WO2021153080A1 - 炭素質材料、炭素質材料の製造方法、リチウムイオン二次電池用負極およびリチウムイオン二次電池 - Google Patents

炭素質材料、炭素質材料の製造方法、リチウムイオン二次電池用負極およびリチウムイオン二次電池 Download PDF

Info

Publication number
WO2021153080A1
WO2021153080A1 PCT/JP2020/047268 JP2020047268W WO2021153080A1 WO 2021153080 A1 WO2021153080 A1 WO 2021153080A1 JP 2020047268 W JP2020047268 W JP 2020047268W WO 2021153080 A1 WO2021153080 A1 WO 2021153080A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbonaceous material
negative electrode
ion secondary
lithium ion
secondary battery
Prior art date
Application number
PCT/JP2020/047268
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
博昭 石
哲夫 塩出
間所　靖
Original Assignee
Ｊｆｅケミカル株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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 CN202080006722.1A priority Critical patent/CN113195405A/zh
Priority to JP2021521446A priority patent/JP6911221B1/ja
Priority to KR1020217014304A priority patent/KR102632742B1/ko
Publication of WO2021153080A1 publication Critical patent/WO2021153080A1/ja

Links

Images

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/205—Preparation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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 carbonaceous material, a method for producing a carbonaceous material, a negative electrode for a lithium ion secondary battery, and a lithium ion secondary battery.
  • a carbonaceous material made from coke may be used as the negative electrode material for lithium-ion secondary batteries.
  • it is common to graphitize the crushed coke, and it has also been proposed to combine granulation and surface modification (Patent Document 1).
  • an object of the present invention is to provide a carbonaceous material having excellent battery characteristics when used as a negative electrode material for a lithium ion secondary battery.
  • the present invention provides the following [1] to [5].
  • [1] Carbon having a minimum particle size of more than 3.00 ⁇ m, a circularity of 0.82 or more and 0.94 or less, an aspect ratio of 1.48 or more and 1.65 or less, and a Raman R value of more than 0.40. Quality material.
  • [2] The carbonaceous material according to the above [1], wherein the carbonaceous material is a graphitized product of coal coke.
  • the method for producing a carbonaceous material according to the above [1] or [2] in which coke as a raw material is crushed and graphitized, and shearing force and compressive force are applied before the graphitization. Or later, a method for producing a carbonaceous material that removes fine powder.
  • the battery characteristics and the negative electrode characteristics are excellent when used as a negative electrode material for a lithium ion secondary battery.
  • the range when the range is indicated by using “ ⁇ ”, the range shall include both ends of “ ⁇ ”.
  • the range A to B includes A and B.
  • the carbonaceous material of the present invention has a minimum particle size of more than 3.00 ⁇ m, a circularity of 0.82 or more and 0.94 or less, an aspect ratio of 1.48 or more and 1.65 or less, and a Raman R value of 0.40. It's super.
  • the negative electrode (negative electrode) for a lithium ion secondary battery obtained by using the carbonaceous material of the present invention has a high density. It is presumed that this is because the carbonaceous material of the present invention has a minimum particle size of more than 3.00 ⁇ m, that is, fine particles having a particle size of 3.00 ⁇ m or less are removed.
  • a lithium ion secondary battery using such a negative electrode is excellent in battery characteristics such as discharge capacity and initial charge / discharge efficiency.
  • the minimum particle size of the carbonaceous material of the present invention is more than 3.00 ⁇ m.
  • the minimum particle size of the carbonaceous material of the present invention is preferably 3.20 ⁇ m or more, more preferably 3.40 ⁇ m or more, still more preferably 3.60 ⁇ m or more, because the negative electrode has a higher density and the battery characteristics are better. 3.80 ⁇ m or more is particularly preferable, and 4.00 ⁇ m or more is most preferable.
  • the upper limit is not particularly limited, the minimum particle size of the carbonaceous material of the present invention is preferably 10.00 ⁇ m or less, more preferably 9.00 ⁇ m or less, further preferably 8.00 ⁇ m or less, and most preferably 4.80 ⁇ m or less. preferable.
  • Particle diameter D 50 of the carbonaceous material of the present invention is preferably at least 25.0 ⁇ m or less 5.00, more preferably at least 20.0 ⁇ m or less 10.0 [mu] m, more preferably more than 18.0 ⁇ m or less 10.0 [mu] m, 12. Most preferably, it is 9 ⁇ m or more and 17.5 ⁇ m or less.
  • the particle size D 50 is a particle size at which the cumulative frequency of the particle size distribution is 50% by volume.
  • the circularity of the carbonaceous material of the present invention is 0.82 or more, preferably 0.83 or more, and more preferably 0.84 or more. The closer the circularity is to 1, the more spherical the shape of the carbonaceous material becomes, and the higher the density of the negative electrode becomes. On the other hand, considering the cost of actually setting the circularity to 1, the circularity of the carbonaceous material of the present invention is 0.94 or less, preferably 0.93 or less, more preferably 0.92 or less, and further. It is preferably 0.91 or less, and most preferably less than 0.88.
  • the aspect ratio of the carbonaceous material of the present invention is 1.65 or less, preferably 1.60 or less, and more preferably 1.55 or less. The closer the aspect ratio is to 1, the more spherical the shape of the carbonaceous material becomes, and the higher the density of the negative electrode becomes. On the other hand, considering the cost of actually setting the aspect ratio to 1, the aspect ratio of the carbonaceous material of the present invention is 1.48 or more, preferably 1.49 or more, and more preferably 1.50 or more.
  • the particle size of the carbonaceous material is determined by measuring with a laser particle size distribution measuring device (manufactured by Seishin Enterprise Co., Ltd., LMS-200e) under the condition that ion-exchanged water is used as a dispersion medium and the amount of sample solution is 40 mL. The value.
  • the circularity and aspect ratio of the carbonaceous material were measured using a particle shape measuring device (PITA-1, manufactured by Seishin Enterprise Co., Ltd.) under the condition that ion-exchanged water was used as a dispersion medium and the amount of sample solution was 1.25 ⁇ L. It is a value that can be obtained.
  • the Raman R value of the carbonaceous material of the present invention is more than 0.40. If the Raman R value is too low, there are too few edges involved in the insertion or desorption of lithium ions, resulting in insufficient battery characteristics.
  • the Raman R value of the carbonaceous material of the present invention is preferably 0.45 or more, more preferably 0.50 or more, still more preferably more than 0.50, because the battery characteristics are more excellent.
  • the upper limit is not particularly limited, but a high Raman R value means that the amount of amorphous carbon on the surface of the carbonaceous material is large. Therefore, when the Raman R value is high, the influence of the irreversible capacity of the amorphous carbon becomes large, and the battery capacity may decrease. From such a viewpoint, the Raman R value of the carbonaceous material of the present invention is preferably 1.20 or less, more preferably 1.10 or less, and even more preferably 0.80 or less.
  • the Raman R value of the carbonaceous material is calculated as follows. Using a Raman spectroscopic measuring device (LabRAM ARAMIS, manufactured by HORIBA, Ltd.), microscopic Raman analysis is performed 100 times at a wavelength of 532 nm to obtain a Raman spectrum. The ratio of the resulting Raman spectrum, the intensity I D of (peak present in the region of 1350 ⁇ 1370cm -1) D band, the intensity I G of the G band (peak present in the region of 1570 ⁇ 1630 cm -1) Is calculated as the Raman R value ( ID / IG).
  • the specific surface area of the carbonaceous material of the present invention is not particularly limited, but is preferably 1.0 ⁇ 5.0m 2 / g, more preferably 1.2 ⁇ 3.0m 2 / g, 1.3 ⁇ 2.6m 2 / g is more preferable.
  • the specific surface area of the carbonaceous material is determined by the BET 1-point method by adsorbing nitrogen gas using a powder analyzer (Monosorb, manufactured by Kantachrome).
  • the method for producing a carbonaceous material of the present invention (hereinafter, also simply referred to as “the production method of the present invention”) is the above-mentioned method for producing a carbonaceous material of the present invention, in which coke as a raw material is crushed and graphite is used. The fine powder is removed before or after the graphitization by applying shearing force and compressive force.
  • Coke is used as a raw material.
  • Examples of coke include coal coke and petroleum coke.
  • Coal coke is a gray-black porous solid with a metallic luster, which is obtained by carbonizing coal at a high temperature (about 1000 to 1100 ° C.).
  • Petroleum coke is coke obtained by thermally decomposing a heavy fraction of petroleum at a high temperature.
  • the coke may be uncalcinated coke (raw coke) or calcined coke (calcinated coke).
  • Coke baking is performed at a temperature of about 900 to 1500 ° C. using, for example, a rotary kiln. It is preferable to use coal coke, and it is more preferable to use unbaked coal coke, because the negative electrode has a higher density and the battery characteristics are better.
  • the raw material coke is crushed to obtain a crushed product.
  • the coke is pulverized so that the average particle size is, for example, 5.00 to 15.00 ⁇ m.
  • the device used for crushing is not particularly limited, and is, for example, a coarse crusher such as a shear mill, a jaw crusher, an impact crusher, or a cone crusher; an intermediate crusher such as a roll crusher or a hammer mill; a mechanical crusher, an air stream. Fine crushers such as a type crusher and a swirl flow type crusher; and the like.
  • coke (raw coke) before calcination is used as a raw material, it may be dried at, for example, 100 to 200 ° C. before pulverization.
  • the crushed coke product is graphitized by heating to obtain a graphitized product.
  • the heating temperature (graphitization temperature) at the time of graphitization is preferably 2500 ° C. or higher, more preferably 2800 ° C. or higher.
  • the graphitization temperature is preferably 4000 ° C. or lower, more preferably 3500 ° C. or lower. When the graphitization temperature is within this range, the crystallinity of the graphitized product is good.
  • Fine powder is removed before or after graphitizing the ground product. That is, fine powder having a particle size of 3.00 ⁇ m or less is removed. As a result, a carbonaceous material having a minimum particle size of more than 3.00 ⁇ m can be obtained.
  • the fine powder before graphitization the fine powder of the crushed product is removed.
  • the fine powder after graphitization the fine powder of the graphitized product is removed.
  • the method for removing fine powder is not particularly limited, and examples thereof include a dry classification method using a wind power classifier or the like.
  • a method of the wind classifier for example, a forced centrifugal separation method in which centrifugal force is generated by an internal rotor and only fine powder is sucked by an external blower to classify; Relative density sorting type; a gravity inertia separation type that puts the object to be processed into the pipe in the airflow and classifies it according to the difference in the flight trajectory of the object to be processed by using the inertia and the resistance of the airflow; You can choose.
  • a shear compression processing apparatus such as hybridization (manufactured by Nara Kikai Seisakusho Co., Ltd.), mechanomicros (manufactured by Nara Kikai Seisakusho Co., Ltd.), mechanofusion system (manufactured by Hosokawa Micron Co., Ltd.) is preferably mentioned. Be done.
  • the negative electrode for a lithium ion secondary battery of the present invention is a negative electrode for a lithium ion secondary battery containing the carbonaceous material of the present invention.
  • the negative electrode for a lithium ion secondary battery is also simply referred to as a "negative electrode”.
  • the negative electrode of the present invention is manufactured according to a normal negative electrode.
  • a negative electrode mixture prepared in advance by adding a binder to the carbonaceous material of the present invention.
  • the negative electrode mixture may contain an active material or a conductive material other than the carbonaceous-coated graphite particles of the present invention.
  • the binder is preferably one that is chemically and electrochemically stable with respect to the electrolyte, and is, for example, a fluororesin such as polytetrafluoroethylene or polyvinylidene fluoride; polyethylene, polyvinyl alcohol, styrene butadiene rubber, or the like. Resin; carboxymethyl cellulose; etc. are used, and two or more of these can be used in combination.
  • the binder is usually used in a proportion of about 1 to 20% by mass in the total amount of the negative electrode mixture.
  • the carbonaceous material of the present invention is optionally adjusted to a desired particle size by classification or the like. Then, the carbonaceous material of the present invention is mixed with a binder, and the obtained mixture is dispersed in a solvent to prepare a paste-like negative electrode mixture.
  • the solvent include water, isopyrpillar alcohol, N-methylpyrrolidone, dimethylformamide and the like.
  • a known stirrer, mixer, kneader, kneader or the like is used for mixing and dispersion.
  • the prepared paste is applied to one or both sides of the current collector and dried. In this way, a negative electrode mixture layer (negative electrode) that is uniformly and firmly adhered to the current collector can be obtained.
  • the thickness of the negative electrode mixture layer is preferably 10 to 200 ⁇ m, more preferably 20 to 100 ⁇ m. After forming the negative electrode mixture layer, crimping such as press pressure can further increase the adhesion strength between the negative electrode mixture layer (negative electrode) and the current collector.
  • the shape of the current collector is not particularly limited, but is, for example, a foil shape, a mesh shape, a mesh shape such as an expanded metal, or the like. As the material of the current collector, copper, stainless steel, nickel and the like are preferable.
  • the thickness of the current collector is preferably about 5 to 20 ⁇ m in the case of a foil.
  • the lithium ion secondary battery of the present invention is a lithium ion secondary battery having the negative electrode of the present invention.
  • the lithium ion secondary battery of the present invention further includes a positive electrode, a non-aqueous electrolyte, and the like, in addition to the negative electrode of the present invention.
  • the lithium ion secondary battery of the present invention is configured by, for example, laminating a negative electrode, a non-aqueous electrolyte, and a positive electrode in this order and accommodating them in the exterior material of the battery.
  • the lithium ion secondary battery of the present invention can be arbitrarily selected from a cylindrical type, a square type, a coin type, a button type, and the like according to an application, an on-board device, a required charge / discharge capacity, and the like.
  • ⁇ Positive electrode> It is preferable to select a material for the positive electrode (positive electrode active material) that can occlude / release a sufficient amount of lithium.
  • the positive electrode active material in addition to lithium, for example, lithium-containing transition metal oxides, transition metal chalcogenides, lithium-containing compounds such as vanadium oxides and lithium compounds thereof; formula M X Mo 6 S 8-Y (wherein M is at least one kind of transition metal element, X is a numerical value in the range of 0 ⁇ X ⁇ 4, Y is a numerical value in the range of 0 ⁇ Y ⁇ 1). Be done.
  • Vanadium oxides are represented by V 2 O 5 , V 6 O 13 , V 2 O 4 , and 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 kinds of transition metals.
  • the composite oxide may be used alone or in combination of two or more.
  • Lithium-containing transition metal oxide specifically, LiM 1 1-X M 2 X O 2 (wherein M 1, M 2 is a transition metal element of at least one, X is the range of 0 ⁇ X ⁇ 1 is a numerical value), or, LiM 1 1-Y M 2 Y O 4 (wherein M 1, M 2 is a transition metal element of at least one, Y is a number in the range 0 ⁇ Y ⁇ 1) Indicated by.
  • the transition metal elements represented by M 1 and M 2 are Co, Ni, Mn, Cr, Ti, V, Fe, Zn, Al, In, Sn and the like, and preferably Co, Fe, Mn, Ti and Cr. , V, Al, etc.
  • Preferred specific 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 uses, for example, lithium, transition metal oxides, hydroxides, salts, etc. as starting materials, and these starting materials are mixed according to the desired composition of the metal oxide, and 600 under an oxygen atmosphere. It can be obtained by firing at a temperature of about 1000 ° C.
  • the above-mentioned compounds 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 conventionally known conductive agents and binders can be appropriately used.
  • a positive electrode mixture composed of a positive electrode active material, a binder, and a conductive agent for imparting conductivity to the positive electrode is applied to both sides of the current collector to form a positive electrode mixture layer.
  • the binder a binder used for producing a negative electrode can be used.
  • the conductive agent a known conductive agent such as graphitized product or carbon black is used.
  • the shape of the current collector is not particularly limited, and examples thereof include a foil shape and a net shape.
  • the material of the current collector is aluminum, stainless steel, nickel, or the like.
  • the thickness of the current collector is preferably 10 to 40 ⁇ m.
  • a paste-like positive electrode mixture may be applied to the current collector, dried, and then crimped by press pressure or the like.
  • the non-aqueous electrolyte may be a liquid non-aqueous electrolyte (non-aqueous electrolyte liquid), or may be 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 battery and a polymer gel electrolyte battery.
  • an electrolyte salt used in the conventional non-aqueous electrolyte solution 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 , LiSiF 6 and other lithium salts are used.
  • the concentration of the electrolyte salt in the non-aqueous electrolyte solution is preferably 0.1 to 5.0 mol / L, more preferably 0.5 to 3.0 mol / L.
  • Solvents for preparing the non-aqueous electrolyte solution include, for example, carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate; 1,1- or 1,2-dimethoxyethane, 1,2-diethoxyethane, Ethers such as tetrahydrofuran, 2-methyl tetrahydrofuran, ⁇ -butyrolactone, 1,3-dioxolane, 4-methyl-1,3-dioxolane, anisole, diethyl ether; thioethers such as sulfolane and methyl sulfolane; acetonitrile, chloronitrile, propio Nitriles such as nitriles; trimethyl borate, tetramethyl silicate, nitromethane, dimethylformamide, N-methylpyrrolidone, ethyl acetate, trimethyl orthoformate, nitrobenzene, benzoyl chloride, benzoyl bro
  • the non-aqueous electrolyte is a polymer electrolyte such as a solid electrolyte or a gel electrolyte
  • a polymer gelled with a plastic agent non-aqueous electrolyte solution
  • the polymer constituting the matrix include polyethylene oxide, an ether-based polymer compound such as a crosslinked product thereof; a poly (meth) acrylate-based polymer compound; polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, and the like. Fluoropolymer compounds; etc. are preferably used.
  • the concentration of the electrolyte salt in the non-aqueous electrolyte solution which is a plasticizer, is preferably 0.1 to 5.0 mol / L, more preferably 0.5 to 2.0 mol / L.
  • the proportion of the plasticizer is preferably 10 to 90% by mass, more preferably 30 to 80% by mass.
  • a separator can also be used.
  • the material of the separator is not particularly limited, but for example, a woven fabric, a non-woven fabric, a microporous membrane made of synthetic resin, or the like is used.
  • synthetic resin microporous membranes are preferable, and among them, polyolefin-based microporous membranes are more preferable in terms of thickness, membrane strength, and membrane resistance.
  • the polyolefin-based microporous membrane include a polyethylene microporous membrane, a polypropylene microporous membrane, and a composite microporous membrane thereof.
  • Example 1 ⁇ Production of carbonaceous materials >> Coal coke before calcination (manufactured by Hobu Coal Materials Technology Co., Ltd., No. 1 for negative electrode) (corresponding to raw coke) was dried at 200 ° C. using a rotary kiln to obtain a dried product. The dried product was pulverized using an air flow crusher (NSTJ-200 manufactured by Seishin Enterprise Co., Ltd.) so that the average particle size was 10 ⁇ m to obtain a pulverized product. The crushed product was graphitized by heating at 3000 ° C. at Tokai Carbon Co., Ltd. in a state of being sealed in a graphite crucible to obtain a graphitized product.
  • NSTJ-200 manufactured by Seishin Enterprise Co., Ltd.
  • the graphitized product fine powder was removed using a wind power classifier (Donna Celec, manufactured by Donaldson of Japan). Then, the graphitized product was subjected to mechanochemical treatment using a dry powder compounding apparatus (Mechanofusion system AMS-MINI manufactured by Hosokawa Micron Co., Ltd.). More specifically, the shearing force and the compressive force of the graphitized product from which the fine powder has been removed are under the conditions of the rotation speed of the rotating drum: 5000 rpm, the processing time: 15 minutes, and the distance between the rotating drum and the internal member: 1 mm. And were repeatedly given. In this way, the carbonaceous material of Example 1 was obtained.
  • FIG. 1 shows an SEM photograph of the carbonaceous material of Example 1. Further, with respect to the carbonaceous material of Example 1, the minimum particle size (D min ), the particle size D 10 , the particle size D 50 , the particle size D 90 , the maximum particle size (D max ), the specific surface area, The circularity, aspect ratio, and Raman R value were determined.
  • the particle size D 10 is a particle size at which the cumulative frequency of the particle size distribution is 10% by volume.
  • the particle size D 90 is a particle size at which the cumulative frequency of the particle size distribution is 90% by volume. The results are shown in Table 1 below.
  • a negative electrode mixture paste is prepared by adding 98 parts by mass of a carbonaceous material (negative electrode material), 1 part by mass of carboxymethyl cellulose (binder), and 1 part by mass of styrene butadiene rubber (binder) to water and stirring. did.
  • the prepared negative electrode mixture paste was applied to a copper foil to a uniform thickness and dried in vacuum at 90 ° C. to form a negative electrode mixture layer.
  • the negative electrode mixture layer was pressed by a roll press at a pressure of 250 MPa.
  • the copper foil and the negative electrode mixture layer were punched into a cylinder having a diameter of 15.5 mm. In this way, a negative electrode in close contact with the current collector made of copper foil was produced.
  • the density of the negative electrode (unit: g / cm 3 ) was determined from the mass and size of the negative electrode. The results are shown in Table 1 below.
  • FIG. 2 is a cross-sectional view showing a button type secondary battery.
  • the peripheral edges of the outer cup 1 and the outer can 3 are crimped via an insulating gasket 6 to form a sealed structure.
  • a current collector 7a, a positive electrode 4, a separator 5, a negative electrode 2, and a current collector 7b are laminated in this order from the inner surface of the outer can 3 toward the inner surface of the outer cup 1.
  • the button-type secondary battery shown in FIG. 2 was manufactured as follows. First, a non-aqueous electrolyte solution was prepared by dissolving LiPF 6 at a concentration of 1 mol / L in a mixed solvent of ethylene carbonate (33% by volume) and methyl ethyl carbonate (67% by volume). A polypropylene porous body (thickness: 20 ⁇ m) was impregnated with the obtained non-aqueous electrolyte solution to prepare a separator 5 impregnated with the non-aqueous electrolyte solution. Next, the produced separator 5 was sandwiched between the negative electrode 2 in close contact with the current collector 7b made of copper foil and the positive electrode 4 in close contact with the current collector 7a made of nickel net, and laminated.
  • the current collector 7b and the negative electrode 2 were housed inside the outer cup 1
  • the current collector 7a and the positive electrode 4 were housed inside the outer can 3
  • the outer cup 1 and the outer can 3 were combined. Further, the peripheral edge portion between the outer cup 1 and the outer can 3 is caulked and sealed with an insulating gasket 6 interposed therebetween. In this way, a button-type secondary battery was manufactured.
  • the initial charge / discharge efficiency was calculated from the following formula (1). It can be evaluated that the larger the value of the initial charge / discharge efficiency is, the better the initial charge / discharge efficiency is.
  • Initial charge / discharge efficiency [%] 100 ⁇ ⁇ (charge capacity of the first cycle-discharge capacity of the first cycle) / discharge capacity of the first cycle ⁇ ... (1)
  • Electrode peel strength test The test piece used is shown in FIG. A negative electrode mixture paste was prepared, and a part of the active material side was attached to an aluminum plate 12 with double-sided tape 11 in a state where the negative electrode material 10 was not pressed. The test piece was subjected to a tensile test in the 180 ° direction (arrow direction 13) by grasping a part of the negative electrode material 10 using a tensile tester (autograph manufactured by Shimadzu Corporation), and the average tensile test stress was taken as the peel strength.
  • a tensile tester autograph manufactured by Shimadzu Corporation
  • Example 2 In Example 1, the evaluation was carried out in the same manner as in Example 1 except that the graphitizing maker was carried out in the commercial city ⁇ county ⁇ Shubishin ⁇ charcoal ⁇ material technology ⁇ departure ⁇ exhibition company. The evaluation results are shown in Table 1.
  • Example 3 In Example 2, the evaluation was carried out in the same manner as in Example 2 except that the mechanochemical treatment time was 30 minutes. The evaluation results are shown in Table 1.
  • Example 4 In Example 2, the evaluation was carried out in the same manner as in Example 2 except that the classification conditions were adjusted so that the minimum particle size Dmin was 4.76 ⁇ m. The evaluation results are shown in Table 1.
  • Example 5 the mechanochemical treatment was evaluated in the same manner as in Example 1 except that the treatment time was 120 minutes using a large-scale dry powder compounding device (Mechanofusion System AMS-30F manufactured by Hosokawa Micron Co., Ltd.). did.
  • the conditions for the mechanochemical treatment were the rotation speed of the rotating drum: 1450 rpm, the processing time: 120 minutes, and the distance between the rotating drum and the internal member: 10 mm.
  • the evaluation results are shown in Table 1.
  • Example 6 In Example 2, the evaluation was carried out in the same manner as in Example 2 except that the classification conditions were adjusted so that the minimum particle size Dmin was 3.01 ⁇ m. The evaluation results are shown in Table 1.
  • ⁇ Comparative example 3> The calcinated petroleum coke (HNP, manufactured by Phillips66) was pulverized using an airflow crusher (NSTJ-200, manufactured by Seishin Enterprise) so that the average particle size was 10 ⁇ m to obtain a pulverized product.
  • a petroleum-based pitch (softening point: 250 ° C.) is added to the crushed product at a mass ratio of 90/10 (crushed product / pitch) and kneaded at 600 ° C. for 10 hours to obtain a granulated body having an average particle size of about 20 ⁇ m. Obtained.
  • the granulated body was graphitized by heating at 3000 ° C.
  • Comparative Example 6 In Comparative Example 6, petroleum coke before calcination was used as a raw material, shearing force and compressive force were applied before graphitization, and fine powder was not removed. The points other than these were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.
  • Example 7 ⁇ Comparative Example 7>
  • the evaluation was carried out in the same manner as in Example 2 except that the classification conditions were adjusted so that the minimum particle size Dmin was 2.23 ⁇ m.
  • the evaluation results are shown in Table 1.
  • Example 2 the evaluation was carried out in the same manner as in Example 2 except that the mechanochemical treatment was not carried out after removing the fine powder. The evaluation results are shown in Table 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Carbon And Carbon Compounds (AREA)
PCT/JP2020/047268 2020-01-28 2020-12-17 炭素質材料、炭素質材料の製造方法、リチウムイオン二次電池用負極およびリチウムイオン二次電池 WO2021153080A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN202080006722.1A CN113195405A (zh) 2020-01-28 2020-12-17 碳质材料、碳质材料的制造方法、锂离子二次电池用负极及锂离子二次电池
JP2021521446A JP6911221B1 (ja) 2020-01-28 2020-12-17 炭素質材料、炭素質材料の製造方法、リチウムイオン二次電池用負極およびリチウムイオン二次電池
KR1020217014304A KR102632742B1 (ko) 2020-01-28 2020-12-17 탄소질 재료, 탄소질 재료의 제조 방법, 리튬 이온 2차 전지용 부극 및 리튬 이온 2차 전지

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020011361 2020-01-28
JP2020-011361 2020-01-28

Publications (1)

Publication Number Publication Date
WO2021153080A1 true WO2021153080A1 (ja) 2021-08-05

Family

ID=77078083

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/047268 WO2021153080A1 (ja) 2020-01-28 2020-12-17 炭素質材料、炭素質材料の製造方法、リチウムイオン二次電池用負極およびリチウムイオン二次電池

Country Status (3)

Country Link
KR (1) KR102632742B1 (zh)
TW (1) TWI767490B (zh)
WO (1) WO2021153080A1 (zh)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003132889A (ja) * 2001-08-10 2003-05-09 Kawasaki Steel Corp リチウムイオン二次電池用負極材料およびその製造方法
JP2012227151A (ja) * 2001-08-10 2012-11-15 Jfe Chemical Corp リチウムイオン二次電池用負極材料、リチウムイオン二次電池用負極合剤、リチウムイオン二次電池負極およびリチウムイオン二次電池
JP2013201125A (ja) * 2012-02-24 2013-10-03 Mitsubishi Chemicals Corp 非水系二次電池用複層構造炭素材、及びそれを用いた非水系二次電池用負極並びに非水系二次電池
WO2017002959A1 (ja) * 2015-07-02 2017-01-05 昭和電工株式会社 リチウムイオン電池用負極材及びその用途
WO2018047939A1 (ja) * 2016-09-09 2018-03-15 昭和電工株式会社 リチウムイオン二次電池用負極材

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5668308B2 (ja) * 2009-03-27 2015-02-12 三菱化学株式会社 非水電解液二次電池用負極材料及びこれを用いた非水電解液二次電池
JP5678414B2 (ja) * 2009-06-17 2015-03-04 三菱化学株式会社 黒鉛負極材料及びその製造方法、並びにそれを用いたリチウム二次電池用負極及びリチウム二次電池
EP2624345B1 (en) 2010-09-29 2020-10-21 Mitsubishi Chemical Corporation Carbon material for negative electrode of nonaqueous electrolyte secondary battery, method for producing same, negative electrode of nonaqueous secondary battery using same, and nonaqueous electrolyte secondary battery
JP6252025B2 (ja) 2013-08-08 2017-12-27 三菱ケミカル株式会社 非水系二次電池負極用複合黒鉛粒子の製造方法、及びその製造方法にて製造された非水系二次電池負極用複合黒鉛粒子、非水系二次電池用負極及び非水系二次電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003132889A (ja) * 2001-08-10 2003-05-09 Kawasaki Steel Corp リチウムイオン二次電池用負極材料およびその製造方法
JP2012227151A (ja) * 2001-08-10 2012-11-15 Jfe Chemical Corp リチウムイオン二次電池用負極材料、リチウムイオン二次電池用負極合剤、リチウムイオン二次電池負極およびリチウムイオン二次電池
JP2013201125A (ja) * 2012-02-24 2013-10-03 Mitsubishi Chemicals Corp 非水系二次電池用複層構造炭素材、及びそれを用いた非水系二次電池用負極並びに非水系二次電池
WO2017002959A1 (ja) * 2015-07-02 2017-01-05 昭和電工株式会社 リチウムイオン電池用負極材及びその用途
WO2018047939A1 (ja) * 2016-09-09 2018-03-15 昭和電工株式会社 リチウムイオン二次電池用負極材

Also Published As

Publication number Publication date
KR20210098965A (ko) 2021-08-11
TWI767490B (zh) 2022-06-11
KR102632742B1 (ko) 2024-02-01
TW202146330A (zh) 2021-12-16

Similar Documents

Publication Publication Date Title
JP4996830B2 (ja) リチウムイオン二次電池負極用金属−黒鉛質系粒子およびその製造方法、ならびにリチウムイオン二次電池用負極材料、リチウムイオン二次電池用負極およびリチウムイオン二次電池
KR20150001810A (ko) 복합 흑연질 재료 및 그 제조 방법, 리튬 이온 2차 전지용 부극 재료, 리튬 이온 2차 전지용 부극 및 리튬 이온 2차 전지
JP6278870B2 (ja) 炭素質被覆黒鉛粒子の製造方法、および、それを含有するリチウムイオン二次電池負極の製造方法
JP2003132889A (ja) リチウムイオン二次電池用負極材料およびその製造方法
JP2018133340A (ja) 炭素質被覆黒鉛粒子、リチウムイオン二次電池用負極およびリチウムイオン二次電池
JP6944082B1 (ja) 炭素質被覆黒鉛粒子、リチウムイオン二次電池用負極およびリチウムイオン二次電池
JP6285350B2 (ja) 炭素質被覆黒鉛粒子の製造方法およびリチウムイオン二次電池用負極材料の製造方法
JP2019019048A (ja) 炭素質被覆黒鉛粒子の製造方法、炭素質被覆黒鉛粒子、リチウムイオン二次電池用負極、および、リチウムイオン二次電池
JP2001243949A (ja) リチウム二次電池正極活物質用リチウム遷移金属複合酸化物、その製造方法およびそれを用いたリチウム二次電池
JP3503688B2 (ja) リチウム二次電池
JP4050072B2 (ja) 黒鉛質粒子の製造方法およびリチウムイオン二次電池用負極材料
JP4996827B2 (ja) リチウムイオン二次電池負極用金属−黒鉛系複合粒子およびその製造方法、リチウムイオン二次電池用負極材料および負極ならびにリチウムイオン二次電池
JP6085259B2 (ja) リチウムイオン二次電池負極用の炭素質被覆黒鉛粒子の製造方法、リチウムイオン二次電池負極及びリチウムイオン二次電池
JP5133543B2 (ja) メソカーボン小球体黒鉛化物の製造方法
JP4870419B2 (ja) リチウムイオン二次電池用負極材料およびその製造方法、リチウムイオン二次電池負極ならびにリチウムイオン二次電池
JP6911221B1 (ja) 炭素質材料、炭素質材料の製造方法、リチウムイオン二次電池用負極およびリチウムイオン二次電池
WO2021153080A1 (ja) 炭素質材料、炭素質材料の製造方法、リチウムイオン二次電池用負極およびリチウムイオン二次電池
JP7189109B2 (ja) 炭素質被覆黒鉛粒子の製造方法
JP6322525B2 (ja) 炭素質被覆黒鉛粒子の製造方法
JP5053541B2 (ja) リチウムイオン二次電池用負極材料の製造方法
JP4643165B2 (ja) 炭素材料、リチウムイオン二次電池用負極材料、負極およびリチウムイオン二次電池
WO2024185614A1 (ja) 炭素質被覆黒鉛粒子、リチウムイオン二次電池用負極、リチウムイオン二次電池および炭素質被覆黒鉛粒子の製造方法
WO2024185615A1 (ja) 炭素質被覆黒鉛粒子、リチウムイオン二次電池用負極、リチウムイオン二次電池および炭素質被覆黒鉛粒子の製造方法
JP2024086602A (ja) リチウムイオン二次電池負極用炭素粉末、リチウムイオン二次電池用負極およびリチウムイオン二次電池
JP2024058623A (ja) 炭素質材料および炭素質材料の製造方法

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2021521446

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20916980

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20916980

Country of ref document: EP

Kind code of ref document: A1