WO2012039477A1 - Batterie lithium-ion et module de batterie l'utilisant - Google Patents

Batterie lithium-ion et module de batterie l'utilisant Download PDF

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WO2012039477A1
WO2012039477A1 PCT/JP2011/071705 JP2011071705W WO2012039477A1 WO 2012039477 A1 WO2012039477 A1 WO 2012039477A1 JP 2011071705 W JP2011071705 W JP 2011071705W WO 2012039477 A1 WO2012039477 A1 WO 2012039477A1
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Prior art keywords
negative electrode
electrode active
active material
coating layer
lithium ion
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PCT/JP2011/071705
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English (en)
Japanese (ja)
Inventor
西村　悦子
明秀 田中
孝亮 馮
本棒　英利
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日立化成工業株式会社
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Priority to CN201180045723.8A priority Critical patent/CN103190018B/zh
Priority to KR1020137008217A priority patent/KR102010093B1/ko
Priority to JP2012535082A priority patent/JP6003648B2/ja
Publication of WO2012039477A1 publication Critical patent/WO2012039477A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a lithium ion battery and a battery module using the lithium ion battery.
  • Lithium ion batteries have a high energy density and are attracting attention as batteries for electric vehicles and power storage.
  • electric vehicles include zero-emission electric vehicles that are not equipped with an engine, hybrid electric vehicles that are equipped with both an engine and a secondary battery, and plug-in hybrid electric vehicles that are directly charged from a system power source.
  • an electric vehicle means the above-mentioned various vehicles.
  • it is expected to be used as a stationary power storage system that stores power and supplies power in an emergency when the power system is cut off.
  • lithium ion batteries are required to have excellent durability. That is, even when the environmental temperature is high, the rate of decrease in capacity that can be charged and discharged is small, and the capacity maintenance rate of the battery is high over a long period of time.
  • lithium-ion batteries for electric vehicles are exposed to a high temperature environment of 40 ° C. to 70 ° C. due to radiant heat from the road surface or heat transfer from inside the vehicle, and it is important to improve the long-term storage characteristics and cycle life in these environments. It is a development issue.
  • JP-A-6-168725 discloses an invention relating to a battery using a negative electrode in which a carbon material is treated and graphitized at a high temperature of 2000 ° C. or higher, pulverized, and further subjected to a heat treatment of 2000 ° C. or higher.
  • Japanese Patent Publication No. 2000-156230 discloses a negative electrode active material composed of secondary particles formed by granulating primary particles having a graphite surface coated with amorphous carbon.
  • Japanese Patent Application Laid-Open No. 2002-134171 discloses an invention relating to a battery in which carbon whose surface is coated with a water-soluble polymer material that is negatively charged in water is used as a negative electrode active material.
  • An invention is disclosed in which the surface is coated with a thin film of lithium ion conductive solid electrolyte.
  • Japanese Patent Laid-Open No. 2000-264614 discloses an invention in which graphite particles are treated with a surfactant and then a coating layer made of carbon is formed on the surface of the graphite particles.
  • Japanese Patent Laid-Open No. 2001-229914 is disclosed on the surface of graphite.
  • An invention is disclosed in which an amorphous carbon coating layer is formed to suppress the decomposition of the electrolytic solution.
  • Japanese Patent Laid-Open No. 2006-24374 discloses an invention relating to carbon secondary particles in which a carbon coating layer is formed on the surface of crystalline carbon particles (primary particles), and primary particles are bonded via the carbon coating layer.
  • Japanese Patent Laid-Open No. 2006-228505 discloses an average particle diameter of 5 ⁇ m to 50 ⁇ m, a true specific gravity of 2.20 g / cm 3 or more, a specific surface area of 8 m 2 / g or less by nitrogen gas adsorption, and a specific surface area of 1 m 2 by carbon dioxide gas adsorption.
  • the invention relating to graphite for negative electrode, characterized in that the oxygen atom concentration measured by X-ray photoelectron spectroscopy spectrum is 0.7 atom% or more.
  • Japanese Patent Application Laid-Open No. 2007-42571 is an invention relating to a carbon material in which the surface distance d002 of the carbon 002 surface obtained by X-ray diffraction measurement is 0.340 nm to 0.390 nm, and specifies the He true density and the CO 2 adsorption amount. is doing.
  • Japanese Patent Application Laid-Open No. 2009-187924 has a crystallite size Lc analyzed by X-ray diffraction of 20 nm to 90 nm, an interplanar spacing d002 of the carbon 002 plane of 0.3354 nm to 0.3370 nm, and a low crystal on the surface.
  • the invention regarding the negative electrode material which formed the active carbon is disclosed.
  • An object of the present invention is to suppress the self-discharge caused by the negative electrode and extend the life of the lithium ion battery.
  • the present inventors have come to find a means that the capacity of the battery is unlikely to decrease even after charging or discharging or leaving the lithium ion battery in a high temperature environment.
  • a negative electrode active material capable of occluding and releasing lithium
  • the negative electrode active material is a composite having a low crystalline carbon coating layer on the surface of graphite particles (graphite core material).
  • a negative electrode containing the negative electrode active material having a peak temperature difference of 300 ° C. or less between an oxidation peak having a peak at the highest temperature and an oxidation peak having a peak at the lowest temperature within the range, a positive electrode, and nonaqueous electrolysis And a non-aqueous solvent, lithium-ion battery comprising provided.
  • the low crystalline carbon is amorphous or low crystalline carbon.
  • the lithium ion in which the content of oxygen of C ⁇ O in the coating layer is 7 atom% to 39 atom% in the total oxygen amount of the coating layer A battery is provided.
  • the lithium ion battery according to the first or second aspect wherein the low crystalline carbon of the coating layer is amorphous carbon.
  • the ratio of C—OH and C ⁇ O in the coating layer is an atomic composition ratio of oxygen in each functional group. Lithium ion batteries in a 1: 1 to 4: 1 range are provided. The ratio of C—OH and C ⁇ O is preferably 1: 1 to 2: 1 as an oxygen atom composition ratio in each functional group.
  • the (002) plane distance d002 obtained by the X-ray diffraction method of the negative electrode active material is 0.3354 nm to 0.3370 nm
  • the crystallite A lithium ion battery having a size Lc of 20 nm to 90 nm is provided.
  • a lithium ion battery having a coating layer thickness of 10 nm to 100 nm is provided.
  • the lithium ion intensity ratio (I 1360 / I 1580 ) of the negative electrode active material is 0.1 to 0.7.
  • a battery is provided.
  • the irreversible capacity per mass of the negative electrode active material is 20 mAh / g to 31 mAh / g, and the discharge of the negative electrode active material A lithium ion battery having a capacity density of 350 mA / g to 365 mA / g is provided.
  • the lithium ion battery according to any one of the first to eighth aspects, wherein the graphite core material is graphite particles subjected to isotropic pressure treatment.
  • the coating layer is formed of the graphite by the low crystalline carbon by thermal decomposition of an organic compound or a mixture thereof in a non-oxidizing atmosphere.
  • a lithium ion battery that is a carbon film formed on the surface of a core material is provided.
  • the coating layer is a lithium film that is a carbon film obtained by thermally decomposing the organic compound or a mixture thereof and the graphite core material under contact conditions. An ion battery is provided.
  • the lithium ion battery according to the tenth or eleventh aspect wherein the organic compound is an organic polymer compound that is carbonized in a liquid phase.
  • the organic compound is an organic resin that is carbonized in a solid phase.
  • the content of the low crystalline carbon in the composite carbon particles is the total mass of the graphite core material and the low crystalline carbon. Lithium ion batteries that are 0.1% to 20% by weight are provided.
  • the lithium ion battery according to any one of the first to fourteenth aspects, wherein the positive electrode includes a positive electrode active material, a conductive additive, a positive electrode binder, and a current collector.
  • the positive electrode includes a positive electrode active material, a conductive additive, a positive electrode binder, and a current collector, and the positive electrode active material is LiCoO.
  • the positive electrode includes a positive electrode active material, a conductive additive, a positive electrode binder, and a current collector, and the positive electrode active material is LiNi 1/1 / A lithium ion battery that is 3 Mn 1/3 Co 1/3 O 2 is provided.
  • a battery module in which two or more lithium ion batteries according to any one of the first to seventeenth aspects are connected in series, parallel or series-parallel.
  • the mobile body or stationary power storage system in which the battery module according to the eighteenth aspect is connected to a charge / discharge circuit connectable to an external device via an external terminal.
  • the present invention it is possible to provide a lithium ion battery with improved cycle life and high-temperature storage characteristics, and a battery module, moving body or stationary power storage system using the lithium ion battery.
  • FIG. 1 shows one embodiment of a cross-sectional structure of a lithium ion battery to which the present invention is applied. It is a graph which shows the differential thermothermal weight simultaneous measurement (TG-DTA) result of the negative electrode active material concerning Example 4 of this invention. It is a graph which shows the differential thermothermal weight simultaneous measurement (TG-DTA) result of the negative electrode active material concerning Example 3 of this invention. It is a plane schematic diagram showing a module of a lithium ion battery to which the present invention is applied.
  • composite carbon particles in which the surface of graphite particles (graphite core material) is coated with a coating layer of low crystalline carbon are included, and the oxygen concentration in the coating layer is set to a specific range. Accordingly, in the thermogravimetric method, at least one oxidation peak (peak of temperature differential value of weight change) in a low temperature region of 350 ° C. or more and less than 600 ° C., and at least one oxidation in a high temperature region of 600 ° C. or more and 850 ° C. or less. Peak temperature difference between an oxidation peak having a peak (a peak of a temperature differential value of weight change) and having a peak at the highest temperature within a range of 350 ° C. to 850 ° C.
  • a lithium ion battery including a negative electrode including composite carbon particles having a temperature of 300 ° C. or less as a negative electrode active material, a positive electrode, a nonaqueous electrolyte, and a nonaqueous solvent.
  • the lithium ion battery of the present invention is a battery excellent in high-temperature storage characteristics and cycle characteristics.
  • the composite carbon particles in the present invention are those in which a graphite core material is coated with a coating layer of low crystalline carbon and constitute a negative electrode active material.
  • Low crystalline carbon includes amorphous or mesomorphic carbon (carbon with very low crystallinity and substantially no crystal peak is observed by X-ray diffraction).
  • This low crystalline carbon coating can be obtained by various methods, and an organic substance that can be thermally decomposed in a liquid phase is heated in a non-oxidizing atmosphere to be deposited on the graphite core material.
  • the graphite core material is preferably graphite particles subjected to isotropic pressure treatment.
  • the low crystalline carbon coating layer may be a low crystalline carbon film formed on the surface of the graphite core material by thermal decomposition of an organic compound or a mixture thereof in a non-oxidizing atmosphere.
  • the organic compound or a mixture thereof may be one that thermally decomposes under contact with the graphite core material, an organic polymer compound that carbonizes in the liquid phase, or an organic resin that carbonizes in the solid phase.
  • the coating layer is preferably 0.1% by mass to 20% by mass of the total mass of the graphite core material and the low crystalline carbon.
  • the present invention provides a battery module in which at least two lithium ion batteries are connected in series, in parallel or in series and parallel, and a moving body in which the battery module is connected to a charging circuit that can be connected to an external device via an external terminal. Alternatively, it can be applied to a stationary power storage system, and these will be specifically described later.
  • FIG. 1 schematically shows an internal structure of a cylindrical lithium ion battery 101 according to an embodiment of the present invention.
  • 110, positive electrode, 111, separator, 112, negative electrode, 113, battery can, 114, positive current collecting tab, 115, negative current collecting tab, 116, inner lid, 117, internal pressure release valve, 118, gasket, 119, positive temperature
  • a coefficient (PTC; Positive temperature coefficient) resistance element 120 is a battery lid.
  • the battery lid 120 is an integrated part including an inner lid 116, an internal pressure release valve 117, a gasket 118, and a PTC resistance element 119.
  • the positive electrode 110 includes a positive electrode active material, a conductive additive, a positive electrode binder, and a current collector.
  • the positive electrode active material include LiCoO 2 , LiNiO 2 , and LiMn 2 O 4 as representative examples.
  • LiNi 1/3 Mn 1/3 Co 1/3 O 2 was selected as the positive electrode active material because high energy density and excellent cycle life could be realized.
  • the present invention is not limited to the positive electrode material, and is not limited to these materials.
  • the particle size of the positive electrode active material is specified to be equal to or less than the thickness of the mixture layer including the positive electrode active material, the conductive auxiliary, and the positive electrode binder.
  • the coarse particles are removed in advance by sieving classification, wind classification or the like to produce particles having a thickness of the mixture layer or less.
  • the positive electrode active material is oxide-based and has high electric resistance
  • a conductive additive made of carbon powder is used to supplement the electric conductivity.
  • the conductive assistant carbon materials such as acetylene black, carbon black, graphite, and amorphous carbon, or a combination of two or more thereof can be used.
  • the particle size of the conductive auxiliary agent is preferably smaller than the average particle size of the positive electrode active material and 1/10 or less of the average particle size.
  • both the positive electrode active material and the conductive additive are powders
  • a positive electrode binder is mixed with the powders, and the powders are bonded together and simultaneously bonded to the current collector.
  • an aluminum foil having a thickness of 10 ⁇ m to 100 ⁇ m, or an aluminum perforated foil having a thickness of 10 ⁇ m to 100 ⁇ m and a diameter of 0.11 mm to 10 mm, an expanded metal, or a foam metal plate is used.
  • stainless steel and titanium are also applicable.
  • any current collector can be used without being limited by the material, shape, manufacturing method and the like.
  • the composition is exemplified by 89 parts by mass of the positive electrode active material, 4 parts by mass of acetylene black, and 7 parts by mass of the positive electrode binder of PVDF (polyvinylidene fluoride). Accordingly, the composition is not limited to the exemplified composition.
  • the positive electrode slurry may be any solvent that dissolves the positive electrode binder, and N-methyl-2-pyrrolidone is frequently used for the positive electrode binder of PVDF. However, the solvent is appropriately selected according to the type of the positive electrode binder. A known kneader or disperser was used for the dispersion treatment of the positive electrode material.
  • a positive electrode slurry in which a positive electrode active material, a conductive additive, a positive electrode binder, and a solvent are mixed and dispersed is attached to a current collector by a doctor blade method, a dipping method, a spray method, and the like. Is formed on the current collector to form a mixture layer containing a positive electrode active material, a conductive additive and a positive electrode binder, and the positive electrode can be produced by the above process. Moreover, it is also possible to laminate
  • the negative electrode 112 includes a negative electrode active material, a negative electrode binder, and a current collector.
  • the negative electrode active material has a core-shell structure in which a coating layer is formed on the surface of a graphite core material (graphite particles).
  • the negative electrode active material is a negative electrode active material capable of occluding and releasing lithium, wherein the negative electrode active material is a composite carbon particle having a low crystalline carbon coating layer on the surface of a graphite core material, It has a functional group of C ⁇ O, C—OH and C—O on the surface, and the content of oxygen atoms in the total amount of carbon atoms and oxygen atoms in the coating layer is 2 atom% to 5 atom%.
  • At least one oxidation peak is present in each temperature range of 350 ° C. or more and less than 600 ° C. and 600 ° C. or more and 850 ° C. or less, and the peak is the highest temperature in the range of 350 ° C. or more and 850 ° C. or less.
  • the negative electrode active material having a peak temperature difference of 300 ° C. or less between an oxidation peak having a peak and an oxidation peak having a peak at the lowest temperature is used.
  • a lithium ion battery was manufactured for each negative electrode active material by using the negative electrode active material manufactured in each Example described later.
  • the composition include 95 parts by mass of the negative electrode active material and 5 parts by mass of the negative electrode binder of PVDF (polyvinylidene fluoride), which are changed according to the type of material, specific surface area, particle size distribution, and the like.
  • the composition is not limited.
  • the solvent for the negative electrode slurry may be any solvent that dissolves the negative electrode binder, and N-methyl-2-pyrrolidone is frequently used as the negative electrode binder for PVDF. However, the solvent is appropriately selected according to the type of the negative electrode binder. A known kneader or disperser was used for the dispersion treatment of the negative electrode material.
  • a negative electrode slurry in which a negative electrode active material, a negative electrode binder, and a solvent are mixed and dispersed is attached to a current collector by a doctor blade method, a dipping method, a spray method, etc., then the solvent is dried, and the negative electrode is pressure-formed by a roll press.
  • a mixture layer containing a negative electrode active material, a conductive additive and a negative electrode binder is formed on the current collector, and a negative electrode can be produced by the above process.
  • a separator 111 is inserted between the positive electrode 110 and the negative electrode 112 to prevent a short circuit between the positive electrode 110 and the negative electrode 112.
  • the separator 111 is made of a polyolefin polymer film made of polyethylene, polypropylene, or the like, or a microporous film having a multilayer structure in which a polyolefin polymer and a fluorine polymer film typified by tetrafluoropolyethylene are welded. It is possible.
  • separators 111 need to allow lithium ions to permeate during charge / discharge of the battery, it is generally desirable that the separators 111 have pores having a pore diameter of 0.01 ⁇ m to 10 ⁇ m and a porosity of 20% to 90%. Further, a mixture of ceramics and an organic resin binder may be formed in a thin layer on the surface of the separator 111 so that the separator 111 does not shrink when the battery temperature becomes high.
  • an integrated structure including the positive electrode 110, the negative electrode 112, and the separator 111 is referred to as an electrode group.
  • the separator 111 is also inserted between the electrode disposed at the end of the electrode group and the battery can 113 so that the positive electrode 110 and the negative electrode 112 do not short-circuit through the battery can 113. Moreover, the electrolyte solution which consists of electrolyte and a nonaqueous solvent is hold
  • the upper part of the electrode group is electrically connected to an external terminal via a lead wire.
  • the positive electrode 110 is connected to the battery lid 120 via the positive electrode current collecting tab 114.
  • the negative electrode 112 is connected to the battery can 113 via the negative electrode current collecting tab 115.
  • the positive electrode current collection tab 114 and the negative electrode current collection tab 115 can take arbitrary shapes, such as wire shape and plate shape.
  • the shape and material of the positive electrode current collector tab 114 and the negative electrode current collector tab 115 are arbitrary as long as the material has a structure that can reduce ohmic loss when a current is applied and does not react with the electrolytic solution.
  • the structure of the electrode group is the wound shape shown in FIG. 1, but it can be formed in any shape according to the shape of the battery can 113. If the battery can 113 is rectangular, the shape can be changed to a shape in which the positive electrode 110, the negative electrode 112, and the separator 111 are laminated, or a flat shape.
  • the material of the battery can 113 is selected from materials that are corrosion resistant to the non-aqueous electrolyte, such as aluminum, stainless steel, and nickel-plated steel. Further, when the positive electrode current collecting tab 114 or the negative electrode current collecting tab 115 is electrically connected to the battery can 113, the battery can 113 is corroded or alloyed with lithium ions in a portion in contact with the nonaqueous electrolyte. Select the material of the tab so that the material does not deteriorate due to.
  • the battery lid 120 is brought into close contact with the battery can 113, and the whole battery is sealed.
  • a caulking method is employed.
  • there are known techniques such as welding and welding for sealing the battery.
  • lithium hexafluorophosphate as an electrolyte in a solvent in which ethylene carbonate is mixed with dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, or a combination of two or more thereof.
  • the present invention is not limited to the type of solvent and electrolyte, and the mixing ratio of solvents, and other electrolytes can be used.
  • the electrolyte can also be used in a state of being contained in an ion conductive polymer such as polyvinylidene fluoride and polyethylene oxide. In this case, the separator becomes unnecessary.
  • Solvents that can be used for the electrolyte include propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, ⁇ -butyrolactone, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, 1,2-dimethoxyethane, 2-methyltetrahydrofuran, dimethyl Sulfoxide, 1,3-dioxolane, formamide, dimethylformamide, methyl propionate, ethyl propionate, phosphoric acid triester, trimethoxymethane, dioxolane, diethyl ether, sulfolane, 3-methyl-2-oxazolidinone, tetrahydrofuran, 1 , 2-diethoxyethane, chloroethylene carbonate, and chloropropylene carbonate. These can be used alone or in combination of two or more. Other solvents may be used as long as they do not decompose on the positive electrode or the negative electrode incorporated in the battery of the
  • the electrolyte LiPF 6, LiBF 4, LiClO 4, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6 or a variety of imide lithium salts represented by lithium trifluoromethane sulfonimide, There is a lithium salt.
  • a lithium salt can be used alone or in combination of two or more.
  • a non-aqueous electrolytic solution obtained by dissolving these salts in the above-described solvent can be used as a battery electrolytic solution.
  • Other electrolytes may be used as long as they do not decompose on the positive electrode or the negative electrode incorporated in the battery of this example.
  • a solid polymer electrolyte polymer electrolyte
  • an ion conductive polymer obtained by polymerizing monomers such as ethylene oxide, acrylonitrile, vinylidene fluoride, methyl methacrylate, hexafluoropropylene and the like can be used as the electrolyte. These can be used alone or in combination of two or more.
  • these solid polymer electrolytes there is an advantage that the separator 111 can be omitted.
  • an ionic liquid can be used.
  • EMI-BF 4 1-ethyl-3-methylimidazolium tetrafluoroborate
  • LiTFSI lithium salt LiN (SO 2 CF 3 ) 2
  • triglyme and tetraglyme LiN (SO 2 CF 3 ) 2
  • a cyclic quaternary ammonium-based cation A combination of N-methyl-N-propylpyrrolidinium) and an imide-based anion (such as bis (trifluoromethylsulfimide)), which does not decompose on the positive electrode or the negative electrode.
  • imide-based anion such as bis (trifluoromethylsulfimide)
  • the battery lid 120 is removed from the battery can 113 and added directly to the electrode group.
  • the battery lid 120 has a liquid inlet
  • a solid polymer electrolyte (polymer electrolyte) or a gel electrolyte can be used.
  • a known polymer electrolyte such as polyethylene oxide or a mixture (gel electrolyte) of polyvinylidene fluoride and a nonaqueous electrolytic solution can be used.
  • an ionic liquid may be used.
  • Example 2 The present embodiment is the same as the first embodiment except for the items specifically described below.
  • ⁇ Preparation of graphite core material> As the graphite core material used in Example 2, artificial graphite produced by isotropic pressure treatment was used, but the present invention is not limited to this material.
  • the isotropic pressurization process is not a pressurization only from a specific direction (anisotropic pressurization process) but a generally known process of pressurization from all directions.
  • the bulk density of the obtained composite carbon particles for a lithium ion battery negative electrode and the fluidity of the negative electrode slurry are improved, and the density variation of the produced lithium ion battery negative electrode And the adhesion to the negative electrode current collector is improved.
  • the cycle characteristics of the obtained lithium ion battery can be improved.
  • the method of isotropic pressure treatment of carbon powder is not particularly limited as long as it is an isotropic pressure method.
  • carbon powder is placed in a rubber mold or the like and water is used as a pressure medium.
  • the pressure treatment include a water pressure isotropic press and a pneumatic isotropic press using a gas such as air as a pressure medium.
  • the pressure of the pressure medium in the isotropic pressure treatment of the carbon powder is preferably in the range of 4.9 ⁇ 10 6 Pa to 1.96 ⁇ 10 8 Pa (50 kgf / cm 2 to 2000 kgf / cm 2 ). It is more preferable that it is in the range of .96 ⁇ 10 7 Pa to 1.96 ⁇ 10 8 Pa (200 kgf / cm 2 to 2000 kgf / cm 2 ), and 4.9 ⁇ 10 7 Pa to 1.77 ⁇ 10 8 Pa (500 kgf). / Cm 2 to 1800 kgf / cm 2 ) is more preferable. If the pressure is 4.9 ⁇ 10 6 Pa (50 kgf / cm 2 ) or more, the effect of improving the cycle characteristics of the obtained lithium ion battery tends to increase.
  • the particles are likely to aggregate. Therefore, after the isotropic pressure treatment, it is preferable to perform a treatment such as crushing and sieving. In addition, when the particles do not aggregate, it is not necessary to crush.
  • the composite carbon particles (negative electrode active material) for a lithium ion battery negative electrode produced by performing isotropic pressure treatment have a crystal interlayer distance.
  • d (002) is in the range of 0.3354 nm to 0.3370 nm
  • the crystallite size Lc (002) in the C-axis direction can be in the range of 20 nm to 90 nm.
  • Crystal interlayer distance d (002) and crystallite size Lc in the C-axis direction were determined by X-ray diffraction. The X-ray diffraction method is measured according to the Gakushin method.
  • the carbon material to be subjected to the above isotropic pressure treatment is not particularly limited. Natural graphite, artificial graphite obtained by graphitizing coke, organic polymer material, artificial graphite obtained by graphitizing pitch, etc., amorphous Examples thereof include carbon, low-temperature treated carbon, etc. Among them, artificial graphite is preferable.
  • Artificial graphite is composed of main materials that can be graphitized, such as coke powder and resin carbide, and pitch, tar, and organic materials such as thermosetting resins and thermoplastic resins.
  • graphite powder and a catalyst for promoting the graphitization reaction are added in part, and the raw material mixture is graphitized and fired at a temperature of 2500 ° C. or higher.
  • Artificial graphite can be produced through the pulverization process of the obtained graphite fired body. The crystallinity of the artificial graphite obtained by the above method is easily developed, and the discharge capacity of the obtained lithium ion battery can be improved.
  • the graphitization catalyst is preferably a metal such as Ti, Si, Fe, Ni, or B, or an oxide or carbide thereof.
  • the graphitization catalyst is preferably added when the main raw material and the organic material are mixed, and mixed at the same time.
  • the mixing temperature is preferably a temperature at which the organic material is softened and melted. The temperature varies depending on the material used, but is preferably in the range of 50 ° C. to 350 ° C.
  • the raw material mixture may be pulverized and molded before graphitization at a temperature of 2500 ° C. or higher, and further pre-fired at a temperature of about 700 ° C. to 1300 ° C. Further, the order of the process may be changed, and after preliminary firing at a temperature of about 700 ° C. to 1300 ° C., the pulverized powder whose particle size has been adjusted may be graphitized and fired at a temperature of 2500 ° C. or higher.
  • the firing temperature during graphitization is preferably 2500 ° C. or higher, more preferably 2800 ° C. or higher, and even more preferably 3000 ° C.
  • the atmosphere during firing is not particularly limited as long as it is difficult to oxidize, and examples thereof include a self-volatile gas atmosphere, a nitrogen atmosphere, an argon atmosphere, and a vacuum.
  • an organic material such as an aromatic organic molecule, coal tar or pitch is once melted in the process of raising the temperature, and volatile components are desorbed and condensed and carbonized.
  • the method for pulverizing the graphitized fired body is not particularly limited, and for example, an impact pulverization method such as a jet mill, a hammer mill, or a pin mill can be employed.
  • an impact pulverization method such as a jet mill, a hammer mill, or a pin mill can be employed.
  • the particle size is adjusted to obtain graphite particles. If the particle size is adjusted by pulverization before graphitization, it is not necessary to pulverize after graphitization.
  • graphite particles of artificial graphite produced as described above isotropic pressure treatment was performed to obtain a graphite core material. Furthermore, it can be set as the composite carbon particle for lithium ion battery negative electrodes suitable for the lithium ion battery excellent in cycling characteristics and rapid charge / discharge characteristics by coat
  • a process for coating the low crystalline carbon for example, a process of applying an ultrasonic wave to a specific organic solvent in which a graphite core material is dispersed may be mentioned.
  • an organic solvent is carbonized and deposited by applying traveling wave type ultrasonic waves. Precipitation occurs on the surface of the dispersed graphite core material, so that a carbonaceous layer free from adsorption of unnecessary functional groups or the like can be formed on the surface of the graphite core material.
  • the specific organic solvent include o-dichlorobenzene, and o-dichlorobenzene was used in this example.
  • heat treatment is performed to fix the deposited carbonaceous layer to the surface of the graphite core material by pyrolysis and form a coating layer of low crystalline carbon.
  • the heat treatment temperature varies depending on the starting material, it is preferably in the range of 400 ° C. to 800 ° C., particularly preferably in the range of 550 ° C. to 750 ° C.
  • the gas atmosphere during the heat treatment is most preferably an inert gas atmosphere made of nitrogen or a rare gas. In this example, the treatment was performed in a state where nitrogen gas was circulated. By doing in this way, combustion of a coating layer and a graphite core material can be prevented.
  • the coating layer is formed in a non-oxidizing atmosphere in which a trace amount of oxygen of 10% or less is mixed with an inert gas.
  • the oxygen concentration can be adjusted.
  • the coating layer may be formed using another organic polymer compound as a starting material of low crystalline carbon.
  • the organic polymer compound include organic polymer compounds that are carbonized in a liquid phase, such as various pitches (crude oil pitch, naphtha pitch, asphalt pitch, coal tar pitch, cracked pitch, and the like).
  • pitches such as various pitches (crude oil pitch, naphtha pitch, asphalt pitch, coal tar pitch, cracked pitch, and the like).
  • a coating layer of low crystalline carbon is formed on the surface of the graphite core material by thermal decomposition.
  • Resins that carbonize in the solid phase can also be used.
  • the amount of the low crystalline carbon covering the surface of the graphite core material is preferably 0.1% by mass or more based on the mass of the composite carbon particles finally obtained, and the effect of the coating and the charge / discharge capacity In view of this balance, it is more preferably 0.1% by mass to 20% by mass, and further preferably 1% by mass to 15% by mass with respect to the mass of the composite carbon particles.
  • the thickness of the coating layer made of low crystalline carbon can be controlled to 10 nm to 100 nm.
  • the content of low crystalline carbon in the composite carbon particles can be determined from the value of the weight change corresponding to the low crystalline carbon in the weight change measurement by thermogravimetric analysis.
  • artificial graphite produced by isotropic pressure treatment was used as a graphite core material, and the thickness of the coating layer was set to 10 nm to 100 nm using o-dichlorobenzene.
  • the heat treatment temperature for forming the coating layer was set to 550 ° C., and composite carbon particles were obtained by performing the treatment in a nitrogen gas atmosphere.
  • the thickness of the coating layer was measured with a transmission electron microscope (TEM) after cutting the cross section of the negative electrode active material with a focused ion beam processing apparatus (FIB). Although the thickness of the coating layer varies depending on the measurement location, it is presumed that if at least the thickness of the coating layer is 10 nm or more, the electrolyte solution is suppressed from passing through a minute gap in the coating layer. This prevents the electrolyte from coming into direct contact with the edge surface of the highly active graphite core material, which reduces the decomposition reaction of the electrolyte during high-temperature storage and charge / discharge cycles, and is thought to improve battery characteristics. . Moreover, if the thickness of the coating layer is 100 nm or less, it is desirable that the migration resistance of the coating layer portion of lithium ions accompanying the charge / discharge reaction is small.
  • TEM transmission electron microscope
  • FIB focused ion beam processing apparatus
  • Example 3 The present embodiment is the same as the first embodiment except for the items specifically described below.
  • artificial graphite is produced by adding coke powder as a main raw material that can be graphitized, petroleum pitch as an organic material that can be graphitized for binding the coke powder, and an iron-based graphitization catalyst. did.
  • a graphitization catalyst with 1% by mass to 50% by mass added is mixed, calcined and graphitized, and then pulverized to produce graphite.
  • the present invention is not limited to the above materials.
  • various cokes such as fluid coke and needle coke can be used.
  • the main raw material that can be graphitized preferably contains coke powder, and more preferably contains needle coke powder, in view of charge / discharge capacity and rapid charge / discharge characteristics.
  • a carbon material that has already been graphitized such as natural graphite or artificial graphite may be added to a part of the main raw material.
  • Various pitches and tars such as coal-based, petroleum-based, and artificial can be used as the graphitizable organic material for binding the main raw material to form a graphite molded body.
  • As the graphitization catalyst iron, nickel, titanium, boron, silicon and the like, oxides, carbides, nitrides and the like thereof can be used.
  • the aspect ratio of the resulting graphite particles can be reduced, and a plurality of flat particles can be assembled or It becomes possible to produce bonded graphite particles.
  • the rapid charge / discharge characteristics and cycle characteristics of the lithium ion battery to be manufactured can be improved.
  • organic materials such as thermosetting resins and thermoplastic resins can also be used as the graphitizable organic materials.
  • the amount of the organic material that can be graphitized varies depending on the residual carbon ratio and binding force of the organic material to be used. For example, when pitch is used, Mass parts to 100 parts by mass are preferable, 10 parts by mass to 70 parts by mass are more preferable, and 10 parts by mass to 50 parts by mass are even more preferable.
  • the blending ratio of the graphitization catalyst can be selected according to the particle characteristics of the target graphite particles (graphite core material), and the main raw materials such as coke, organic materials such as pitch and the graphitization catalyst are combined. It is preferable to add 1% by mass to 50% by mass of the graphitization catalyst with respect to the total mass of the raw material mixture.
  • the blending ratio of the graphitization catalyst is selected according to the particle characteristics of the target graphite particles (graphite core material). With respect to the graphitization catalyst, if the addition amount is 1% by mass or more, the development of the graphite particle crystals is improved, the charge / discharge capacity is improved, and the discharge capacity of the resulting lithium ion battery can be increased. it can.
  • the amount of the graphitization catalyst when the amount of the graphitization catalyst is 50% by mass or less, it becomes easy to mix uniformly, and it is possible to avoid deterioration of workability and increase in variation in characteristics of the obtained graphite particles.
  • the addition amount of the graphitization catalyst is more preferably 10% by mass or less, further preferably 5% by mass or less, and further preferably 1% by mass to 5% by mass.
  • metals such as Ti, Si, Fe, Ni, and B, or oxides or carbides thereof are preferable, and are preferably added at the time of mixing the main raw material and the organic material and mixed at the same time.
  • the temperature at which the graphitization catalyst is mixed is preferably a temperature at which the graphitizable organic material is softened and melted.
  • the temperature varies depending on the material used, but is preferably in the range of 50 ° C to 350 ° C. Further, when a graphitizable organic material is made into a solution with a solvent or the like, it may be mixed at room temperature.
  • the raw material mixture obtained by mixing the main material that can be graphitized, the organic material that can be graphitized, and the graphitization catalyst is pre-fired at 500 ° C. to 2000 ° C., and the fired product is pulverized to obtain an average particle size of 10 ⁇ m to It is preferable to adjust to 100 ⁇ m and further graphitize the pulverized product at a temperature of 2500 ° C. or higher.
  • the pre-baking temperature before pulverization is preferably 500 ° C. to 1500 ° C., more preferably 700 ° C. to 1500 ° C. If the pre-calcination temperature before pulverization is 2000 ° C. or less, the resulting graphite particles (graphite core material) tend to have a high bulk density, a small specific surface area, and a small aspect ratio. In addition, if the pre-calcination temperature before pulverization is 500 ° C. or higher, the carbonization of the added graphitizable organic material is sufficient, and as a result, there is a tendency that the bonding between particles can be suppressed after pulverization / graphitization. .
  • the raw material mixture may be formed into an appropriate shape as necessary.
  • Pre-baking is preferably performed in an atmosphere in which the raw material mixture is difficult to oxidize, and examples thereof include a method of baking in a nitrogen atmosphere, argon gas, and vacuum.
  • the graphitization method is not particularly limited.
  • the crystallinity and discharge capacity of graphitized particles obtained at a temperature of 2500 ° C. or higher in a self-volatile gas atmosphere, nitrogen atmosphere, argon atmosphere, vacuum, etc. is preferable.
  • the graphitization temperature is more preferably 2700 ° C or higher, further preferably 2900 ° C, particularly preferably 3000 ° C or higher.
  • the upper limit of the graphitization temperature is preferably 3200 ° C. or lower. The higher the graphitization temperature, the better the development of graphite crystals, and the more difficult it remains on the graphite particles produced by the graphitization catalyst. In either case, the charge / discharge capacity tends to be improved.
  • pulverization is performed.
  • the pulverization method There is no particular limitation on the pulverization method, and for example, an impact pulverization method such as a jet mill, a hammer mill, or a pin mill can be adopted.
  • the graphite particles (graphite core material) obtained as described above are coated with low crystalline carbon as follows.
  • the type of organic polymer compound that is the starting material for the low crystalline carbon that coats the graphite core material and the amount of low crystalline carbon that is obtained by carbonizing this.
  • the organic polymer compound include organic polymer compounds that are carbonized in a liquid phase, such as various pitches (crude oil pitch, naphtha pitch, asphalt pitch, coal tar pitch, cracked pitch, and the like).
  • phenol resin, furfuryl alcohol resin, cellulose resin, polyacrylonitrile, and vinyl halide resins such as polyvinyl chloride, polyvinylidene chloride, chlorinated polyvinyl chloride, and the like can be given.
  • the amount of the low crystalline carbon covering the surface of the graphite core material is preferably 0.1% by mass or more based on the mass of the composite carbon particles finally obtained, and the effect of the coating and the charge / discharge capacity In view of this balance, the content is more preferably 0.1% by mass to 20% by mass, and further preferably 1% by mass to 15% by mass.
  • the thickness of the coating layer made of low crystalline carbon can be controlled to 10 nm to 100 nm.
  • Example 3 the thickness of the coating layer was 10 nm to 100 nm using carboxymethylcellulose resin, and the heat treatment temperature when forming the coating layer was 750 ° C.
  • the gas atmosphere was nitrogen gas.
  • the thickness of the coating layer was measured by TEM after cutting a cross section of the negative electrode active material with FIB. Although the thickness of the coating layer varies depending on the measurement location, it is presumed that if at least the thickness of the coating layer is 10 nm or more, the electrolyte solution is suppressed from passing through a minute gap in the coating layer. This prevents the electrolyte from coming into direct contact with the edge surface of the highly active graphite core material, which reduces the decomposition reaction of the electrolyte during high-temperature storage and charge / discharge cycles, and is thought to improve battery characteristics. . Moreover, if the thickness of the coating layer is 100 nm or less, it is desirable that the migration resistance of the coating layer portion of lithium ions accompanying the charge / discharge reaction is small.
  • Example 4 The present embodiment is the same as the first embodiment except for the items specifically described below.
  • the graphite core material used in Example 4 is a carbon material having a graphene structure. That is, natural graphite, artificial graphite, mesophase carbon, expanded graphite, carbon fiber, vapor grown carbon fiber, pitch-based carbonaceous material, needle coke, petroleum coke that can occlude and release lithium ions electrochemically, Uses carbonaceous materials such as polyacrylonitrile-based carbon fiber and carbon black, or amorphous carbon materials synthesized by thermal decomposition of 5-membered or 6-membered cyclic hydrocarbons or cyclic oxygen-containing organic compounds. Is possible.
  • the graphite core material was produced as follows. 50 parts by mass of coke powder having an average particle diameter of 5 ⁇ m, 20 parts by mass of tar pitch, 7 parts by mass of silicon carbide having an average particle diameter of 48 ⁇ m, and 10 parts by mass of coal tar were mixed and mixed at 200 ° C. for 1 hour. The obtained mixture was pulverized, pressure-molded into pellets, and then fired at 3000 ° C. in a nitrogen atmosphere. The obtained fired product was pulverized by a hammer mill to produce graphite particles (graphite core material) having an average particle size of 20 ⁇ m.
  • the coke powder used here is not limited to the above conditions, and a material of 1 ⁇ m to several tens of ⁇ m can be selected.
  • the composition of the coke powder and the tar pitch can be changed as appropriate.
  • Other conditions such as the heat treatment temperature are not limited to those described above.
  • a coating layer of low crystalline carbon can be formed on the graphite core material produced in Example 4 by the following procedure. First, 100 parts by mass of the graphite particles (graphite core material) obtained above are immersed and dispersed in 160 parts by mass of a novolak type phenol resin methanol solution (manufactured by Hitachi Chemical Co., Ltd.) to prepare a graphite particle / phenol resin mixture solution. did. This solution was filtered, dried, and heat-treated at a temperature in the range of 800 ° C. to 1000 ° C. to obtain composite carbon particles in which a coating layer of low crystalline carbon was formed on the surface of the graphite core material.
  • a novolak type phenol resin methanol solution manufactured by Hitachi Chemical Co., Ltd.
  • the gas atmosphere was a mixed gas atmosphere (non-oxidizing atmosphere) in which 0.5% to 1% oxygen was added to nitrogen gas.
  • phenol resin it can be replaced with polycyclic aromatics such as naphthalene, anthracene and creosote oil.
  • the specific surface area by the BET method of the composite carbon particles described above was 3.6 m 2 / g.
  • the interlayer distance d002 of the graphite crystal by X-ray wide angle diffraction method was 0.3354 nm to 0.3370 nm, and the crystallite size Lc was in the range of 20 nm to 90 nm.
  • the intensity ratio (I 1360 / I 1580 ) of the Raman peaks at the positions of 1580 cm ⁇ 1 and 1360 cm ⁇ 1 was in the range of 0.1 to 0.7.
  • the heat treatment temperature is desirably in the range of 500 ° C to 800 ° C.
  • particles such as polyvinyl chloride and polyvinyl pyrrolidone can be directly added and heat-treated. These compounds are mixed with graphite particles (graphite core material) and then heated to a temperature at which they are thermally decomposed to form a coating layer.
  • surface modification such as oxidation treatment using ozone or the like, plasma treatment, or ultraviolet (UV) treatment is performed.
  • oxidation treatment using ozone or the like
  • plasma treatment or ultraviolet (UV) treatment
  • UV treatment ultraviolet treatment
  • the coating material is thermally decomposed, a small amount of oxygen of 10% or less can be added to the inert gas, and surface modification can be performed using the mixed gas.
  • a coating layer of low crystalline carbon was formed on the surface of the graphite core material, a cross section of the powder was cut out by FIB, and the thickness of the carbon layer was measured by TEM. As a result, although there was variation, the thickness of the low crystalline carbon coating layer was in the range of 10 nm to 100 nm. If the thickness of the coating layer is 10 nm or more, it is presumed that the electrolyte solution is suppressed from passing through a minute gap in the coating layer.
  • the coating layer is 100 nm or less, it is desirable that the migration resistance of the coating layer portion of lithium ions accompanying the charge / discharge reaction is small.
  • Example 5 The surface of the negative electrode active material (composite carbon particles) of Example 3 described above was treated with ozone to produce a negative electrode active material having an increased oxygen content.
  • the third embodiment is the same as the third embodiment.
  • Example 6 In the formation of the coating layer of Example 3 described above, the starting material of low crystalline carbon that coats the graphite core material was changed from carboxymethyl cellulose resin to crude oil pitch, and a negative electrode active material was produced. Other than that, the third embodiment is the same as the third embodiment.
  • Example 4 The negative electrode active material (composite carbon particles) produced in Example 4 was subjected to differential thermothermal gravimetric simultaneous measurement (TG-DTA) in air. It is known that the combustion behavior of carbon materials reflects crystallinity and specific surface area. By using this difference in combustion behavior, the oxidation peak of carbon derived from the coating layer and carbon derived from the graphite core material should be separated. Can do. Generally, a peak derived from highly crystalline graphite appears at around 900 ° C. (for example, FIG. 1 of JP-A-2001-229914), and it is known that the lower the crystal and the higher the specific surface area, the lower the temperature. ing.
  • TG-DTA differential thermothermal gravimetric simultaneous measurement
  • thermothermal gravimetric simultaneous measurement apparatus For the measurement, a differential thermothermal gravimetric simultaneous measurement apparatus was used. The measurement temperature range was from room temperature to 1100 ° C., the heating rate was 5 ° C./min, and the atmosphere was 80 mL / min in air. A 70 ⁇ l alumina cell was used for the measurement container, and the sample mass was 10 mg.
  • the results are shown in FIG.
  • the TG-DTA data in FIG. 2 is a measurement result of composite carbon particles corresponding to Example 4 in Table 1.
  • the change in processing weight (vertical axis on the left) is almost constant up to 350 ° C, but when the temperature reaches 350 ° C or higher, the weight begins to gradually decrease, and at about 700 ° C, the weight becomes zero (ie, it is completely oxidized). Burned.)
  • the temperature differential value (right vertical axis) of the weight change at this time showed two oxidation peaks in a low temperature region near 411 ° C. and a high temperature region of 678 ° C.
  • the former suggested an oxidation reaction of the coating layer, and the weight loss at that time was 10% by mass.
  • the coating layer of Example 4 Since the coating layer of Example 4 has an oxygen functional group on the surface, it is presumed that the coating layer is more easily oxidized at a lower temperature than general graphite. The latter is an oxidation reaction of the graphite core material.
  • the temperature differential value peak (right axis) of the weight change attributed to this oxidation reaction is 678 ° C., which is lower than the peak position of a general highly crystalline graphite material. It is considered that this is because the coating layer of Example 4 is highly reactive to oxygen and affects the oxidation reaction of the graphite core material inside covered with the coating layer of low crystalline carbon.
  • the oxidation peak temperature (678 ° C.) of the graphite core material is within 300 ° C. with respect to the oxidation peak temperature (411 ° C.) of the coating layer.
  • the content of the coating layer in the composite carbon particles corresponds to a weight reduction amount (10% by mass) associated with the oxidation reaction, and in this example, the content of low crystalline carbon in the composite carbon particles is 0.1. Another characteristic is that the content is 20% by mass to 20% by mass.
  • FIG. 3 shows the results of simultaneous differential thermothermal gravimetric measurement (TG-DTA) of the negative electrode active material (composite carbon particles) of Example 3 with the coating layer generation conditions changed.
  • the change in weight (left vertical axis) is almost constant up to 450 ° C, but when the temperature reaches 450 ° C or higher, the weight begins to gradually decrease, and at about 900 ° C, the weight becomes zero (ie, completely oxidized and burned).
  • the temperature differential value (right vertical axis) of the weight change at this time showed two oxidation peaks of a low temperature region of 599 ° C. and a high temperature region of 801 ° C.
  • the former suggested an oxidation reaction of the coating layer, and the weight loss at that time was 15% by mass. Since the coating layer of Example 3 has an oxygen functional group on the surface, it is presumed that it is more easily oxidized than Example 4.
  • the temperature differential temperature peak (right axis) attributed to the latter oxidation reaction (right axis) (801 ° C.) is lower than the oxidation peak temperature of a general highly crystalline graphite material. Same as 2.
  • the coating layer of Example 3 is highly reactive to oxygen and affects the oxidation reaction of the graphite core material inside the coating layer. That is, it is one of the features of this embodiment that the oxidation peak temperature (801 ° C.) of the graphite core material is within 300 ° C. with respect to the oxidation peak temperature (599 ° C.) of the coating layer.
  • the TG-DTA measurement data has at least one oxidation peak in each temperature range of at least 400 ° C. to 600 ° C. and 650 ° C. to 850 ° C., and each oxidation peak has a general high crystalline property. It is another feature of this embodiment that all appear on the low temperature side with respect to the temperature at which the oxidation peak seen in the graphite material appears. Further, the content of the coating layer in the composite carbon particles corresponds to a weight reduction amount (15% by mass) due to the oxidation reaction, and the content of low crystalline carbon in the composite carbon particles is 0.1% by mass to 20%. It is also one of the characteristics that it is mass%.
  • Example 2 In the result of simultaneous differential thermothermal gravimetric measurement (TG-DTA) of the negative electrode active material (composite carbon particles) in Example 2, the oxidation peak derived from the coating layer on the low temperature side of 540 ° C. to 560 ° C. An oxidation peak derived from the graphite core material was obtained on the high temperature side of 810 ° C. to 830 ° C. The weight loss due to the oxidation reaction of the coating layer was 1% by mass. From this, it can be seen that both the tendency of the two oxidation peaks of the negative electrode active material in Example 2 and the content of low crystalline carbon in the composite carbon material satisfy the above characteristics.
  • TG-DTA simultaneous differential thermothermal gravimetric measurement
  • Example 5 the negative electrode active material (composite carbon particles) in Example 5 was a material in which the surface of the negative electrode active material in Example 3 was treated with ozone to increase the oxygen content. It is.
  • TG-DTA simultaneous differential thermothermal gravimetric measurement
  • an oxidation peak derived from the coating layer was observed at 530 ° C. to 550 ° C.
  • an oxidation peak derived from the graphite core material was observed at 750 ° C. to 770 ° C. Each of them appeared, and the weight loss due to the oxidation reaction of the coating layer was 0.1% by mass.
  • Example 3 Compared with the measurement result obtained about the negative electrode active material in Example 3, it turns out that the peak temperature shifted to the low temperature side in all. This is presumably because the oxygen content of the coating layer in Example 5 was more easily oxidized due to the increase in oxygen content than in Example 3. It is considered that the reactivity with oxygen is higher and the oxidation reaction of carbon inside the coating layer is more likely to occur. Further, although the coating layer was reduced by the ozone treatment, it was shown that the content of low crystalline carbon in the composite carbon particles was 0.1% by mass to 20% by mass.
  • Example 6 In the result of simultaneous differential thermothermal weight measurement (TG-DTA) of the negative electrode active material (composite carbon particles) in Example 6, the oxidation peak derived from the coating layer on the low temperature side of 500 ° C. to 520 ° C. An oxidation peak derived from the graphite core material was obtained on the high temperature side of 760 ° C. to 780 ° C. The weight loss due to the oxidation reaction of the coating layer is 20% by mass, which satisfies the characteristics of the present invention.
  • TG-DTA simultaneous differential thermothermal weight measurement
  • the attribution of the chemical bonding state from the XPS spectrum of C1s was performed as follows.
  • the C—O or C—OH bond is at a peak position in the range of 286.3 ⁇ 0.3 eV
  • the C—H bond is at a peak position in the range of 285.1 ⁇ 0.3 eV
  • the C—C bond is 284.3.
  • Curve fitting of each spectrum was performed at the peak position in the range of ⁇ 0.3 eV, and the respective binding ratio (atom%) was calculated.
  • assignment of chemical bonding state from XPS of O1s was performed as follows.
  • the C—O bond is at the peak position in the range of 533.6 ⁇ 0.3 eV
  • the C—OH bond is at the peak position in the range of 532.3 ⁇ 0.3 eV
  • the C ⁇ O bond is 531.2 ⁇ 0.
  • Curve fitting of each spectrum was performed at a peak position in a range of .3 eV, and each bond ratio (atom%) was calculated.
  • the carbon concentration (atomic percentage) of the negative electrode active material surface (coating layer) of Example 2 is 97.9 atom%, and the oxygen concentration is 2.1 atom%.
  • carbon in the state of C—O or C—OH is contained in 4 atom% with respect to the total amount of carbon, and most of the carbon is in a C—C or C—H bonded state, of which The bonding state of C—C was 70 atom% to 80 atom% of the total carbon content. In the cases of Examples 3, 4, and 5, the carbon state was the same, and no significant difference was observed.
  • the carbon concentration (atomic percentage) of the negative electrode active material surface (coating layer) of Example 4 is 97.1 atom%, and the oxygen concentration is 2.9 atom%. Further, from the result of XPS analysis of O1s, it was found that C—OH and C—O are the main components on the surface of the negative electrode active material of Example 4 and that C ⁇ O in a high oxidation number state exists. It was.
  • the carbon concentration (atomic percentage) of the negative electrode active material surface (coating layer) of Example 5 is 95.7 atom%, and the oxygen concentration is 4.3 atom%.
  • C O, C—OH, and C—O were present in an equivalent amount.
  • C O in a high oxidation number state contained 36 atom% of the total oxygen amount.
  • the measurement error by this analysis is ⁇ 3%
  • the C ⁇ O amount is in the range of 33 atom% to 39 atom% of the total oxygen amount. Is done.
  • the carbon concentration (atomic percentage) of the negative electrode active material surface (coating layer) of Example 6 is 97.5 atom%, and the oxygen concentration is 2.5 atom%. Further, from the XPS analysis result of O1s, it was found that C—OH and C—O were the main components and that C ⁇ O in a high oxidation number state was present on the negative electrode active material surface of Example 6. It was.
  • the oxygen-containing carbon layer shown in Table 1 was formed on the surface of the graphite core material as a coating layer. It is estimated that this coating layer is in close contact with the graphite core material inside and has some influence on the characteristics of the oxidation reaction shown in FIGS.
  • the effects and effects are as follows.
  • the oxidation peak on the high temperature side shown in FIGS. 2 and 3 is due to the oxidation reaction of the graphite core material of the negative electrode active material (composite carbon particles) of the present invention.
  • the temperature of this oxidation reaction is shifted to a lower temperature side than the oxidation peak of conventional graphite alone (for example, the oxidation peak around 900 ° C. in FIG.
  • the oxygen atom content of the functional group in the coating layer is reduced to 2 atom% to 5 atom% oxygen in the total amount of carbon atoms and oxygen atoms of the coating layer.
  • the amount can be equivalent.
  • the oxygen amount of C ⁇ O attributed from the XPS spectrum of O1s is 7 atom% to 39 atom% with respect to the total oxygen amount of the coating layer. It is desirable.
  • Such a negative electrode active material has at least one oxidation peak in each temperature range of 350 ° C. or more and less than 600 ° C. and 600 ° C. or more and 850 ° C. or less in the simultaneous differential thermogravimetric measurement method in the atmosphere, The material is characterized in that the difference in peak temperature between the oxidation peak having the peak at the highest temperature and the oxidation peak having the peak at the lowest temperature in the range of 950 ° C. or more and 850 ° C. or less is 300 ° C. or less. It has been found that the use of a negative electrode active material satisfying such requirements for a lithium ion battery is effective in improving the storage characteristics and cycle life of the battery. Detailed test results will be described later.
  • the adhesion between the coating layer and the surface of the graphite core material is increased, and the coating layer coats the surface of the graphite core material uniformly and densely, thereby preventing the electrolyte from directly contacting the surface of the graphite core material. It is estimated that. As a result, the electrolytic solution is unlikely to reach the edge portion (the end portion of the graphene structure) of the highly active graphite core material, and therefore, it is estimated that reductive decomposition of the electrolytic solution is suppressed and contributes to improvement of battery characteristics.
  • the carbon / oxygen atomic ratio of the functional group on the surface of the low crystalline carbon coating layer, the C1s analysis result, and the O1s analysis result are shown in Table 1. Show. In addition, the numerical value shown in the column of C1s analysis result of Table 1 and O1s analysis result shows each coupling
  • the coating layers of the negative electrode active materials (composite carbon particles) of Examples 2 to 6 are largely characterized in that they contain a functional group containing a C ⁇ O bond. The ratios of C—OH and C ⁇ O are respectively The atomic composition ratio of oxygen in the functional group is 1: 1 to 4: 1.
  • a conductive additive may be added to the negative electrode. Since the conductive auxiliary agent does not participate in the insertion and release of lithium ions and acts as an electron medium, it does not affect the lithium ion storage and release reaction in the negative electrode active material.
  • a conductive polymer material composed of polyacene, polyparaphenylene, polyaniline, and polyacetylene can be used by adding to the negative electrode.
  • the negative electrode active material is a powder
  • a negative electrode binder is mixed with the negative electrode active material, and the powders are bonded to each other at the same time.
  • the particle size of the negative electrode active material is equal to or less than the thickness of the mixture layer including the negative electrode active material and the negative electrode binder.
  • the coarse particles are removed in advance by sieving classification, wind classification, etc., and particles having a thickness of the mixture layer or less are used. It is preferable to do.
  • any current collector can be used without being limited by the material, shape, manufacturing method and the like.
  • the negative electrode slurry in which the negative electrode active material, the negative electrode binder, and an appropriate solvent are mixed is attached to the current collector by a doctor blade method, a dipping method, a spray method, etc., the solvent is dried, and the negative electrode is removed by a roll press.
  • the negative electrode was produced by pressure molding.
  • ⁇ Electrochemical evaluation 1> Using the negative electrode active material (composite carbon particles) shown in Table 1, an electrochemical cell using Li metal as a counter electrode and Li metal as a reference electrode was assembled.
  • the cell using the negative electrode active material of Example 2 was C1
  • the cell using the negative electrode active material of Example 3 was C2
  • the cell using the negative electrode active material of Example 4 was C3, and the negative electrode active material of Example 5 was The cell used is C4, the cell using the negative electrode active material of Example 6 is C5, and the cell using the negative electrode active material of Comparative Example 1 is C6.
  • N-methyl as a solvent is mixed so that 95 parts by mass of each negative electrode active material is mixed with 5 parts by mass of PVDF as a negative electrode binder, and the total solid content of the negative electrode active material and PVDF in the negative electrode slurry is 55% by mass.
  • -2-pyrrolidone was added.
  • the resulting negative electrode slurry was sufficiently kneaded using a planetary mixer, and applied to the surface of a copper foil current collector having a thickness of 10 ⁇ m by a doctor blade method.
  • N-methyl-2-pyrrolidone was dried using a drying oven in an air atmosphere at 120 ° C., and then subjected to pressure molding using a roll press machine to produce each negative electrode.
  • the negative electrode mixture density was 1.5 g / cm 3 .
  • a microporous sheet (thickness 25 ⁇ m) in which polyethylene and polypropylene were laminated was used.
  • an electrolytic solution composed of ethylene carbonate, dimethyl carbonate, and ethyl methyl carbonate in which 1M LiPF 6 was dissolved was used. The volume ratio of each solvent was 1: 1: 1.
  • the above six types of cells were charged at a current density of 0.1 mA / cm 2 (current density corresponding to a rate of about 8 hours) under the conditions of a lower limit voltage of 10 mV and a maximum charging time of 8 hours, and then rested for 30 minutes. After a lapse of time, discharging was performed at a constant current density (0.1 mA / cm 2 ) up to an upper limit voltage of 1V. After another 30 minute rest period, the above charge-discharge cycle was repeated.
  • Table 2 shows the “irreversible capacity” results obtained from the difference between the “initial discharge capacity” and the initial charge capacity and discharge capacity. In addition, each capacity
  • the cells (C1 to C5) using the negative electrode active material according to the example of the present invention have smaller irreversible capacity and larger initial discharge capacity than the cell C6 using the negative electrode active material according to Comparative Example 1. all right.
  • B1 is a battery using the negative electrode active material of Example 2 shown in Table 1
  • B2 is a battery using the negative electrode active material of Example 3
  • B3 is a battery using the negative electrode active material of Example 4.
  • B4 is a battery using the negative electrode active material
  • B5 is a battery using the negative electrode active material of Example 6
  • B6 is a battery using the negative electrode active material of Comparative Example 1.
  • N-methyl as a solvent is mixed so that 95 parts by mass of each negative electrode active material is mixed with 5 parts by mass of PVDF as a negative electrode binder, and the total solid content of the negative electrode active material and PVDF in the negative electrode slurry is 55% by mass.
  • -2-pyrrolidone was added.
  • the resulting negative electrode slurry was sufficiently kneaded using a planetary mixer, and applied to the surface of a copper foil current collector having a thickness of 10 ⁇ m by a doctor blade method.
  • N-methyl-2-pyrrolidone was dried using a drying oven in an air atmosphere at 120 ° C., and then subjected to pressure molding using a roll press machine to produce each negative electrode.
  • the positive electrode active material used for each battery was LiNi 1/3 Mn 1/3 Co 1/3 O 2 . 89 parts by mass of this positive electrode active material, 4 parts by mass of acetylene black and 7 parts by mass of PVDF as a positive electrode binder were mixed to prepare a positive electrode slurry to which N-methyl-2-pyrrolidone was added. A known kneader or disperser was used for the material dispersion treatment. The mass per unit area of the positive electrode active material and the thickness and density of the positive electrode were set to be the same for each battery.
  • a microporous sheet (thickness 25 ⁇ m) in which polyethylene and polypropylene were laminated was used.
  • electrolytic solution an electrolytic solution composed of ethylene carbonate, dimethyl carbonate, and ethyl methyl carbonate in which 1M LiPF 6 was dissolved was used.
  • the volume ratio of each solvent was 1: 1: 1.
  • Each battery was supplied with a charging current having a current value (15 A) equivalent to a one hour rate, and charged at a constant voltage of 4.2 V for one hour.
  • a discharge current of 15 A was applied, and the battery was discharged until the battery voltage reached 3.0V.
  • the charge / discharge cycle was continued 100 times under the same conditions, and the capacity retention rate after 100 cycles was determined from the ratio of the discharge capacity at the 100th cycle to the initial discharge capacity. The results are shown in the column of “Capacity maintenance rate (%) after 100 cycles” in Table 2.
  • ⁇ Electrochemical evaluation 3> 1 were connected in series to assemble the assembled battery (battery module) 401 shown in FIG. 4 and assembled into the power supply system shown in FIG.
  • the lithium ion battery is manufactured by the electrochemical evaluation 2 described above.
  • This power storage system is useful as a mobile body or a stationary power storage system.
  • 401 is an assembled battery
  • 402 is a lithium ion battery (single cell)
  • 403 is a positive terminal
  • 404 is a bus bar
  • 405 is a battery can
  • 406 is a support component
  • 407 is a positive external terminal
  • 408 is an external negative electrode.
  • 409 is an arithmetic processing unit
  • 410 is a charge / discharge circuit
  • 411 is an external device
  • 412 is a power line
  • 413 is a signal line
  • 414 is an external power cable.
  • a cylindrical lithium ion battery (hereinafter simply referred to as “battery”) 402 is fixed by a support component 406. Each battery is connected in series via a bus bar 404 by alternately switching the directions of the positive electrode terminal 403 and the battery can 405.
  • the positive terminal 403 corresponds to the battery lid 120 in FIG. 1
  • the battery can 405 corresponds to the battery can 113 in FIG.
  • the ends of the eight batteries 402 connected in series are connected to the positive external terminal 407 and the negative external terminal 408.
  • the assembled battery 401 eight batteries 402 are connected in series.
  • the number of the batteries 402 to be connected is not limited to eight, and if the number is two or more, the number is appropriately set according to the size of the assembled battery 401. Is set.
  • the connection mode of the battery 402 in the assembled battery 401 is not limited to this, A parallel may be sufficient and a series-parallel may be sufficient.
  • the positive external terminal 407 and the negative external terminal 408 are connected to a charge / discharge circuit 410 that performs charging and discharging of the assembled battery 401 via a power line 412.
  • the operation of the charging / discharging circuit 410 is controlled by the arithmetic processing unit 409 via the signal line 413.
  • the arithmetic processing unit 409 controls the current and voltage of the charging / discharging circuit 410, and discharge current flowing between the external terminals (positive external terminal 407 and negative external terminal 408) of the assembled battery 401 and the external device 411. Controls the voltage during discharge.
  • power is supplied to the external device 411 via the external power cable 414.
  • the composition of the negative electrode active material in this evaluation is a composition obtained by adding 5 parts by mass of PVDF as a negative electrode binder to 95 parts by mass of the negative electrode active material (composite carbon particles) of Example 4.
  • the positive electrode active material is LiNi 1/3 Mn 1/3 Co 1/3 O 2 .
  • a reverse current was passed from the positive external terminal 407 and the negative external terminal 408 to the charge / discharge circuit 410, and power was consumed by the power supply load device as the external device 411.
  • the discharge current was set to a 0.5 hour rate condition (7.5 A discharge current) and was discharged until the voltage between the positive external terminal 407 and the negative external terminal 408 reached 24V.
  • the above three types of systems were charged under the same conditions and left at an environmental temperature of 50 ° C. for 30 days. Thereafter, the charge / discharge cycle test was restarted from the discharge, the discharge capacity at the 10th cycle was measured, and the capacity retention rate after standing at 50 ° C. was obtained.
  • the capacity retention rate is a value obtained as a ratio to the initial capacity before being left at 50 ° C. as 100%.
  • S1 was 93%
  • S2 was 92%
  • S3 was 75%
  • the negative electrode active materials of Examples 4 and 5 of the present invention were also effective for storage characteristics at 50 ° C. It was.
  • the lithium ion battery and the battery module of the present invention are used for power supplies for electric vehicles, storage batteries for storing renewable energy, unmanned mobile vehicles, nursing care devices, etc., in addition to consumer products such as portable electronic devices, mobile phones, and power tools. It is possible. Furthermore, the lithium ion battery of the present invention can be applied to a power source of a space exploration ship for searching for the moon, Mars, and the like. Also, space stations, structures on earth or other celestial bodies or living spaces (closed or open), spacecraft for interplanetary movement, planetary rover, sealed space in water or underwater It can be used for various power sources such as air conditioning, temperature control, sewage and air purification, and power for various spaces such as submarines and fish observation equipment.
  • a lithium ion battery having improved cycle life and high temperature storage characteristics can be provided.
  • the present invention can be applied to a lithium ion battery such as a lithium ion secondary battery, a mobile body using the same, a stationary power storage system, or the like.

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  • Chemical & Material Sciences (AREA)
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  • Electrochemistry (AREA)
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  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

L'invention concerne une batterie lithium-ion comportant une électrode négative constituée de : un matériau actif d'électrode négative capable d'absorber et de désorber le lithium, une électrode positive, un électrolyte non aqueux et un solvant non aqueux ; un module de batterie qui utilise la batterie lithium-ion ; ainsi qu'un système de stockage d'énergie pour un corps mobile et un système de stockage d'énergie stationnaire. Le matériau actif d'électrode négative se compose de particules de carbone composites, chacune d'entre elles ayant une couche de revêtement en carbone à faible cristallinité sur la surface d'un matériau de noyau en graphite. La couche de revêtement a des groupes fonctionnels, à savoir des groupes C=O, des groupes C-OH et des groupes C-O sur la surface, et la proportion des atomes d'oxygène dans le total des atomes de carbone et d'oxygène contenus dans la couche de revêtement est de 2 à 5 % d'atomes. Le matériau actif d'électrode négative a au moins un pic respectivement dans une fourchette de température supérieure ou égale à 350 °C mais inférieure à 600 °C et dans une fourchette de température de 600 °C à 850 °C (inclus) déterminée par mesure thermogravimétrique, et la différence de température de pointe entre un pic d'oxydation qui a la température de pointe la plus haute dans la fourchette de température de 350 à 850 °C (inclus) et un pic d'oxydation qui a la température de pointe la plus basse dans la fourchette de température de 350 à 850 °C (inclus) est inférieure ou égale à 300 °C.
PCT/JP2011/071705 2010-09-24 2011-09-22 Batterie lithium-ion et module de batterie l'utilisant WO2012039477A1 (fr)

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CN201180045723.8A CN103190018B (zh) 2010-09-24 2011-09-22 锂离子电池、以及使用该电池的电池模块
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JP2012535082A JP6003648B2 (ja) 2010-09-24 2011-09-22 負極活物質、リチウムイオン電池、及びそれを利用した電池モジュール

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CN103190018A (zh) 2013-07-03
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