a polymer compound, a lithium salt, and a non-aqueous solvent (plasticizer) are dissolved in, and an organic solvent for mixing is evaporated, a polymerizable monomer, a lithium salt, and a non-aqueous solvent (plasticizer) are mixed, and the mixture is mixed
  • Examples thereof include a method of polymerizing a polymerizable monomer by irradiating an ultraviolet ray, an electron beam, a molecular beam or the like to obtain a polymer.
  • the proportion of the non-aqueous solvent (plasticizer) in the 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 in the lithium ion secondary battery of the present invention, 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. can be used.
  • a microporous membrane made of synthetic resin is suitable.
  • a polyolefin microporous membrane is suitable in terms of thickness, membrane strength, and membrane resistance. Specifically, polyethylene and polypropylene microporous membranes, or microporous membranes composed of these are suitable.
  • the lithium ion secondary battery of the present invention is configured by laminating the negative electrode, the positive electrode, and the nonaqueous electrolyte having the above-described configuration 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.
  • a non-aqueous electrolyte may be disposed outside the negative electrode and the positive electrode.
  • the structure of the lithium ion secondary battery of the present invention is not particularly limited, and the shape and form thereof are not particularly limited, and are cylindrical, depending on the application, mounted equipment, required charge / discharge capacity, and the like. , Square shape, coin shape, button shape, and the like.
  • a battery equipped with means for detecting an increase in the internal pressure of the battery and shutting off the current when an abnormality such as overcharging occurs In the case where the lithium ion secondary battery is a polymer solid electrolyte battery or a polymer gel electrolyte battery, a structure in which the lithium ion secondary battery is enclosed in a laminate film may be used.
  • a button-type secondary battery for single electrode evaluation composed of An actual battery can be produced according to a known method based on the concept of the present invention. Each physical property in this specification is measured by the following method. 1) Average particle size ( ⁇ m): The particle size at which the cumulative frequency of the particle size distribution measured with a laser diffraction particle size distribution meter is 50% by volume percentage.
  • Carbonaceous ratio (%) A carbonaceous precursor raw material (including a plurality of types) is provided with the same thermal history as the carbonaceous coated graphite particles to prepare a carbonaceous carbide. The residual coal rate of the raw material was obtained. The ratio of carbonaceous matter in the carbonaceous coated graphite particles was calculated in terms of the residual carbon ratio obtained.
  • DBP oil absorption (mL / 100 g): According to JIS K6217, 40 g of measurement material was added, and measurement was performed until the maximum value of torque was confirmed under the conditions of a dropping speed of 4 mL / min and a rotation speed of 125 rpm. The amount of oil dropped when the torque was 70% of the maximum torque in the range from the start of measurement to the maximum torque was calculated per 100 g of material.
  • Example 1 [Production of carbon-coated graphite particles as negative electrode material] Natural graphite particles processed into a spherical shape with an average particle diameter of 15 ⁇ m were anisotropically pressurized at 50 MPa using a mold press. After pulverizing this so that the average particle diameter is 15 ⁇ m, the tar-in-oil solution of coal tar pitch (residual carbon ratio 50%) becomes 2.0 parts by mass with respect to 100 parts by mass. And heated to 150 ° C. with a biaxial kneader and mixed for 60 minutes. The obtained mixture was heat-treated at 1300 ° C. for 3 hours under a flow of nitrogen 2 L / min using a tubular furnace to obtain a final product.
  • the copper foil and the negative electrode mixture layer were punched into a cylindrical shape having a diameter of 15.5 mm to prepare a working electrode (negative electrode) composed of a current collector and a negative electrode mixture adhered to the current collector.
  • a working electrode negative electrode
  • a negative electrode mixture adhered to the current collector.
  • counter electrode positive electrode
  • a lithium metal foil is pressed against a nickel net and punched into a circular shape with a diameter of 15.5 mm.
  • 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.
  • a copper 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 electrolytic solution, and a negative electrode mixture 2 are attached to the inside of the outer can 3 in that order.
  • This is a battery system in which a current collector (negative electrode) 7b made of foil is laminated.
  • the separator 5 impregnated with the electrolytic solution was laminated between the current collector 7b and the counter electrode 4 in close contact with the current collector 7a, and then the current collector 7b was placed in the outer cup 1 4 is accommodated in the outer can 3, the outer cup 1 and the outer can 3 are combined, and further, an insulating gasket 6 is interposed between the outer peripheral portion of the outer cup 1 and the outer can 3, and both peripheral portions are caulked and sealed. And produced.
  • the charge / discharge characteristics were measured by the following method. The results are shown in Table 1.
  • the current values of 1C and 2C were calculated from the discharge capacity of the first cycle and the active material weight of the negative electrode.
  • the initial charge / discharge efficiency was calculated from the following equation (1).
  • Initial charge / discharge efficiency (%) 100 ⁇ ((first cycle charge capacity ⁇ first cycle discharge capacity) / first cycle discharge capacity) (1)
  • 1C charge rate was computed from following Formula (2).
  • 1C charge rate (%) 100 ⁇ (charge capacity of CC portion at 1C current value / discharge capacity of first cycle) (2)
  • the 2C discharge rate was calculated from the following equation (3).
  • 2C discharge rate (%) 100 ⁇ (discharge capacity at 2C current value / discharge capacity of first cycle) (3)
  • the cycle characteristics were measured as follows.
  • Cycle characteristics (%) 100 ⁇ (50th cycle discharge capacity / first cycle discharge capacity) (4) In this test, the process of occluding lithium ions in the negative electrode material was charged, and the process of detaching lithium ions from the negative electrode material was discharge.
  • Example 2 In Example 1, evaluation was performed in the same manner as in Example 1 except that the electrode density at the time of battery performance evaluation was 1.75 g / cm 3 . The evaluation results are shown in Table 1.
  • Example 3 In Example 1, except that the carbonaceous coating amount was changed to the amount shown in Table 1, carbonaceous coated graphite particles were produced in the same manner as in Example 1, and evaluation batteries were produced and evaluated in the same manner as in Example 1. did.
  • Example 4 carbonaceous coated graphite particles were produced in the same manner as in Example 1 except that the pressure during the pressure treatment was 100 MPa, and the electrode density was evaluated as 1.70 g / cm 3 . The evaluation results are shown in Table 1.
  • Example 5 carbonaceous coated graphite particles were produced in the same manner as in Example 1 except that the pressure during the pressure treatment was 150 MPa, and the electrode density was evaluated as 1.70 g / cm 3 . The evaluation results are shown in Table 1.
  • Example 6 Evaluation was made in the same manner as in Example 1 except that the carbonaceous coating amount was changed to the amount shown in Table 1 in Example 1. The evaluation results are shown in Table 1.
  • Example 1 carbonaceous coated graphite particles were produced in the same manner as in Example 1 except that no pressure treatment was performed, and an evaluation battery was produced and evaluated in the same manner as in Example 1.
  • Example 2 a coated natural graphite material was produced in the same manner as in Example 1 except that 50 MPa was isotropically pressurized using a cold isostatic press as the method of pressure treatment. An evaluation battery was prepared and evaluated.
  • Comparative Example 3 In Comparative Example 2, the evaluation was performed in the same manner as in Comparative Example 2 except that the electrode density during battery performance evaluation was 1.75 g / cm 3 . The evaluation results are shown in Table 1.
  • Example 6 (Comparative Example 6) In Example 1, it evaluated similarly to Example 1 except the pressure at the time of a pressurizing process being 10 Mpa. The evaluation results are shown in Table 1.
  • Example 7 (Comparative Example 7) In Example 1, it evaluated similarly to Example 1 except the pressure at the time of a pressurizing process being 10 Mpa, and making a carbonaceous coating amount into 3.0 mass parts. The evaluation results are shown in Table 1.
  • Example 8 (Comparative Example 8) In Example 1, it evaluated similarly to Example 1 except the pressure at the time of a pressurizing process being 30 Mpa, and making a carbonaceous coating amount into 3.0 mass parts. The evaluation results are shown in Table 1.
  • Example 9 (Comparative Example 9) In Example 1, it evaluated similarly to Example 1 except the pressure at the time of a pressurizing process being 10 Mpa, and making a carbonaceous coating amount into 0.15 mass part. The evaluation results are shown in Table 1.
  • Examples 1 to 6 in which the graphite particles formed by anisotropic pressure satisfy the following (1) to (3) have good discharge capacity, initial charge / discharge efficiency, high-speed charge / discharge characteristics, and cycle characteristics. . As is clear from the comparison between Examples 1 and 2, this characteristic is maintained even when the electrode density is increased.
  • the content of the carbonaceous material is 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the graphite particles formed by anisotropic pressure in the carbonaceous coated graphite particles.
  • the pore volume with a pore diameter of 1.1 ⁇ m or less measured with a mercury porosimeter is 0.100 mL / g or less, and the ratio of the pore volume with a pore diameter of 0.54 ⁇ m or less to the pore volume is 80% or more .
  • Dibutyl phthalate (DBP) oil absorption is 40.0 mL / 100 g or less.
  • Comparative Example 1 in which the graphite particles are not pressure-treated
  • Comparative Examples 2 and 3 in which the isotropic pressure treatment is performed
  • Comparative Example 4 in which the coating amount of the carbonaceous material is less than 0.1%
  • carbon Comparative Example 5 in which the covering amount of the porous material exceeds 3%, the pore volume with a pore diameter of 1.1 ⁇ m or less exceeds 0.100 mL / g, and the ratio of the pore volume with a pore diameter of 0.54 ⁇ m or less to the pore volume is Comparative Example 6 having a DBP oil absorption of less than 80% and a DBP oil absorption of more than 40.0 mL / 100 g
  • Comparative Example 7 having a pore volume of 1.1 ⁇ m or less and a pore volume of more than 0.1 mL / g, and a pore diameter of 1.1 ⁇ m or less
  • Comparative Example 8 in which the ratio of the pore volume with a pore diameter of 0.54 ⁇ m
  • the negative electrode material composed of carbonaceous coated graphite particles of the present invention is a negative electrode material having good discharge capacity, initial charge / discharge efficiency, fast charge / discharge characteristics, and cycle characteristics as a negative electrode material for a lithium ion secondary battery. Taking advantage of these characteristics, it can be used for negative electrodes of high-performance lithium ion secondary batteries ranging from small to large.

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Abstract

L'invention concerne un matériau d'électrode négative avec lequel il est possible d'obtenir des propriétés de pile exceptionnelles quand ledit matériau est utilisé comme matériau d'électrode négative d'une pile rechargeable lithium-ion. Des particules de graphite à revêtement carboné pour le matériau d'électrode négative d'une pile rechargeable lithium-ion sont décrites, dans lesquelles un matériau carboné est disposé sur au moins une partie des surfaces de particules de graphite qui sont obtenues par application de pression anisotrope à du graphite sphéroïdal et/ou ellipsoïdal, les particules de graphite à revêtement carboné satisfaisant les conditions (1) à (3) qui suivent. (1) La teneur en matériau carboné est de 0,1 à 3,0 parties en poids pour 100 parties en poids des particules de graphite soumises à la pression anisotrope dans les particules de graphite à revêtement carboné. (2) Le volume poreux de pores dont le diamètre est inférieur ou égal à 1,1 µm est inférieur ou égal à 0,100 ml/g, mesuré par un porosimètre à mercure, et la proportion du volume poreux de pores dont le diamètre est inférieur ou égal à 0,54 µm par rapport audit volume poreux est supérieure ou égale à 80 %. (3) L'absorption d'huile de phtalate de dibutyle (DBP) est inférieure ou égale à 40,0 ml/g.
PCT/JP2016/002602 2015-06-01 2016-05-30 Particules de graphite à revêtement carboné pour matériau d'électrode négative de pile rechargeable lithium-ion, électrode négative pour pile rechargeable lithium-ion, et pile rechargeable lithium-ion WO2016194355A1 (fr)

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CN201680025230.0A CN107534148B (zh) 2015-06-01 2016-05-30 锂离子二次电池负极材料用碳质包覆石墨粒子、锂离子二次电池负极和锂离子二次电池

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