WO2011016406A1 - Matériau carboné - Google Patents

Matériau carboné Download PDF

Info

Publication number
WO2011016406A1
WO2011016406A1 PCT/JP2010/062980 JP2010062980W WO2011016406A1 WO 2011016406 A1 WO2011016406 A1 WO 2011016406A1 JP 2010062980 W JP2010062980 W JP 2010062980W WO 2011016406 A1 WO2011016406 A1 WO 2011016406A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode
carbon material
solvent
lithium ion
lithium
Prior art date
Application number
PCT/JP2010/062980
Other languages
English (en)
Japanese (ja)
Inventor
鈴木純次
倉金孝輔
有瀬一郎
Original Assignee
住友化学株式会社
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 住友化学株式会社 filed Critical 住友化学株式会社
Publication of WO2011016406A1 publication Critical patent/WO2011016406A1/fr

Links

Classifications

    • 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
    • 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
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • 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
    • H01M4/13—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
    • H01M4/58—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • 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 material.
  • Carbon materials such as carbon powder are used as electrode materials for lithium ion capacitors and lithium ion secondary batteries.
  • JP-A-10-188978 a cured product obtained by curing a polymer obtained by reacting orthocresol and formaldehyde with hexamethylenetetramine is heated at 1000 ° C. in an inert gas atmosphere.
  • a lithium ion secondary battery having a carbon material obtained in this manner and a negative electrode containing the carbon material is described, and the initial charge / discharge capacity of the lithium ion secondary battery is 341 mAh / g.
  • the present invention ⁇ 1> A carbon material obtained by heating ⁇ -naphtholphthalein, metacresol purple or phenylfluorone at 600 to 3000 ° C .; ⁇ 2> An electrode material comprising the carbon material according to ⁇ 1>, a binder, and a solvent; ⁇ 3> The electrode material according to ⁇ 2>, wherein the binder is a polymer of a fluorine compound; ⁇ 4> The electrode material according to ⁇ 2> or ⁇ 3>, wherein the solvent is at least one selected from the group consisting of an alcohol solvent, an amide solvent, a ketone solvent, an ester solvent, an amine solvent, an ether solvent, and water; ⁇ 5> An electrode containing the carbon material according to ⁇ 1>; ⁇ 6> A lithium ion secondary battery including the electrode according to ⁇ 5>; ⁇ 7> A lithium ion capacitor including the electrode according to ⁇ 5>; ⁇ 8> A method for producing a carbon material having a step of heating
  • the carbon material of the present invention can be obtained by heating ⁇ -naphtholphthalein, metacresol purple or phenylfluorone at 600 to 3000 ° C.
  • ⁇ -Naphtholphthalein, metacresol purple or phenylfluorone is heated preferably at 800 to 1200 ° C., more preferably at 900 to 1100 ° C.
  • ⁇ -naphtholphthalein [3,3-bis (4-hydroxy-1-naphthyl) isobenzofuran-1 (3H) -one] is a compound having the following structure, and a commercially available product may be used. You may use what was manufactured by arbitrary well-known methods.
  • Metacresol purple [3,3-bis (4-hydroxy-2-methylphenyl) -3H-2,1-benzooxathiol 1,1-dioxide] is a compound having the following structure, and a commercially available product is used. Or what was manufactured by arbitrary well-known methods may be used.
  • Phenylfluorone [2,6,7-trihydroxy-9-phenyl-3H-xanthen-3-one] is a compound having the following structure, a commercially available product may be used, or any known method You may use what was manufactured by. Two kinds selected from the group consisting of ⁇ -naphtholphthalein, metacresol purple, and phenylfluorone can be mixed and used.
  • ⁇ -naphtholphthalein, metacresol purple, and phenylfluorone can be mixed and used. Heating of ⁇ -naphtholphthalein, metacresol purple or phenylfluorone is preferably performed in an atmosphere of an inert gas such as nitrogen gas or argon gas. The heating time is preferably in the range of 1 minute to 24 hours. The heating temperature during heating may be constant or may vary within a range of 600 to 3000 ° C.
  • the container After replacing the gas in the container containing ⁇ -naphtholphthalein, metacresol purple or phenylfluorone with an inert gas, the container may be sealed and heated, or ⁇ -naphtholphthalein, metacresol purple Alternatively, heating may be performed while passing an inert gas in a container containing phenylfluorone.
  • the heating of ⁇ -naphtholphthalein, metacresol purple or phenylfluorone is usually performed using a firing furnace such as a rotary kiln, roller hearth kiln, pusher kiln, multi-stage furnace, fluidized furnace, high-temperature firing furnace or the like.
  • metacresol purple or phenylfluorone is placed in the firing furnace, and the gas in the firing furnace is replaced with an inert gas, followed by heating.
  • ⁇ -naphtholphthalein a fired ⁇ -naphtholphthalein obtained by heating ⁇ -naphtholphthalein in an oxidizing gas atmosphere at 400 ° C. or lower in advance may be used.
  • a metacresol purple fired product obtained by heating the metacresol purple at 400 ° C. or lower in an oxidizing gas atmosphere in advance may be used as the metacresol purple.
  • a phenylfluorone fired product obtained by heating phenylfluorone under an oxidizing gas atmosphere at 400 ° C. or lower in advance may be used.
  • the oxidizing gas include air, water, carbon dioxide, and oxygen.
  • Such oxidizing gas may be diluted with the inert gas.
  • Such a baked product is usually one in which a part or all of ⁇ -naphtholphthalein, metacresol purple or phenylfluorone is crosslinked to have a high molecular weight, and / or ⁇ -naphtholphthalein, metacresol purple or phenyl. A part or all of fluorone is carbonized. Heating at 400 ° C.
  • the obtained carbon material is a material for electrodes of dry batteries, piezoelectric element sensors, electric double layer capacitors, lithium ion capacitors, lithium ion secondary batteries, sodium ion secondary batteries and fuel cells;
  • a carrier for chromatography it can be used for an adsorbent and the like, and is particularly suitably used for an electrode material capable of occluding and releasing lithium ions, such as a lithium ion secondary battery and a lithium ion capacitor.
  • the carbon material is usually used after being pulverized into a powdery carbon material having a volume-based median diameter (D 50 ) of 4 to 10 ⁇ m.
  • Suitable pulverization methods include an impact friction pulverizer such as a jet mill, a centrifugal pulverizer, a ball mill (for example, a tube mill, a compound mill, a conical ball mill, a rod mill, a planetary ball mill), a vibration mill, a colloid mill, and a friction disk mill.
  • a method using a pulverizer for fine pulverization such as a jet mill. Of these, a jet mill and a ball mill are preferable.
  • the electrode of the present invention is suitably used as a negative electrode for a lithium ion secondary battery or a negative electrode for a lithium ion capacitor.
  • a binder is usually used so that it can be easily formed as an electrode.
  • the electrode of the present invention is usually produced by a method of forming a mixture containing a carbon material, a binder and the like on a current collector.
  • the electrode of the present invention is a method of applying an electrode material containing a carbon material, a binder and a solvent on a current collector by a doctor blade method or the like, or after immersing the current collector in the electrode material, It can also be produced by a drying method.
  • the electrode of the present invention is prepared by kneading an electrode material containing a carbon material, a binder and a solvent, and further drying to prepare a sheet. The obtained sheet is placed on a current collector via a conductive adhesive. After pasting, it can also be produced by a method of pressing, heating and drying.
  • an electrode material containing a carbon material, a binder and a solvent is removed to obtain a sheet, and then the obtained sheet is stretched in a uniaxial or multiaxial direction.
  • the electrode of the present invention can also be manufactured.
  • an electrode material containing a carbon material, a binder, and a solvent is suitably used for manufacturing the electrode of the present invention.
  • the thickness is preferably in the range of 5 to 1000 ⁇ m.
  • the current collector material is nickel, aluminum, titanium, copper, gold, silver, platinum, aluminum alloy, stainless steel, etc .; plasma spraying or arc spraying, nickel, aluminum, zinc, copper, tin, lead or these A carbon material or activated carbon fiber coated with an alloy of the above; and a conductive material formed of a resin such as rubber or styrene-ethylene-butylene-styrene copolymer (SEBS) and a conductive agent, wherein the conductive agent is dispersed in the resin.
  • SEBS styrene-ethylene-butylene-styrene copolymer
  • Examples of the shape of the current collector include a foil shape, a flat plate shape, a mesh shape, a net shape, a lath shape, a punching shape, an embossed shape, and a combination thereof (for example, a mesh-like flat plate).
  • a corrugated surface may be formed on the surface of the current collector by etching.
  • Examples of the binder include a polymer of a fluorine compound.
  • the fluorine atom is C2-C10 olefin attached to the double bond carbons.
  • the binder include a polymer produced by addition polymerization of a monomer containing an ethylenic double bond and not containing a fluorine atom.
  • Examples of such monomers include C1-C22 alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, lauryl acrylate, and octadecyl acrylate; methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl C1-C22 alkyl methacrylate such as methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, octadecyl methacrylate; C3-C22 cycloalkyl acrylate such as cyclohexyl acrylate; C3-C22 cycloalkyl methacrylate such as cyclohexyl methacrylate; benzyl acrylate Ac
  • Carboxylic alkenyl monomers such as methallyl ester of C12 carboxylic acid; Monomers having epoxy group such as glycidyl acrylate, allyl glycidyl ether, glycidyl methacrylate, methallyl glycidyl ether; ethylene, propylene, 1-butene, 1-octene C2-C12 monoolefins such as 1-dodecene; monomers having chlorine, bromine or iodine atoms such as vinyl chloride and vinylidene chloride; acrylic acid; methacrylic acid; and conjugated double bonds such as butadiene and isoprene Monomers are exemplified with.
  • the polymer produced by addition polymerization may be a copolymer composed of a plurality of monomers such as an ethylene-vinyl acetate copolymer, a styrene-butadiene copolymer, and an ethylene-propylene copolymer.
  • the polymer of vinyl carboxylate may be partially or completely saponified, such as polyvinyl alcohol.
  • the conjugate may be a copolymer comprising a fluorine compound and an ethylenic double bond and a monomer not containing a fluorine atom.
  • binders include starch, methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylhydroxyethylcellulose, nitrocellulose and other polysaccharides; phenol resins; melamine resins; polyurethane resins; urea resins : Polyimide resin; Polyamide-imide resin; Petroleum pitch; and Coal pitch.
  • a polymer of a fluorine compound is preferable, and polyvinylidene fluoride which is a polymer of vinylidene fluoride is more preferable. Multiple binders may be used.
  • the amount of the binder compounded in the electrode is usually 0.5 to 30 parts by weight, preferably 2 to 30 parts by weight with respect to 100 parts by weight of the carbon material.
  • an organic solvent or water that can dissolve the binder is usually used.
  • alcohol solvents such as isopropanol, ethanol and methanol
  • amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide
  • ketone solvents such as methyl ethyl ketone and cyclohexanone
  • acetic acid examples include ester solvents such as methyl and methyl acrylate, amine solvents such as diethyltriamine and N, N-dimethylaminopropylamine, ether solvents such as ethylene oxide and tetrahydrofuran, and water.
  • a carbon material can be slurried with a latex such as SBR by further adding a dispersant, a thickener or the like.
  • the amount of the solvent used is preferably 0.8 to 2 parts by weight with respect to 1 part by weight of the carbon material.
  • a plasticizer can be used to facilitate application of an electrode material including a carbon material, a binder, and a solvent to the current collector.
  • a lithium ion secondary battery usually includes a positive electrode, a separator, an electrolytic solution, and a negative electrode, and a lithium oxidation-reduction reaction is performed at both the positive electrode and the negative electrode, and electric energy can be stored and released.
  • the electrode of the present invention is usually used as a negative electrode.
  • the positive electrode usually includes a current collector, a material capable of occluding and releasing lithium ions, a conductive material and a binder, and a mixture of the material capable of occluding and releasing lithium ions, a conductive material and a binder is disposed on the current collector. It is carried on.
  • Examples of the material capable of inserting and extracting lithium ions include lithium composite oxides including at least one transition metal selected from the group consisting of V, Mn, Fe, Co, and Ni and lithium, and lithium foil.
  • a layered lithium composite oxide based on an ⁇ -NaFeO 2 type structure such as a composite oxide of cobalt and lithium, a transition metal other than nickel or aluminum, and a composite oxide of lithium in that the average discharge potential is high
  • a lithium composite oxide based on a spinel structure such as lithium manganese spinel is preferred.
  • Examples of the binder used for the positive electrode include the same binder as in the electrode A.
  • Examples of the conductive material include the carbon material, natural graphite, artificial graphite, coke and carbon black of the present invention.
  • the electrolytic solution examples include a non-aqueous electrolyte solution obtained by dissolving a lithium salt in an organic solvent.
  • Lithium salts include LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (SO 2 CF 3 ) 2 , LiC (SO 2 CF 3 ) 3 , Li 2 B 10 Cl 10 ,
  • LiAlCl 4 lower aliphatic carboxylic acid lithium salts, and mixtures thereof.
  • At least one fluorine-containing lithium salt selected from the group consisting of LiPF 6 , LiAsF 6 , LiSbF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 and LiC (CF 3 SO 2 ) 3.
  • organic solvents include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 4-trifluoromethyl-1,3-dioxolan-2-one, and 1,2-di (methoxycarbonyloxy) ethane.
  • Carbonate solvents such as 1,2-dimethoxyethane, 1,3-dimethoxypropane, pentafluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyl difluoromethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, formic acid
  • Ester solvents such as methyl, methyl acetate and ⁇ -butyrolactone
  • nitrile solvents such as acetonitrile and butyronitrile
  • amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide
  • Carbamate solvent such as-2-oxazolidone, sulfolane, dimethyl sulfoxide, the solvent having a sulfur-containing solvent and a fluorine-containing substituent such as 1,3-propane sultone and the like.
  • the separator separates the working electrode and the counter electrode and holds the electrolytic solution, and a film having a large ion permeability, a predetermined mechanical strength, and an insulating property is usually used.
  • paper made from viscose rayon, natural cellulose, etc . mixed paper made from fibers such as cellulose and polyester; electrolytic paper; craft paper; manila paper; polyethylene nonwoven fabric, polypropylene nonwoven fabric, polyester nonwoven fabric, glass fiber, porous Non-woven fabric such as modified polyethylene, aramid fiber, polybutylene terephthalate nonwoven fabric, para-type wholly aromatic polyamide; vinylidene fluoride, tetrafluoroethylene, copolymer of vinylidene fluoride and hexafluoropropylene, fluorine-containing resin such as fluorine rubber And porous membranes such as porous polyethylene, porous polypropylene, and porous polyester.
  • the separator may be a molded product made of ceramic powder particles such as silica and the binder.
  • the molded article is usually molded integrally with both the working electrode and the counter electrode.
  • a separator formed of polyethylene, polypropylene, or the like may contain a surfactant or silica particles in order to improve the hydrophilicity.
  • the separator may further contain an organic solvent such as acetone and a plasticizer such as dibutyl phthalate (DBP).
  • a proton conductive polymer may be used as DBP.
  • electrolytic paper paper made from viscose rayon or natural cellulose, kraft paper, Manila paper, mixed paper made from cellulose or polyester fibers, polyethylene nonwoven fabric, polypropylene nonwoven fabric, polyester nonwoven fabric, Manila hemp sheet and glass fiber sheet are preferred.
  • the pore diameter of the separator is usually 0.01 to 10 ⁇ m.
  • the thickness of the separator is usually 1 to 300 ⁇ m, preferably 5 to 30 ⁇ m.
  • a plurality of separators having different pore ratios in the separator may be laminated.
  • a separator made of a polyolefin porous membrane and a polyester resin porous membrane is particularly suitable.
  • the lithium ion secondary battery of the present invention can be produced by assembling the above positive electrode, separator, electrolyte and negative electrode by a conventional method.
  • the electrode of the present invention is excellent in cycle characteristics when charging and discharging are repeated.
  • the electrode of the present invention can also be used as an electrode of a lithium ion capacitor.
  • a lithium ion capacitor is a capacitor that is charged and discharged by adsorption and desorption of lithium ions and electrolyte ions, and is an improved energy density of an electric double layer capacitor.
  • the electrode of the present invention is usually used as a negative electrode.
  • the positive electrode is usually a material in which a mixture containing a material capable of reversibly supporting lithium ions and anions such as tetrafluoroborate, a conductive material, and a binder is supported on a current collector.
  • a material capable of reversibly supporting lithium ions and anions such as tetrafluoroborate, a conductive material, and a binder is supported on a current collector.
  • materials that can reversibly carry lithium ions and anions include carbon isotopes, and electrode active materials used in electric double layer capacitors can be widely used.
  • Specific examples of the allotrope of carbon include activated carbon, polyacene (PAS), carbon whisker, and graphite, and those in powder form or fiber form can be used. Among these, activated carbon is preferable.
  • the binder contained in the positive electrode are the same as those in the above-described electrode of the present invention.
  • Examples of the conductive material contained in the positive electrode include the carbon material, natural graphite, artificial graphite, coke and carbon black of the present invention. These may be used singly or as a mixture of artificial graphite and carbon black, two or more kinds of mixtures may be used.
  • As the electrolyte solution of the lithium ion capacitor a non-aqueous electrolyte solution in which a lithium salt similar to the electrolyte solution of the lithium ion secondary battery is dissolved in an organic solvent is preferably used.
  • the lithium ion capacitor may include a separator similar to the separator of the lithium ion secondary battery.
  • the lithium ion capacitor of the present invention can be manufactured by assembling the above positive electrode, separator, electrolyte and negative electrode by a conventional method.
  • the electrode of the present invention exhibits excellent performance even after repeated use. Moreover, since the lithium ion capacitor containing the electrode containing the carbon material of this invention has the small electrical resistance of an electrode, the improvement of the output density can be anticipated.
  • Example 1 After replacing the gas in the baking furnace containing ⁇ -naphtholphthalein (special grade reagent purchased from Wako Pure Chemical Industries, Ltd.) with nitrogen, 0.1 L per minute per 1 g of ⁇ -naphtholphthalein, nitrogen gas was heated from the room temperature to 900 ° C. at a heating rate of 5 ° C./min. After reaching 900 ° C., it was held at 900 ° C.
  • ⁇ -naphtholphthalein special grade reagent purchased from Wako Pure Chemical Industries, Ltd.
  • Example 2 In Example 1, a powdery carbon material was obtained in the same manner as in Example 1 except that the heating temperature was 1000 ° C.
  • Example 3 In Example 1, instead of ⁇ -naphtholphthalein, a powdery carbon material was prepared in the same manner as in Example 1 except that metacresol purple (special grade reagent purchased from Wako Pure Chemical Industries, Ltd.) was used. Obtained.
  • Example 4 In Example 3, a powdery carbon material was obtained in the same manner as in Example 3 except that the heating temperature was 1000 ° C.
  • Example 5 In Example 3, a powdery carbon material was obtained in the same manner as in Example 3 except that the heating temperature was 1100 ° C.
  • Example 6 In Example 1, a powdery carbon material was used in the same manner as in Example 1 except that phenylfluorone (a reagent purchased from Tokyo Chemical Industry Co., Ltd., grade GR) was used instead of ⁇ -naphtholphthalein. Got.
  • Example 7 In Example 6, a powdery carbon material was obtained in the same manner as in Example 6 except that the heating temperature was 1000 ° C.
  • Example 8 In Example 6, a powdery carbon material was obtained in the same manner as in Example 6 except that the heating temperature was 1100 ° C.
  • Example 9 In Example 6, a powdery carbon material was obtained in the same manner as in Example 6 except that the heating temperature was 1200 ° C.
  • Example 10 An appropriate amount of N-methyl-2-pyrrolidone was added to a mixture of 91 parts of the carbon material obtained in Example 1 and 9 parts of polyvinylidene fluoride (PVDF) (solid content), and the resulting mixture was kneaded. The obtained mixture was applied onto a copper current collector having a thickness of 20 ⁇ m by a doctor blade method. The applied current collector was dried at 50 ° C. for 2 hours.
  • PVDF polyvinylidene fluoride
  • the dried current collector was cut into a circle having a diameter of 1.45 cm and vacuum-dried at 120 ° C. for 8 hours to obtain an electrode.
  • the obtained electrode contained 4.7 mg of a mixture of carbon material and PVDF.
  • the negative electrode the obtained electrode was used as the positive electrode
  • the lithium foil was used as the separator
  • TF40-50 manufactured by Nippon Kogyo Paper Industries Co., Ltd.
  • LiPF 6 / propylene carbonate having a concentration of 1 mol / liter was used as the electrolyte.
  • a bipolar cell was produced using a coin cell of type (IEC / JIS standard).
  • the initial discharge capacity of the produced coin-type battery was 376 mAh / g, and the initial charge / discharge efficiency (ratio of the initial discharge capacity to the initial charge capacity) was 69%.
  • the charge / discharge capacity of the produced battery was measured by the following measurement method using a charge / discharge evaluation apparatus (“TOSCAT (registered trademark) -3100” manufactured by Toyo System Co., Ltd.).
  • TOSCAT charge / discharge evaluation apparatus
  • the battery was subjected to constant current charging at a current density of 60 mA / g until the voltage reached 0 V, and then constant potential charging was performed at 0 V.
  • the total time of constant current charging at a current density of 60 mA / g and constant potential charging at 0 V was 12 hours.
  • Example 11 In Example 10, a bipolar cell was fabricated in the same manner as in Example 10 except that the carbon material obtained in Example 2 was used instead of the carbon material obtained in Example 1. According to the measurement method described in Example 10, the initial charge capacity and initial discharge capacity of the produced cell were measured, and the initial charge / discharge efficiency was determined. The results are shown in Table 1.
  • Example 12 a bipolar cell was produced in the same manner as in Example 10 except that the carbon material obtained in Example 3 was used instead of the carbon material obtained in Example 1. According to the measurement method described in Example 10, the initial charge capacity and initial discharge capacity of the produced cell were measured, and the initial charge / discharge efficiency was determined. The results are shown in Table 1.
  • Example 13 a bipolar cell was produced in the same manner as in Example 10 except that the carbon material obtained in Example 4 was used instead of the carbon material obtained in Example 1. According to the measurement method described in Example 10, the initial charge capacity and initial discharge capacity of the produced cell were measured, and the initial charge / discharge efficiency was determined. The results are shown in Table 1.
  • Example 14 In Example 10, a bipolar cell was produced in the same manner as in Example 10 except that the carbon material obtained in Example 5 was used instead of the carbon material obtained in Example 1. According to the measurement method described in Example 10, the initial charge capacity and initial discharge capacity of the produced cell were measured, and the initial charge / discharge efficiency was determined. The results are shown in Table 1.
  • Example 15 In Example 10, a bipolar cell was produced in the same manner as in Example 10 except that the carbon material obtained in Example 6 was used instead of the carbon material obtained in Example 1. According to the measurement method described in Example 10, the initial charge capacity and initial discharge capacity of the produced cell were measured, and the initial charge / discharge efficiency was determined. The results are shown in Table 1.
  • Example 16 In Example 10, a bipolar cell was produced in the same manner as in Example 10 except that the carbon material obtained in Example 7 was used instead of the carbon material obtained in Example 1. According to the measurement method described in Example 10, the initial charge capacity and initial discharge capacity of the produced cell were measured, and the initial charge / discharge efficiency was determined. The results are shown in Table 1.
  • Example 17 In Example 10, a bipolar cell was produced in the same manner as in Example 10 except that the carbon material obtained in Example 8 was used instead of the carbon material obtained in Example 1. According to the measurement method described in Example 10, the initial charge capacity and initial discharge capacity of the produced cell were measured, and the initial charge / discharge efficiency was determined. The results are shown in Table 1.
  • Example 18 In Example 10, a bipolar cell was produced in the same manner as in Example 10 except that the carbon material obtained in Example 9 was used instead of the carbon material obtained in Example 1. According to the measurement method described in Example 10, the initial charge capacity and initial discharge capacity of the produced cell were measured, and the initial charge / discharge efficiency was determined. The results are shown in Table 1.
  • Example 19 An appropriate amount of N-methyl-2-pyrrolidone was added to a mixture of 91 parts of the carbon material obtained in Example 2 and 9 parts of polyvinylidene fluoride (PVDF) (solid content), and the resulting mixture was kneaded. The obtained mixture was applied onto a copper current collector having a thickness of 20 ⁇ m by a doctor blade method. The applied current collector was dried at 50 ° C.
  • PVDF polyvinylidene fluoride
  • the dried current collector was cut into a circle having a diameter of 1.45 cm and vacuum-dried at 120 ° C. for 8 hours to obtain an electrode.
  • the resulting electrode contained 4.25 mg of a mixture of carbon material and PVDF.
  • the negative electrode the obtained electrode was used as the positive electrode
  • the lithium foil was used as the separator
  • TF40-50 manufactured by Nippon Kogyo Paper Industries Co., Ltd.
  • LiPF 6 / propylene carbonate having a concentration of 1 mol / liter was used as the electrolyte.
  • a bipolar cell was produced using a coin cell of type (IEC / JIS standard). On page 6 of Japanese Patent No.
  • Lithium doping / undoping may be performed under a constant current, under a constant voltage, or under conditions where the current and voltage change”. Therefore, the prepared bipolar cell was charged with constant current-constant voltage to prepare a pre-doped electrode.
  • preparation of the electrode was performed by the following method using the charging / discharging evaluation apparatus ("TOSCAT (trademark) -3100" by Toyo System Co., Ltd.). The battery was subjected to constant current charging at a current density of 40 mA / g until the voltage reached 0 V, and then constant voltage charging was performed at 0 V until the amount of charge reached 508 mAh / g.
  • the obtained pre-doped electrode is used as a positive electrode, a commercially available activated carbon electrode (manufactured by Hosen Co., Ltd.), a separator, TF40-50 manufactured by Nippon Kogyo Paper Industries Co., Ltd., and a concentration of 1 mol / liter as an electrolyte.
  • LiPF 6 / propylene carbonate was used, and a lithium ion capacitor was assembled using a CR2032 type (IEC / JIS standard) coin cell.
  • the weight ratio of the positive electrode active material to the negative electrode active material was 1.7 / 1.
  • the assembled lithium ion capacitor was fixed at a current density of 40 mA / g for 3.5 hours until the voltage reached 3.8 V.
  • the battery was discharged at a current density of 2 mA / cm 2 until the voltage reached 2.2V.
  • the accumulated amount of electricity (discharge capacity) during discharge was 0.21 mAh.
  • the lithium ion capacitor was charged with a constant current at a current density of 40 mA / g for 3.5 hours until the voltage reached 3.8 V, and then discharged at a current density of 15 mA / cm 2 until the voltage reached 2.2 V.
  • the accumulated amount of electricity (discharge capacity) during discharge was 0.15 mAh. Further, the resistance value calculated based on the IR drop for 1 second immediately after the start of discharge at this time was 12.1 ⁇ . Thereafter, the lithium ion capacitor was charged with a constant current at a current density of 40 mA / g for 3.5 hours until the voltage reached 3.8 V, and then discharged at a current density of 30 mA / cm 2 until the voltage reached 2.2 V. The accumulated amount of electricity (discharge capacity) during discharge was 0.12 mAh.
  • Example 20 An appropriate amount of N-methyl-2-pyrrolidone was added to a mixture of 91 parts of the carbon material obtained in Example 4 and 9 parts of polyvinylidene fluoride (PVDF) (solid content), and the resulting mixture was kneaded. The obtained mixture was applied onto a copper current collector having a thickness of 20 ⁇ m by a doctor blade method. The applied current collector was dried at 50 ° C. for 2 hours.
  • PVDF polyvinylidene fluoride
  • the dried current collector was cut into a circle having a diameter of 1.45 cm and vacuum-dried at 120 ° C. for 8 hours to obtain an electrode.
  • the resulting electrode contained 4.62 mg of a mixture of carbon material and PVDF.
  • the negative electrode the obtained electrode was used as the positive electrode
  • the lithium foil was used as the separator
  • TF40-50 manufactured by Nippon Kogyo Paper Industries Co., Ltd.
  • LiPF 6 / propylene carbonate having a concentration of 1 mol / liter was used as the electrolyte.
  • a bipolar cell was produced using a coin cell of type (IEC / JIS standard). On page 6 of Japanese Patent No.
  • Lithium doping / undoping may be performed under a constant current, under a constant voltage, or under conditions where the current and voltage change”. Therefore, the prepared bipolar cell was charged with constant current-constant voltage to prepare a pre-doped electrode.
  • preparation of the electrode was performed by the following method using the charging / discharging evaluation apparatus ("TOSCAT (trademark) -3100" by Toyo System Co., Ltd.). The battery was subjected to constant current charging at a current density of 40 mA / g until the voltage reached 0 V, and then constant voltage charging was performed at 0 V until the amount of charge reached 535 mAh / g.
  • the obtained pre-doped electrode is used as a positive electrode, a commercially available activated carbon electrode (manufactured by Hosen Co., Ltd.), a separator, TF40-50 manufactured by Nippon Kogyo Paper Industries Co., Ltd., and a concentration of 1 mol / liter as an electrolyte.
  • LiPF 6 / propylene carbonate was used, and a lithium ion capacitor was assembled using a CR2032 type (IEC / JIS standard) coin cell.
  • the weight ratio of the positive electrode active material to the negative electrode active material was 1.5 / 1.
  • the assembled lithium ion capacitor was fixed at a current density of 40 mA / g for 3.5 hours until the voltage reached 3.8 V.
  • the battery was discharged at a current density of 2 mA / cm 2 until the voltage reached 2.2V.
  • the accumulated amount of electricity (discharge capacity) during discharge was 0.22 mAh.
  • the lithium ion capacitor was charged with a constant current at a current density of 40 mA / g for 3.5 hours until the voltage reached 3.8 V, and then discharged at a current density of 15 mA / cm 2 until the voltage reached 2.2 V.
  • the cumulative amount of electricity (discharge capacity) during discharge was 0.17 mAh. Further, the resistance value calculated based on the IR drop for 1 second immediately after the start of discharge at this time was 9.4 ⁇ . Thereafter, the lithium ion capacitor was charged with a constant current at a current density of 40 mA / g for 3.5 hours until the voltage reached 3.8 V, and then discharged at a current density of 30 mA / cm 2 until the voltage reached 2.2 V. The accumulated amount of electricity (discharge capacity) during discharge was 0.13 mAh.
  • Example 21 An appropriate amount of N-methyl-2-pyrrolidone was added to a mixture of 91 parts of the carbon material obtained in Example 7 and 9 parts of polyvinylidene fluoride (PVDF) (solid content), and the resulting mixture was kneaded. The obtained mixture was applied onto a copper current collector having a thickness of 20 ⁇ m by a doctor blade method. The applied current collector was dried at 50 ° C. for 2 hours.
  • PVDF polyvinylidene fluoride
  • the dried current collector was cut into a circle having a diameter of 1.45 cm and vacuum-dried at 120 ° C. for 8 hours to obtain an electrode.
  • the resulting electrode contained 4.18 mg of a mixture of carbon material and PVDF.
  • the negative electrode the obtained electrode was used as the positive electrode
  • the lithium foil was used as the separator
  • TF40-50 manufactured by Nippon Kogyo Paper Industries Co., Ltd.
  • LiPF 6 / propylene carbonate having a concentration of 1 mol / liter was used as the electrolyte.
  • a bipolar cell was produced using a coin cell of type (IEC / JIS standard). On page 6 of Japanese Patent No.
  • Lithium doping / undoping may be performed under a constant current, under a constant voltage, or under conditions where the current and voltage change”. Therefore, the prepared bipolar cell was charged with constant current-constant voltage to prepare a pre-doped electrode.
  • preparation of the electrode was performed by the following method using the charging / discharging evaluation apparatus ("TOSCAT (trademark) -3100" by Toyo System Co., Ltd.). The battery was subjected to constant current charging at a current density of 40 mA / g until the voltage reached 0 V, and then constant voltage charging was performed at 0 V until the amount of charge reached 582 mAh / g.
  • the pre-doping method was based on the method described in the evaluation method for lithium-in capacitors described in the 3rd October Seminar Material 133-138 (held in October 2008) of the Carbon Materials Society of Japan.
  • the obtained pre-doped electrode is used as a positive electrode, a commercially available activated carbon electrode (manufactured by Hosen Co., Ltd.), a separator, TF40-50 manufactured by Nippon Kogyo Paper Industries Co., Ltd., and a concentration of 1 mol / liter as an electrolyte.
  • LiPF 6 / propylene carbonate was used, and a lithium ion capacitor was assembled using a CR2032 type (IEC / JIS standard) coin cell.
  • the weight ratio of the positive electrode active material to the negative electrode active material was 1.7 / 1.
  • the assembled lithium ion capacitor was fixed at a current density of 40 mA / g for 3.5 hours until the voltage reached 3.8 V.
  • the battery was discharged at a current density of 2 mA / cm 2 until the voltage reached 2.2V.
  • the accumulated amount of electricity (discharge capacity) during discharge was 0.22 mAh.
  • the lithium ion capacitor was charged with a constant current at a current density of 40 mA / g for 3.5 hours until the voltage reached 3.8 V, and then discharged at a current density of 15 mA / cm 2 until the voltage reached 2.2 V.
  • the accumulated amount of electricity (discharge capacity) during discharge was 0.18 mAh.
  • the resistance value calculated based on the IR drop for 1 second immediately after the start of discharge at this time was 8.3 ⁇ . Thereafter, the lithium ion capacitor was charged with a constant current at a current density of 40 mA / g for 3.5 hours until the voltage reached 3.8 V, and then discharged at a current density of 30 mA / cm 2 until the voltage reached 2.2 V.
  • the accumulated amount of electricity (discharge capacity) during discharge was 0.15 mAh.
  • the current density at the time of discharging is referred to the value described in JP-A-2006-286841, and the charging voltage and the discharging voltage are referred to the values described in JP-A-2006-303118, respectively. Set.
  • the carbon material of the present invention is useful as an electrode of a lithium ion secondary battery or a lithium ion capacitor.
  • a lithium ion secondary battery with improved initial charge / discharge capacity can be provided. Improvement of the output density of the lithium ion capacitor can be expected.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Power Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

La présente invention concerne un matériau carboné produit par chauffage de α-naphtolphtaléine, de pourpre de métacrésol ou de phénylfluorone à 600 à 3000 °C.
PCT/JP2010/062980 2009-08-04 2010-07-26 Matériau carboné WO2011016406A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2009-181345 2009-08-04
JP2009181345 2009-08-04
JP2009181343 2009-08-04
JP2009181344 2009-08-04
JP2009-181344 2009-08-04
JP2009-181343 2009-08-04

Publications (1)

Publication Number Publication Date
WO2011016406A1 true WO2011016406A1 (fr) 2011-02-10

Family

ID=43544302

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/062980 WO2011016406A1 (fr) 2009-08-04 2010-07-26 Matériau carboné

Country Status (2)

Country Link
TW (1) TW201125817A (fr)
WO (1) WO2011016406A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103560270A (zh) * 2013-10-30 2014-02-05 河南师范大学 一种锂离子电池用电解液

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09204918A (ja) * 1995-11-25 1997-08-05 Sony Corp 非水電解液二次電池用負極材料、その製造方法及び非水電解液二次電池
JP2009049236A (ja) * 2007-08-21 2009-03-05 Air Water Inc 炭素電極材、炭素電極材混合物および炭素電極材の製造方法、ならびに電気二重層キャパシタ、リチウムイオン電池およびリチウムイオンキャパシタ
JP2009132593A (ja) * 2007-10-30 2009-06-18 Sumitomo Chemical Co Ltd 炭素材料及び該炭素材料を有する電極

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09204918A (ja) * 1995-11-25 1997-08-05 Sony Corp 非水電解液二次電池用負極材料、その製造方法及び非水電解液二次電池
JP2009049236A (ja) * 2007-08-21 2009-03-05 Air Water Inc 炭素電極材、炭素電極材混合物および炭素電極材の製造方法、ならびに電気二重層キャパシタ、リチウムイオン電池およびリチウムイオンキャパシタ
JP2009132593A (ja) * 2007-10-30 2009-06-18 Sumitomo Chemical Co Ltd 炭素材料及び該炭素材料を有する電極

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KHOO, S. B. ET AL.: "Determination of Trace Amounts of Antimony(III) by Differential-pulse Anodic Stripping Voltammetry at a Phenylfluorone-modified Carbon Paste Electrode", ANALYST, vol. 121, no. 12, 1996, pages 1983 - 1988 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103560270A (zh) * 2013-10-30 2014-02-05 河南师范大学 一种锂离子电池用电解液

Also Published As

Publication number Publication date
TW201125817A (en) 2011-08-01

Similar Documents

Publication Publication Date Title
JP6045581B2 (ja) 非水電解質二次電池用樹脂膜の製造方法および非水電解質二次電池用樹脂膜
JP6038141B2 (ja) 樹脂組成物、非水電解質二次電池用フィラー含有樹脂膜、および非水電解質二次電池用フィラー含有樹脂膜の製造方法
US20100255356A1 (en) Electric storage device and its production method
JP6273956B2 (ja) 二次電池多孔膜用バインダー、二次電池多孔膜用スラリー組成物、二次電池用多孔膜及び二次電池
KR20150106808A (ko) 이차 전지 및 이의 제조 방법
KR20150135207A (ko) 축전 디바이스용 결합제 조성물
KR101509280B1 (ko) 탄소 재료의 제조 방법
JP2013258392A (ja) 電極活物質、電極及び蓄電デバイス
JP6813350B2 (ja) 二次電池用バインダ、二次電池用バインダ樹脂組成物、二次電池用電極、および二次電池
JP2016126856A (ja) 二次電池用バインダ、二次電池用セパレータ、及び二次電池
CN105742638B (zh) 用于可再充电锂离子电池的粘合剂、用于可再充电锂离子电池的隔板和可再充电锂离子电池
JP2009205918A (ja) 蓄電デバイス
WO2015098116A1 (fr) Pâte de matériau conducteur pour électrode de batterie rechargeable, procédé de production de suspension épaisse pour cathode de batterie rechargeable, procédé de production de cathode de batterie rechargeable, et batterie rechargeable
WO2011002013A1 (fr) Matière active pour une électrode destinée à une batterie secondaire à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux
WO2011078263A1 (fr) Électrode pour batterie secondaire et batterie secondaire
JP6452609B2 (ja) 正極を製造する方法
CN116250095A (zh) 二次电池用正极和包含其的二次电池
WO2016108495A1 (fr) Séparateur destiné à une batterie rechargeable au lithium, et batterie rechargeable au lithium le comprenant
JP2011192888A (ja) リチウムイオンキャパシタおよびその製造方法、正極およびその製造方法、並びに、蓄電デバイス
WO2010082645A1 (fr) Procede de production de matiere carbonee
KR20130140395A (ko) 리튬 이차전지용 음극 및 그 제조방법과 이를 이용한 리튬 이차전지
KR20210021950A (ko) 탄소 재료, 도전 보조제, 축전 디바이스용 전극, 및 축전 디바이스
JP5717929B2 (ja) 窒素含有ポリマーを含む電気化学セル
JPWO2018230597A1 (ja) 正極用組成物
WO2011016406A1 (fr) Matériau carboné

Legal Events

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

Ref document number: 10806405

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: 10806405

Country of ref document: EP

Kind code of ref document: A1