WO2012011247A1 - リチウムイオン二次電池負極材用粉末、リチウムイオン二次電池負極およびキャパシタ負極、ならびに、リチウムイオン二次電池およびキャパシタ - Google Patents
リチウムイオン二次電池負極材用粉末、リチウムイオン二次電池負極およびキャパシタ負極、ならびに、リチウムイオン二次電池およびキャパシタ Download PDFInfo
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- WO2012011247A1 WO2012011247A1 PCT/JP2011/003938 JP2011003938W WO2012011247A1 WO 2012011247 A1 WO2012011247 A1 WO 2012011247A1 JP 2011003938 W JP2011003938 W JP 2011003938W WO 2012011247 A1 WO2012011247 A1 WO 2012011247A1
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- Prior art keywords
- negative electrode
- secondary battery
- ion secondary
- lithium ion
- powder
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 114
- 239000000843 powder Substances 0.000 title claims abstract description 97
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 69
- 239000003990 capacitor Substances 0.000 title claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 50
- 238000004438 BET method Methods 0.000 claims abstract description 9
- 125000001475 halogen functional group Chemical group 0.000 claims abstract description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 15
- 230000005260 alpha ray Effects 0.000 claims description 4
- 238000005259 measurement Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 238000000151 deposition Methods 0.000 description 9
- 230000008021 deposition Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 239000002131 composite material Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- -1 nickel metal hydride Chemical class 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910004283 SiO 4 Inorganic materials 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000002427 irreversible effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
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- 230000007423 decrease Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000011863 silicon-based powder Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005211 surface analysis Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
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- 229910052804 chromium Inorganic materials 0.000 description 1
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- 239000002482 conductive additive Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011158 quantitative evaluation Methods 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Images
Classifications
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- 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
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- 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
-
- 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
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
- H01G9/0425—Electrodes or formation of dielectric layers thereon characterised by the material specially adapted for cathode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
Definitions
- the present invention provides a negative electrode material powder capable of providing a lithium ion secondary battery that has a large discharge capacity and good cycle characteristics when used in a lithium ion secondary battery and can withstand use at a practical level.
- the present invention relates to a lithium ion secondary battery negative electrode and a capacitor negative electrode using powder for a negative electrode material, and a lithium ion secondary battery and a capacitor using the lithium ion secondary battery negative electrode and the capacitor negative electrode.
- high energy density secondary batteries include nickel cadmium batteries, nickel metal hydride batteries, lithium ion secondary batteries, and polymer batteries.
- lithium ion secondary batteries have a much longer lifespan and higher capacity than nickel cadmium batteries and nickel metal hydride batteries, and thus the demand thereof has shown high growth in the power supply market.
- FIG. 1 is a diagram showing a configuration example of a coin-shaped lithium ion secondary battery.
- the lithium ion secondary battery maintains the electrical insulation between the positive electrode 1, the negative electrode 2, the separator 3 impregnated with the electrolyte, and the positive electrode 1 and the negative electrode 2 and seals the battery contents. It consists of a gasket 4.
- lithium ions reciprocate between the positive electrode 1 and the negative electrode 2 through the electrolytic solution of the separator 3.
- the positive electrode 1 includes a counter electrode case 1a, a counter electrode current collector 1b, and a counter electrode 1c.
- Lithium cobaltate (LiCoO 2 ) and manganese spinel (LiMn 2 O 4 ) are mainly used for the counter electrode 1c.
- the negative electrode 2 is composed of a working electrode case 2a, a working electrode current collector 2b, and a working electrode 2c, and the negative electrode material used for the working electrode 2c is generally an active material capable of occluding and releasing lithium ions (negative electrode active material). And a conductive assistant and a binder.
- a negative electrode active material of a lithium ion secondary battery a composite oxide of lithium and boron, a composite oxide of lithium and a transition metal (V, Fe, Cr, Mo, Ni, etc.), Si, Ge, or Sn A compound containing N and O, Si particles whose surface is coated with a carbon layer by chemical vapor deposition, and the like have been proposed.
- silicon oxide powder represented by SiO x (0 ⁇ x ⁇ 2) such as SiO As the negative electrode active material.
- Silicon oxide has a low electrode potential with respect to lithium (base), and does not occlude lithium ions during charging / discharging, and does not degrade the crystal structure due to release or generation of irreversible substances, and reversibly occludes lithium ions. And since it can discharge
- silicon oxide powder is used as the negative electrode active material
- carbon powder or the like is generally mixed as a conductive aid in order to compensate for the low electrical conductivity of silicon oxide.
- the electrical conductivity of the contact part vicinity of a silicon oxide powder and a conductive support agent is securable.
- electrical conductivity cannot be ensured at a location away from the contact portion, and it is difficult to function as a negative electrode active material.
- Patent Document 1 discloses a non-aqueous electrolyte secondary battery negative electrode material in which a carbon film is formed on the surface of particles (conductive silicon composite) having a structure in which silicon microcrystals are dispersed in silicon dioxide.
- conductive silicon composite and a method for producing the same have been proposed.
- Patent Document 1 According to the method proposed in Patent Document 1, a uniform carbon film is formed on the conductive silicon composite, and sufficient electrical conductivity can be imparted.
- the lithium ion secondary battery using the conductive silicon composite of Patent Document 1 uses silicon dioxide in which silicon microcrystals are dispersed as the negative electrode material. The expansion / contraction at the time of desorption of lithium ions is increased, and there is a problem that the capacity suddenly decreases at a certain point when charging and discharging are repeated. Further, the discharge capacity and cycle characteristics were not sufficient.
- the present invention has been made in view of this problem, and has a large discharge capacity, good cycle characteristics, and a negative electrode material powder for a lithium ion secondary battery that can withstand use at a practical level, and the negative electrode material.
- An object of the present invention is to provide a lithium ion secondary battery negative electrode and a capacitor negative electrode using the powder for use, and a lithium ion secondary battery and a capacitor using the lithium ion secondary battery negative electrode and the capacitor negative electrode.
- Li 22 Si 5 in the first term on the right side of the equation (1) is a component responsible for reversible capacity, and Li 4 SiO 4 in the second term is responsible for irreversible capacity. Li 4 SiO 4 cannot release lithium ions.
- the theoretical characteristic of the lithium ion secondary battery when silicon oxide (SiO x ) is used as the negative electrode material powder and x 1 is a reversible capacity of 2007 mAh / g, The initial efficiency was found to be 76%.
- Conventional lithium ion secondary batteries using silicon oxide as a negative electrode material powder have a reversible capacity of about 1500 mAh / g, so a lithium ion secondary battery using silicon oxide as a negative electrode material powder. It was found that there is still room for improvement in the reversible capacity of the battery.
- the present inventors examined suppression of the generation of irreversible capacity components. It is considered that the generation of the irreversible capacity component during the first charge / discharge can be suppressed as the specific surface area (surface area per unit mass) of the silicon oxide powder is smaller. As a result of examination based on this viewpoint, excellent initial efficiency is obtained when the specific surface area of the silicon oxide powder measured by the BET method is 40 m 2 / g or less, and more excellent when it is 5.0 m 2 / g or less. It was found that the initial efficiency was obtained. However, in order to reduce the specific surface area, it is necessary to increase the size of the particles. If particles having a large specific surface area are excessively demanded, the yield during the production of the silicon oxide powder is lowered and it is difficult to industrialize economically. For this reason, the specific surface area is set to 0.3 m 2 / g or more.
- the present inventors can particularly increase the capacity of the lithium ion secondary battery and make the initial efficiency and cycle characteristics relatively good.
- the cause of the decrease in the capacity of the lithium ion secondary battery was investigated for silicon oxide on which a carbon film was formed.
- silicon oxide with the same composition and the same average particle size was subjected to carbon film formation treatment under the same conditions, and then subjected to heat treatment under various conditions to graphitize the carbon component for negative electrode materials.
- capacitance by repetition of charging / discharging was investigated.
- the negative electrode material powder was analyzed using an X-ray diffractometer (XRD).
- the initial capacity of the lithium ion secondary battery was particularly small when a SiC peak appeared in the XRD chart and its half-value width was less than 2 °.
- the appearance of the SiC peak means that SiC was generated in the vicinity of the interface between the silicon oxide and the carbon film, and the half-value width of the peak is less than 2 ° means that the generation of crystalline SiC is excessive. It means that the state has progressed to. From these facts, it is considered that the reason why the initial capacity was small was that SiC converted to Si could no longer contribute to the battery capacity. Furthermore, it is considered that one of the reasons is that the formed SiC layer hinders the entry of lithium ions into silicon oxide.
- SiC is likely to be generated in the case of high-temperature heat treatment in which silicon oxide and the carbon film are likely to react.
- the heat treatment temperature is as high as 1100 ° C.
- the present invention has been made on the basis of the above knowledge, and the gist thereof is as follows. (1) to (4) Lithium ion secondary battery negative electrode powder, (5) Lithium ion secondary battery negative electrode and It exists in a capacitor negative electrode and the lithium ion secondary battery and capacitor of the following (6).
- a characteristic powder for a negative electrode material of a lithium ion secondary battery is
- the “lower silicon oxide powder” is a SiO x powder satisfying 0.4 ⁇ x ⁇ 1.2. A method for measuring x and a method for measuring the specific surface area by the BET method will be described later.
- “having a conductive carbon film on the surface” of the lower silicon oxide powder is a result of surface analysis using an X-ray photoelectron spectroscopic analyzer.
- the Si / C molar ratio value Si / C Is 0.02 or less that is, the surface of the lower silicon oxide powder is almost covered with C and Si is hardly exposed.
- Lithium ion secondary battery negative electrode powder according to the present invention, and lithium ion secondary battery negative electrode or capacitor negative electrode are used to provide lithium having a large discharge capacity and good cycle characteristics, and can be used at a practical level. An ion secondary battery and a capacitor can be obtained. Moreover, the lithium ion secondary battery and capacitor of the present invention have a large discharge capacity and good cycle characteristics.
- FIG. 1 is a diagram illustrating a configuration example of a coin-shaped lithium ion secondary battery.
- FIG. 2 is a diagram showing a configuration example of a silicon oxide manufacturing apparatus.
- the powder for a negative electrode material of a lithium ion secondary battery of the present invention is a powder for a negative electrode material of a lithium ion secondary battery having a conductive carbon film on the surface of a lower silicon oxide powder.
- the SiC peak at 1 ° does not exist or the half width of the peak is 2 ° or more.
- the specific surface area measured by the BET method is larger than 0.3 m 2 / g and preferably 5.0 m 2 / g or less.
- the lower silicon oxide powder is a SiO x powder satisfying 0.4 ⁇ x ⁇ 1.2 as described above.
- the reason why x is in this range is that when the value of x is less than 0.4, the lithium ion secondary battery using the negative electrode material powder of the present invention and the capacitor are severely deteriorated due to charge / discharge cycles, and 1.2. This is because the capacity of the battery is reduced when the value exceeds.
- x preferably satisfies 0.8 ⁇ x ⁇ 1.05.
- the proportion of the conductive carbon film (hereinafter referred to as “carbon film ratio”) is preferably 0.2% by mass or more and 2.5% by mass or less.
- the carbon film also contributes to the charge / discharge capacity of the lithium ion secondary battery as in the case of lower silicon oxide, but its charge / discharge capacity per unit mass is smaller than that of lower silicon oxide. Therefore, it is preferable that the carbon film rate of the powder for a negative electrode material for a lithium ion secondary battery is as small as possible in order to ensure the charge / discharge capacity of the lithium ion secondary battery. On the other hand, if the carbon film rate is too small, the effect of imparting conductivity by the conductive carbon film cannot be obtained. From these, the carbon film rate is preferably 0.2% by mass or more and 2.5% by mass or less.
- the average particle size of the lithium ion secondary battery negative electrode powder is preferably 1 ⁇ m or more and 15 ⁇ m or less, and more preferably 3 ⁇ m or more and 12 ⁇ m or less. If the average particle size is too small, a uniform slurry cannot be obtained during electrode production, and the powder tends to fall off from the current collector. On the other hand, if the average particle diameter is too large, it is difficult to produce the electrode film constituting the working electrode 2c shown in FIG. 1, and the powder may be peeled off from the current collector.
- the average particle diameter is a value measured as a weight average value D 50 (particle diameter or median diameter when the cumulative weight is 50% of the total weight) in the particle size distribution measurement by the laser light diffraction method.
- the specific resistance of the powder for a negative electrode material for a lithium ion secondary battery is preferably 100000 ⁇ cm or less. This is because when the specific resistance is larger than 100,000 ⁇ cm, it is difficult to act as an electrode active material of a lithium ion secondary battery. The smaller the specific resistance, the better the electric conduction and the better the electrode active material of the lithium ion secondary battery, so there is no need to provide a lower limit.
- the specific surface area of the lower silicon oxide powder can be measured by the following BET method in both cases where the conductive carbon film is formed and not formed. 0.5 g of sample is put in a glass cell and dried under reduced pressure at 200 ° C. for about 5 hours. Then, the specific surface area is calculated from the nitrogen gas adsorption isotherm at the liquid nitrogen temperature ( ⁇ 196 ° C.) measured for this sample. The measurement conditions are as shown in Table 2.
- Carbon film ratio measurement method The carbon film ratio is determined by measuring the mass of the powder for the negative electrode material of the lithium ion secondary battery and the CO 2 gas by an oxygen gas flow combustion-infrared absorption method using a carbon concentration analyzer (Leco, CS400). It is calculated from the result of carbon amount quantitatively evaluated by analysis.
- the crucible is a ceramic crucible, the auxiliary combustor is copper, and the analysis time is 40 seconds.
- Measuring method of O content O content in powder for lithium ion secondary battery negative electrode material was analyzed by 10% of sample by inert gas melting / infrared absorption method using oxygen concentration analyzer (Leco, TC436). It is calculated from the O content in the sample quantitatively evaluated.
- Si content in the negative electrode powder for lithium ion secondary batteries was determined by adding nitric acid and hydrofluoric acid to the sample to dissolve the sample, and then adding the resulting solution to an ICP emission spectrometer (Shimadzu Corporation). And the Si content in the sample under quantitative evaluation. In this method, Si, SiO and SiO 2 are dissolved, and Si constituting them can be detected.
- Calculation method of x of SiO x x of SiO x is a molar ratio (O / Si) of O content and Si content in the powder for negative electrode of lithium ion secondary battery, and O content measured by the above measurement method It calculates using a rate and Si content rate.
- the specific resistance ⁇ ( ⁇ cm) of the powder for a negative electrode material for a lithium ion secondary battery is calculated using the following equation (2).
- ⁇ R ⁇ A / L
- R electrical resistance ( ⁇ ) of the sample
- A bottom area (cm 2 ) of the sample
- L thickness (cm) of the sample.
- the electrical resistance of the sample was as follows: 0.20 g of the sample was filled in a powder resistance measurement jig (jig part: stainless steel with an inner diameter of 20 mm, frame part: made of polytetrafluoroethylene), and pressurized at 20 kgf / cm 2 for 60 seconds. After that, the measurement is performed by a two-terminal method using a digital multimeter (VOAC7513, manufactured by Iwatatsu Measurement Co., Ltd.). The thickness of the sample is measured with a micrometer.
- VOAC7513 digital multimeter
- FIG. 2 is a diagram showing a configuration example of a silicon oxide manufacturing apparatus.
- This apparatus includes a vacuum chamber 5, a raw material chamber 6 disposed in the vacuum chamber 5, and a deposition chamber 7 disposed on the upper portion of the raw material chamber 6.
- the raw material chamber 6 is formed of a cylindrical body, and a cylindrical raw material container 8 and a heating source 10 surrounding the raw material container 8 are disposed at the center thereof.
- a heating source 10 for example, an electric heater can be used.
- the deposition chamber 7 is composed of a cylindrical body arranged so that its axis coincides with the raw material container 8.
- a deposition base 11 made of stainless steel is provided on the inner peripheral surface of the deposition chamber 7 for vapor deposition of gaseous silicon oxide generated by sublimation in the raw material chamber 6.
- a vacuum device (not shown) for discharging the atmospheric gas is connected to the vacuum chamber 5 that accommodates the raw material chamber 6 and the deposition chamber 7, and the gas is discharged in the direction of arrow A.
- a mixed granulated raw material 9 in which silicon powder and silicon dioxide powder are blended at a predetermined ratio as a raw material, mixed, granulated and dried is used.
- the mixed granulated raw material 9 is filled in the raw material container 8 and heated (heated by a heating source 10) in an inert gas atmosphere or vacuum to generate (sublimate) SiO.
- Gaseous SiO generated by the sublimation rises from the raw material chamber 6 and enters the deposition chamber 7, is vapor-deposited on the surrounding deposition base 11, and is deposited as lower silicon oxide 12. Thereafter, the lower silicon oxide 12 deposited from the deposition base 11 is removed and pulverized using a ball mill or the like to obtain a lower silicon oxide powder.
- the conductive carbon film is formed on the surface of the lower silicon oxide powder by CVD or the like. Specifically, a rotary kiln is used as an apparatus, and a gas mixture of a hydrocarbon gas or an organic substance-containing gas and an inert gas is used as a gas.
- the forming temperature of the conductive carbon film is 600 ° C. or higher and 900 ° C. or lower.
- the treatment time is 20 minutes or more and 120 minutes or less, and is set according to the thickness of the conductive carbon film to be formed. This treatment time is a range in which SiC is not formed in the vicinity of the interface between the surface of the lower silicon oxide powder and the carbon film.
- the negative electrode material used for the negative electrode 2, that is, the working electrode 2c constituting the negative electrode of the lithium ion secondary battery of the present invention is configured using the powder for negative electrode material of the lithium ion secondary battery of the present invention. Specifically, it can be comprised with the powder for lithium ion secondary battery negative electrode materials of this invention which is an active material, another active material, a conductive support material, and a binder. Of the constituent materials in the negative electrode material, the ratio of the powder for the negative electrode material of the lithium ion secondary battery of the present invention to the total of the constituent materials excluding the binder is 20% by mass or more. It is not always necessary to add an active material other than the powder for a negative electrode material of the lithium ion secondary battery of the present invention.
- the conductive additive for example, acetylene black or carbon black can be used
- the binder for example, polyacrylic acid (PAA) or polyvinylidene fluoride can be used.
- the lithium ion secondary battery of the present invention uses the above-described powder for a lithium ion secondary battery negative electrode material and a lithium ion secondary battery negative electrode of the present invention, the discharge capacity is large, the cycle characteristics are good, and the practical level. Can withstand use in
- the powder for negative electrode material of the present invention and the negative electrode using the same can also be applied to capacitors.
- Test conditions 1-1 Configuration of Lithium Ion Secondary Battery
- the configuration of the lithium ion secondary battery was the coin shape shown in FIG.
- Silicon powder and silicon dioxide powder are blended at a predetermined ratio, and mixed, granulated and dried mixed granulated raw materials are used as raw materials, and lower silicon oxide is deposited on the deposition substrate using the apparatus shown in FIG. .
- the deposited lower silicon oxide was pulverized for 24 hours using an alumina ball mill to obtain a powder having an average particle diameter (D 50 ) of 5.1 ⁇ m.
- a conductive carbon film was formed on the surface of the lower silicon oxide powder using a rotary kiln as an apparatus and a mixed gas of C 3 H 8 and Ar as a gas.
- the carbon film rate was 2.4% by mass.
- the lower silicon oxide powder on which the conductive carbon film was formed was heat-treated to obtain a powder for a negative electrode material for a lithium ion secondary battery.
- the heat treatment conditions (temperature and time) were as shown in Table 3.
- Test Nos. 1 and 2 are examples of the present invention in which no peak of SiC was present or the half width of the peak was 2 ° or more as a result of XRD measurement of the powder for a negative electrode material for a lithium ion secondary battery
- the examples of test numbers 3 to 6 are comparative examples in which the half width of the SiC peak was less than 2 °.
- a slurry is prepared by adding n-methylpyrrolidone to a mixture containing 65% by mass of the negative electrode powder for a lithium ion secondary battery, 10% by mass of acetylene black, and 25% by mass of PAA. This slurry was applied to a copper foil having a thickness of 20 ⁇ m, dried in an atmosphere at 120 ° C. for 30 minutes, and then punched out to a size with an area of 1 cm 2 on one side to obtain a negative electrode 2.
- the counter electrode 1c was a lithium foil.
- LiPF 6 lithium phosphorous hexafluoride
- EC ethylene carbonate
- DEC diethyl carbonate
- a polyethylene porous film having a thickness of 30 ⁇ m was used as the separator.
- Test results A lithium-ion secondary battery produced under the above conditions was subjected to a charge / discharge test and evaluated using the initial discharge capacity as an index. Moreover, the specific resistance of the powder for lithium ion secondary battery negative electrode materials was also measured. These values are shown in Table 3 together with the test conditions.
- Test No. 1 which is an example of the present invention
- SiC was not generated in the vicinity of the interface between the silicon oxide and the carbon film, and no peak existed in the XRD chart.
- Test No. 2 which is an example of the present invention
- SiC was produced, but a small amount and low crystallinity, and an SiC peak having a peak half-value width of 2 ° or more appeared in the XRD chart. Therefore, the initial discharge capacity was an excellent value of 1796 mAh / g or more.
- both the lithium ion secondary batteries of Test Nos. 1 and 2 have good cycle characteristics.
- test numbers 3 to 6 which are comparative examples, since the heat treatment temperature was high, the generation of crystalline SiC progressed in the vicinity of the interface between the silicon oxide and the carbon film, and the SiC half peak width of the XRD chart was less than 2 °. The peak appeared. Therefore, the initial discharge capacity was inferior to that of the inventive example.
- Lithium ion secondary battery negative electrode powder according to the present invention, and lithium ion secondary battery negative electrode or capacitor negative electrode are used to provide lithium having a large discharge capacity and good cycle characteristics, and can be used at a practical level. An ion secondary battery and a capacitor can be obtained. Moreover, the lithium ion secondary battery and capacitor of the present invention have a large discharge capacity and good cycle characteristics. Therefore, the present invention is a useful technique in the field of secondary batteries and capacitors.
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Abstract
Description
SiOx+(44-x)/10Li++(44-x)/10e-
→ (4-x)/20Li22Si5+x/4Li4SiO4 …(1)
本発明のリチウムイオン二次電池負極材用粉末は、低級酸化珪素粉末の表面に導電性炭素皮膜を有するリチウムイオン二次電池負極材用粉末であって、BET法で測定した比表面積が0.3m2/gを超えて大きく、40m2/g以下であり、CuKα線を用いたXRDで測定した場合に、2θ=35.6°±0.1°におけるSiCのピークが存在しないまたはピークの半値幅が2°以上であることを特徴とする。BET法で測定した比表面積は、0.3m2/gを超えて大きく、5.0m2/g以下であることが好ましい。
3-1.導電性炭素皮膜の形成状態の評価方法
本発明のリチウムイオン二次電池負極材用粉末において、「低級酸化珪素粉末の表面に導電性炭素皮膜を有する」とは、AlKα線(1486.6eV)を用いたX線光電子分光分析装置(XPS)で、導電性炭素皮膜の形成処理を施した低級酸化珪素粉末の表面分析を行った場合に、SiとCとのモル比の値Si/Cが0.02以下であることをいう。XPSの測定条件は表1に示すとおりとする。「Si/Cが0.02以下」とは、低級酸化珪素粉末の表面のほとんどがCに覆われており、Siがほとんど露出していない状態である。
低級酸化珪素粉末の比表面積は、導電性炭素皮膜を形成した状態および形成しない状態のいずれの場合でも、以下のBET法によって測定することができる。試料0.5gをガラスセルに入れて、200℃で約5時間、減圧乾燥する。そして、この試料について測定した液体窒素温度(-196℃)における窒素ガス吸着等温線から比表面積を算出する。測定条件は表2に示すとおりとする。
炭素皮膜率は、リチウムイオン二次電池負極材用粉末の質量と、炭素濃度分析装置(Leco社製、CS400)を用いて酸素気流燃焼-赤外線吸収法によってCO2ガスを分析することで定量評価した炭素量の結果から算出する。ルツボはセラミックルツボを、助燃剤は銅を用い、分析時間は40秒とする。
リチウムイオン二次電池負極材用粉末中のO含有率は、酸素濃度分析装置(Leco社製、TC436)を用いて、試料10mgを不活性ガス融解・赤外線吸収法によって分析することで定量評価した試料中のO含有量から算出する。
リチウムイオン二次電池負極材用粉末中のSi含有率は、試料に硝酸およびフッ酸を加えて試料を溶解させ、得られた溶液をICP発光分光分析装置(株式会社島津製作所製)で分析することによって定量評価下試料中のSi含有量から算出する。この方法では、Si、SiOおよびSiO2が溶解され、これらを構成するSiを検出できる。
SiOxのxは、リチウムイオン二次電池負極材用粉末中のO含有率とSi含有率のモル比(O/Si)であり、上記測定方法で測定したO含有率およびSi含有率を用いて算出する。
リチウムイオン二次電池負極材用粉末の比抵抗ρ(Ωcm)は、下記(2)式を用いて算出する。
ρ=R×A/L …(2)
ここで、R:試料の電気抵抗(Ω)、A:試料の底面積(cm2)、L:試料の厚さ(cm)である。
試料の電気抵抗は、粉末抵抗測定用治具(治具部:内径20mmのステンレス製、枠部:ポリテトラフルオロエチレン製)に試料0.20gを充填し、20kgf/cm2で60秒間加圧した後、デジタルマルチメーター(岩通計測株式会社製、VOAC7513)を用いた二端子法で測定する。試料の厚さはマイクロメーターで測定する。
図2は、酸化珪素の製造装置の構成例を示す図である。この装置は、真空室5と、真空室5内に配置された原料室6と、原料室6の上部に配置された析出室7とを備える。
低級酸化珪素粉末の表面への導電性炭素皮膜の形成は、CVD等により行う。具体的には、装置としてロータリーキルンを用い、ガスとして炭化水素ガスまたは有機物含有ガスと、不活性ガスとの混合ガスを用いて行う。
導電性炭素皮膜を形成した低級酸化珪素粉末は、800℃以上900℃以下の不活性ガス雰囲気下で、2時間以下の熱処理を施す。これにより、導電性炭素皮膜の炭素成分を黒鉛化させ、電気伝導度を向上させる。熱処理温度が上記範囲である場合には、酸化珪素と炭素皮膜との界面近傍におけるSiCの生成が抑制される。
本発明のリチウムイオン二次電池負極材用粉末およびリチウムイオン二次電池負極を用いた、コイン形状のリチウムイオン二次電池の構成例を、前記図1を参照して説明する。同図に示すリチウムイオン二次電池の基本的構成は、上述の通りである。
1-1.リチウムイオン二次電池の構成
リチウムイオン二次電池の構成は、前記図1に示すコイン形状とした。
充放電試験には、二次電池充放電試験装置(株式会社ナガノ製)を用いた。充電は、リチウムイオン二次電池の両極間の電圧が0Vに達するまでは1mAの定電流で行い、電圧が0Vに達した後は、0Vを維持したまま充電を行った。その後、電流値が20μAを下回った時点で充電を終了した。放電は、リチウムイオン二次電池の両極間の電圧が1.5Vに達するまでは1mAの定電流で行った。
上記条件で作製したリチウムイオン二次電池について充放電試験を行い、初回放電容量を指標として評価を行った。また、リチウムイオン二次電池負極材用粉末の比抵抗も測定した。これらの値を試験条件と併せて表3に示す。
2:負極、 2a:作用極ケース、 2b:作用極集電体、
2c:作用極、 3:セパレーター、 4:ガスケット、 5:真空室、
6:原料室、 7:析出室、 8:原料容器、 9:混合造粒原料、
10:加熱源、 11:析出基体、 12:低級酸化珪素
Claims (6)
- 低級酸化珪素粉末の表面に導電性炭素皮膜を有するリチウムイオン二次電池負極材用粉末であって、
BET法で測定した比表面積が0.3m2/gを超えて大きく、40m2/g以下であり、
CuKα線を用いたX線回折装置で測定した場合に、2θ=35.6°±0.1°におけるSiCのピークが存在しないまたはピークの半値幅が2°以上であることを特徴とするリチウムイオン二次電池負極材用粉末。 - 前記導電性炭素皮膜の占める割合が0.2質量%以上2.5質量%以下であることを特徴とする請求項1に記載のリチウムイオン二次電池負極材用粉末。
- 比抵抗が100000Ωcm以下であることを特徴とする請求項1または2に記載のリチウムイオン二次電池負極材用粉末。
- CuKα線を用いたX線回折装置で測定した場合に、2θ=10°~30°に現れるSiOxに由来するハローの最大値P1と、2θ=28.4±0.3°に現れるSi(111)の最強線ピークの値P2が、P2/P1<0.01を満たすことを特徴とする請求項1~3のいずれかに記載のリチウムイオン二次電池負極材用粉末。
- 請求項1~4のいずれかに記載のリチウムイオン二次電池負極材用粉末を用いたリチウムイオン二次電池負極またはキャパシタ負極。
- 請求項5に記載のリチウムイオン二次電池負極またはキャパシタ負極を用いたリチウムイオン二次電池またはキャパシタ。
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KR1020137003667A KR101495451B1 (ko) | 2010-07-20 | 2011-07-08 | 리튬 이온 이차 전지 음극재용 분말, 리튬 이온 이차 전지 음극 및 캐패시터 음극, 및, 리튬 이온 이차 전지 및 캐패시터 |
JP2012525309A JP5497177B2 (ja) | 2010-07-20 | 2011-07-08 | リチウムイオン二次電池負極材用粉末、リチウムイオン二次電池負極およびキャパシタ負極、ならびに、リチウムイオン二次電池およびキャパシタ |
EP11809423.4A EP2597708A4 (en) | 2010-07-20 | 2011-07-08 | POWDER FOR LITHIUM ION SECONDARY ELECTRODE NEGATIVE ELECTRODE MATERIAL, NEGATIVE LITHIUM ION SECONDARY BATTERY ELECTRODE AND NEGATIVE CAPACITOR ELECTRODE, AND LITHIUM ION SECONDARY BATTERY AND CAPACITOR |
US13/810,554 US8900749B2 (en) | 2010-07-20 | 2011-07-08 | Negative electrode material powder for lithium ion secondary battery, negative electrode for lithium ion secondary battery, negative electrode for capacitor, lithium ion secondary battery, and capacitor |
CN2011800354547A CN103003986A (zh) | 2010-07-20 | 2011-07-08 | 锂离子二次电池负极材料用粉末、锂离子二次电池负极及电容器负极、以及锂离子二次电池及电容器 |
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JP2012178269A (ja) * | 2011-02-25 | 2012-09-13 | Toyota Industries Corp | リチウムイオン二次電池用負極活物質、および、その負極活物質を用いたリチウムイオン二次電池 |
WO2014002356A1 (ja) * | 2012-06-25 | 2014-01-03 | 株式会社大阪チタニウムテクノロジーズ | リチウムイオン二次電池負極材用粉末、これを用いたリチウムイオン二次電池負極およびキャパシタ負極、ならびにリチウムイオン二次電池およびキャパシタ |
CN104737337A (zh) * | 2012-10-26 | 2015-06-24 | 日立化成株式会社 | 锂离子二次电池用负极材料、锂离子二次电池用负极和锂离子二次电池 |
JP2016164870A (ja) * | 2015-02-26 | 2016-09-08 | 信越化学工業株式会社 | 非水電解質二次電池用負極活物質、非水電解質二次電池用負極、及び非水電解質二次電池、並びに非水電解質二次電池用負極材の製造方法 |
JP2019012646A (ja) * | 2017-06-30 | 2019-01-24 | 日立化成株式会社 | リチウムイオン二次電池用負極材、リチウムイオン二次電池用負極、及びリチウムイオン二次電池 |
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EP3142174B1 (en) | 2015-09-14 | 2021-02-17 | Toyota Jidosha Kabushiki Kaisha | All-solid-state battery system and method of manufacturing the same |
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JPWO2014002356A1 (ja) * | 2012-06-25 | 2016-05-30 | 株式会社大阪チタニウムテクノロジーズ | リチウムイオン二次電池負極材用粉末、これを用いたリチウムイオン二次電池負極およびキャパシタ負極、ならびにリチウムイオン二次電池およびキャパシタ |
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EP2913871A1 (en) * | 2012-10-26 | 2015-09-02 | Hitachi Chemical Company, Ltd. | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
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US10693130B2 (en) | 2012-10-26 | 2020-06-23 | Hitachi Chemical Company, Ltd. | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
US11251421B2 (en) | 2012-10-26 | 2022-02-15 | Showa Denko Materials Co., Ltd. | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
JP2016164870A (ja) * | 2015-02-26 | 2016-09-08 | 信越化学工業株式会社 | 非水電解質二次電池用負極活物質、非水電解質二次電池用負極、及び非水電解質二次電池、並びに非水電解質二次電池用負極材の製造方法 |
JP2019012646A (ja) * | 2017-06-30 | 2019-01-24 | 日立化成株式会社 | リチウムイオン二次電池用負極材、リチウムイオン二次電池用負極、及びリチウムイオン二次電池 |
JP2021193672A (ja) * | 2017-06-30 | 2021-12-23 | 昭和電工マテリアルズ株式会社 | リチウムイオン二次電池用負極材、リチウムイオン二次電池用負極、及びリチウムイオン二次電池 |
JP7279757B2 (ja) | 2017-06-30 | 2023-05-23 | 株式会社レゾナック | リチウムイオン二次電池用負極材、リチウムイオン二次電池用負極、及びリチウムイオン二次電池 |
Also Published As
Publication number | Publication date |
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JP5497177B2 (ja) | 2014-05-21 |
KR20130054347A (ko) | 2013-05-24 |
CN103003986A (zh) | 2013-03-27 |
US20130164621A1 (en) | 2013-06-27 |
JPWO2012011247A1 (ja) | 2013-09-09 |
EP2597708A4 (en) | 2014-08-06 |
EP2597708A1 (en) | 2013-05-29 |
KR101495451B1 (ko) | 2015-02-24 |
US8900749B2 (en) | 2014-12-02 |
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