WO2015080288A1 - リチウムイオンキャパシタ用負極活物質 - Google Patents
リチウムイオンキャパシタ用負極活物質 Download PDFInfo
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- WO2015080288A1 WO2015080288A1 PCT/JP2014/081769 JP2014081769W WO2015080288A1 WO 2015080288 A1 WO2015080288 A1 WO 2015080288A1 JP 2014081769 W JP2014081769 W JP 2014081769W WO 2015080288 A1 WO2015080288 A1 WO 2015080288A1
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- Prior art keywords
- active material
- electrode active
- lithium ion
- average particle
- weight
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 46
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 45
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000003990 capacitor Substances 0.000 title claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 45
- 239000006229 carbon black Substances 0.000 claims abstract description 33
- 239000007833 carbon precursor Substances 0.000 claims abstract description 17
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 11
- 238000001493 electron microscopy Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- 238000010277 constant-current charging Methods 0.000 claims description 2
- 238000010280 constant potential charging Methods 0.000 claims 1
- 238000007600 charging Methods 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 13
- 239000011295 pitch Substances 0.000 description 13
- 230000001590 oxidative effect Effects 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 230000031864 metaphase Effects 0.000 description 10
- 229910001873 dinitrogen Inorganic materials 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 238000010304 firing Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- -1 nickel metal hydride Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011802 pulverized particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- 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]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
-
- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/42—Powders or particles, e.g. composition thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/364—Composites as mixtures
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
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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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/58—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
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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
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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
- Y02E60/13—Energy storage using capacitors
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a carbonaceous porous powder used for a negative electrode active material for a lithium ion capacitor obtained by mixing, firing, and crushing carbon black and a carbon precursor.
- a device used as a power source for automobiles is required to have both high output characteristics and high energy density.
- Lithium ion capacitors are attracting attention as a power source that complements the high output characteristics that are the disadvantages of lithium ion batteries and the high energy density that is the difficulty of electric double layer capacitors.
- activated carbon used in an electric double layer capacitor is used as a positive electrode active material, and a carbon material capable of inserting and extracting lithium ions is used as a negative electrode.
- Lithium ion capacitors are required to have a higher energy density, and as one of the methods to increase the energy density, the thickness of the negative electrode active material layer is reduced while maintaining the same energy density as before, and the cell volume is reduced. Reduction is considered effective.
- the negative electrode active material is doped with lithium ions, that is, the initial charge capacity per unit weight when lithium metal of the negative electrode active material is used as the counter electrode. Need to be larger.
- An object of the present invention is to enable charging at a higher energy density, so that the negative electrode active material is doped with lithium ions, that is, per unit weight of the first time when lithium metal of the negative electrode active material is used as a counter electrode. It is to increase the charging capacity.
- carbon black having an average particle size of 12 to 300 nm by electron microscopy is mixed with a carbon precursor, calcined at 800 ° C. to 3200 ° C., and pulverized to obtain an average particle size (D 50 ) of 1 to 20 ⁇ m, More preferably, it is a porous composite carbon material comprising carbon black and a carbonaceous material having a thickness of 5 to 20 ⁇ m, and a negative electrode active material for a lithium ion capacitor having a BET specific surface area of 100 m 2 / g or more and 350 m 2 / g or less. is there.
- the average particle size after pulverization is preferably in the range of 1 to 20 ⁇ m.
- the average particle size is larger than 20 ⁇ m, when mixed with a binder to form a slurry, applied onto a metal foil and dried to form an electrode, the electrode thickness becomes thick and resistance cannot be reduced.
- an average particle diameter is smaller than 1 micrometer, when mixing with a binder and making it a slurry, dispersion
- the BET specific surface area is preferably 150 m 2 / g or more and 300 m 2 / g or less, more preferably 180 m 2 / g or more and 240 m 2 / g or less. If the BET specific surface area is 100 m 2 / g or more, the initial charge capacity per unit weight when lithium metal of the negative electrode active material is used as the counter electrode can be 700 mAh / g or more. Even if the cell volume is reduced, the same energy can be maintained, and high energy density can be achieved.
- the BET specific surface area becomes too large, when the active material for lithium ion capacitors is applied to the copper foil using a binder, the binding area becomes large, so the binding effect of the binder is diminished and peeling easily occurs. For this reason, the BET specific surface area is set to 350 m 2 / g or less, and the coating property of the negative electrode is excellent.
- the carbon precursor is preferably mixed in an amount of 30 to 200 parts by weight with respect to 100 parts by weight of carbon black. More preferably, it is 30 parts by weight or more and 150 parts by weight or less with respect to 100 parts by weight of carbon black. If the weight ratio of the carbon black to the carbon precursor is 30 parts by weight or more with respect to 100 parts by weight of the carbon black, high output characteristics can be realized by the effect of the combination of the carbon black and the carbon precursor. .
- the carbon precursor by setting the carbon precursor to 200 parts by weight or less with respect to 100 parts by weight of carbon black, the BET specific surface area of the negative electrode material can be maintained within a preferable range, and the lithium metal of the negative electrode active material is used as a counter electrode. When used, the initial charge capacity per unit weight can be increased.
- carbon black having an average particle diameter of 12 to 300 nm and a BET specific surface area of 200 to 1500 m 2 / g as measured by electron microscopy is mixed with a carbon precursor, and the mixture is 800 to 3200 ° C.
- the average particle size (D 50 ) is preferably 1 to 20 ⁇ m, more preferably 5 to 20 ⁇ m.
- the method for measuring the particle size of carbon black used in the negative electrode active material of the present invention is to take several fields of view several hundreds of times with an electron microscope and 2,000 to 3,000 of the photographed particles with a fully automatic image processing apparatus or the like. Use the method of measuring and obtaining about one piece. (Carbon Black Handbook 3rd Edition, 4 pages, Book Publishing Co., Ltd., issued on May 25, 1973).
- carbon precursor coal, petroleum pitch, phenol resin, furan resin, divinylbenzene or other resin can be used, and these are used alone or in combination of two or more.
- carbon precursors it is advantageous in terms of manufacturing cost to use an inexpensive pitch.
- the carbon black and the carbon precursor are kneaded using a heating kneader or the like, and then kneaded or graphitized at 800 to 3200 ° C. in a non-oxidizing atmosphere.
- the heat treatment temperature is less than 800 ° C.
- the functional group on the particle surface remains and reacts with Li ions.
- the heat treatment temperature exceeds 3400 ° C., the graphitized particles are sublimated, so the graphitization treatment at 3200 ° C. is the limit.
- the product obtained by firing or graphitization is pulverized so that the average particle diameter (D 50 ) is 1 to 20 ⁇ m, more preferably 5 to 20 ⁇ m. After pulverization, it may be refired at 800 to 3200 ° C. or graphitized as necessary.
- the particle size of the pulverized particles was measured by a laser diffraction method (using MT-3300EX manufactured by Nikkiso Co., Ltd.).
- the negative electrode active material of the present invention is an aggregate bound by a carbon material (carbon or graphite) obtained by mixing and firing carbon black having an average particle size of 12 to 300 nm and a carbon precursor such as pitch. It is a porous carbon material and graphite material having a pore structure, and exhibits the following characteristics.
- the change in the amount of adsorption of nitrogen gas is small until the relative pressure of nitrogen gas (P / P 0 ) is around 0.8, and when it exceeds 0.8, it increases rapidly.
- the nitrogen gas relative pressure (P / P 0 ) is around 0.99
- the nitrogen gas adsorption amount is 10 to 1000 cm 3 / g
- the pore diameter is 2 nm.
- the pore volume of the following micropores is 20% or less of the total pore volume.
- a negative electrode active material that exhibits both high output characteristics and high energy density can be obtained.
- the raw materials are inexpensive carbon black and carbon precursor, and the carbon porous powder of the present invention can be obtained by a simple process of pulverizing the mixture after firing.
- the pore structure can be controlled by selecting the type of carbon black and the mixing ratio with the carbon precursor.
- the lithium ion capacitor using the negative electrode active material for a lithium ion capacitor of the present invention has an initial charge capacity of 700 mAh / g or more when the lithium metal of the negative electrode active material is used as a counter electrode, and has an energy density. It is higher than the conventional one, and the cell volume of the lithium ion capacitor can be reduced.
- Example 1 100 parts by weight of carbon black having an average particle size of 30 nm, a BET specific surface area of 254 m 2 / g, a softening point of 110 ° C., and 50 parts by weight of an optically isotropic pitch with a metaphase amount (QI amount) of 13% are mixed with a heating kneader. This is fired at 1000 ° C. in a non-oxidizing atmosphere. This was pulverized to an average particle size of 2 ⁇ m to obtain a negative electrode active material for a lithium ion capacitor.
- Example 2 100 parts by weight of carbon black having an average particle size of 30 nm, a BET specific surface area of 1000 m 2 / g, a softening point of 110 ° C., and an optically isotropic pitch of 100% by weight of the metaphase amount (QI amount) of 13% are mixed with a heating kneader. This is fired at 1000 ° C. in a non-oxidizing atmosphere. This was pulverized to an average particle size of 2 ⁇ m to obtain a negative electrode active material for a lithium ion capacitor.
- Example 3 100 parts by weight of carbon black having an average particle size of 30 nm, a BET specific surface area of 1000 m 2 / g, a softening point of 110 ° C., and 30 parts by weight of an optically isotropic pitch having a metaphase amount (QI amount) of 13% are mixed with a heating kneader. This is fired at 1000 ° C. in a non-oxidizing atmosphere. This was pulverized to an average particle size of 2 ⁇ m to obtain a negative electrode active material for a lithium ion capacitor.
- QI amount metaphase amount
- Example 4 100 parts by weight of carbon black having an average particle size of 30 nm, a BET specific surface area of 254 m 2 / g, a softening point of 110 ° C., and 30 parts by weight of an optically isotropic pitch having a metaphase amount (QI amount) of 13% are mixed with a heating kneader. This is fired at 1000 ° C. in a non-oxidizing atmosphere. This was pulverized to an average particle size of 2 ⁇ m to obtain a negative electrode active material for a lithium ion capacitor.
- QI amount metaphase amount
- Example 5 100 parts by weight of carbon black having an average particle diameter of 30 nm, a BET specific surface area of 1000 m 2 / g, a softening point of 110 ° C., and an optically isotropic pitch of 150% by weight of metaphase amount (QI amount) of 13% are mixed with a heating kneader. This is fired at 1000 ° C. in a non-oxidizing atmosphere. This was pulverized to an average particle size of 2 ⁇ m to obtain a negative electrode active material for a lithium ion capacitor.
- QI amount metaphase amount
- Example 6 100 parts by weight of carbon black having an average particle size of 30 nm, a BET specific surface area of 1000 m 2 / g, a softening point of 110 ° C., and an optically isotropic pitch of 200 parts by weight of a metaphase amount (QI amount) of 13% are mixed with a heating kneader. This is fired at 1000 ° C. in a non-oxidizing atmosphere. This was pulverized to an average particle size of 2 ⁇ m to obtain a negative electrode active material for a lithium ion capacitor.
- QI amount metaphase amount
- Example 7 The carbide used in Example 3 was fired again at 2000 ° C. in a non-oxidizing atmosphere to obtain a negative electrode active material for a lithium ion capacitor.
- Example 8 It was produced in the same manner as in Example 2 except that the average particle size after pulverization was changed to 5 ⁇ m.
- Example 9 It was produced in the same manner as in Example 2 except that the average particle size after pulverization was 10 ⁇ m.
- Example 10 It was produced in the same manner as in Example 1 except that the optically isotropic pitch was 60 parts by weight.
- Example 11 100 parts by weight of carbon black having an average particle size of 34 nm and a BET specific surface area of 1270 m 2 / g and a softening point of 110 ° C. and 100 parts by weight of an optically isotropic pitch having a metaphase amount (QI amount) of 13% are mixed with a heating kneader. This is fired at 1000 ° C. in a non-oxidizing atmosphere. This was pulverized to an average particle size of 2 ⁇ m to obtain a negative electrode active material for a lithium ion capacitor.
- QI amount metaphase amount
- Comparative Example 1 100 parts by weight of carbon black having an average particle size of 48 nm, a BET specific surface area of 39 m 2 / g, a softening point of 110 ° C., and 133 parts by weight of an optically isotropic pitch with a metaphase amount (QI amount) of 13% are mixed with a heating kneader. This is fired at 1000 ° C. in a non-oxidizing atmosphere. This was pulverized to an average particle size of 2 ⁇ m to obtain a negative electrode active material for a lithium ion capacitor.
- QI amount metaphase amount
- Comparative Example 2 100 parts by weight of carbon black having an average particle size of 48 nm, a BET specific surface area of 39 m 2 / g, a softening point of 110 ° C., and 54 parts by weight of an optically isotropic pitch with a metaphase amount (QI amount) of 13% are mixed with a heating kneader. This is fired at 1000 ° C. in a non-oxidizing atmosphere. This was pulverized to an average particle size of 2 ⁇ m to obtain a negative electrode active material.
- QI amount metaphase amount
- Comparative Example 3 100 parts by weight of carbon black having an average particle size of 24 nm, a BET specific surface area of 117 m 2 / g, a softening point of 110 ° C., and an optically isotropic pitch of 50% by weight of metaphase amount (QI amount) of 13% are mixed with a heating kneader. This is fired at 1000 ° C. in a non-oxidizing atmosphere. This was pulverized to an average particle size of 12 ⁇ m to obtain a negative electrode active material for a lithium ion capacitor.
- the measuring method and measuring device of each numerical value in the examples and comparative examples of the present invention are as follows.
- the specific surface area, pore volume, and pore diameter of the negative electrode active material of the present invention are measured by adsorption / desorption of nitrogen gas, and the measurement device is an automatic specific surface area / pore distribution measuring device Tristar 3000 manufactured by Micromeritics. did.
- the micropore volume with a pore diameter of 2 nm or less was determined by the t-plot method in which the adsorption amount was plotted against the thickness t of the adsorption film of nitrogen gas.
- the particle size was measured using an MT3300EX system manufactured by Nikkiso Co., Ltd. in a state where ultrasonic dispersion was performed using water as a dispersion medium and a small amount of surfactant as a dispersant.
- the initial charge capacity is 5 parts by weight of SBR and CMC as binders with respect to 100 parts by weight of the negative electrode active material, and an aqueous slurry is prepared and applied to a copper foil to a thickness of 50 ⁇ m using a doctor blade. After drying at 120 ° C. and applying a roll press, a punched electrode was formed at ⁇ 12. The electrode after pressing had a thickness of 50 ⁇ m. Lithium metal was used as a counter electrode, opposed to each other through a separator to form an electrode group, and then a coin cell was formed by adding an electrolyte solution of 1M LiPF 6 / EC: DEC (3: 7), which was subjected to a charge / discharge test. .
- Charging conditions were constant at measurement temperature 25 ° C., after the voltage value at a current value 0.5 mA / cm 2 was subjected to constant current charging until 0.01 V, until the current value reached 0.01 mA / cm 2 The battery was charged and finished.
- the initial charge capacity per unit weight when lithium metal of the negative electrode active material is used as a counter electrode is 700 mAh / g or more, and the energy density
- the cell volume of the lithium ion capacitor can be reduced, and the device can be miniaturized.
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Abstract
Description
平均粒径を5~20μmとしたものがスラリー化の作業性を向上させることができるので、この範囲とするのが更に好ましい。
BET比表面積が100m2/g以上であれば、負極活物質のリチウム金属を対極に用いた際の初回の単位重量当りの充電容量を700mAh/g以上を達成することができ、リチウムイオンキャパシタのセル体積を縮小させても同じエネルギーを維持でき、高エネルギー密度化が達成できる。
一方、BET比表面積が大きくなりすぎると、リチウムイオンキャパシタ用活物質を銅箔にバインダーを用いて塗布する際、結着させる面積が大きくなるためバインダーの結着効果が薄れ、剥離が起き易くなるため、BET比表面積を350m2/g以下として負極の塗工性に優れたものとする。
このカーボンブラックと炭素前駆体の重量比が、カーボンブラック100重量部に対してカーボンブラックが30重量部以上であれば、カーボンブラックと炭素前駆体との複合化による効果により高出力特性を実現できる。
また、カーボンブラック100重量部に対して、炭素前駆体を200重量部以下とすることによって、負極材のBET比表面積を好ましい範囲内に保持することができ、負極活物質のリチウム金属を対極に用いた際の初回の単位重量当りの充電容量を高めることができる。
また、原材料は安価なカーボンブラックと炭素前駆体であり、これらの混合物を焼成後に粉砕するという簡単な工程によって、本発明の炭素多孔性粉末が得られるものである。
更に、カーボンブラックの種類の選択、炭素前駆体との配合比により細孔構造の制御も可能である。
実施例1
平均粒径30nm、BET比表面積254m2/gのカーボンブラック100重量部と軟化点110℃、メタフェーズ量(QI量)13%の光学的等方性ピッチ50重量部を加熱ニーダーで混捏し、これを非酸化性雰囲気下1000℃で焼成する。これを平均粒径2μmに粉砕し、リチウムイオンキャパシタ用負極活物質を得た。
平均粒径30nm、BET比表面積1000m2/gのカーボンブラック100重量部と軟化点110℃、メタフェーズ量(QI量)13%の光学的等方性ピッチ100重量部を加熱ニーダーで混捏し、これを非酸化性雰囲気下1000℃で焼成する。これを平均粒径2μmに粉砕し、リチウムイオンキャパシタ用負極活物質を得た。
平均粒径30nm、BET比表面積1000m2/gのカーボンブラック100重量部と軟化点110℃、メタフェーズ量(QI量)13%の光学的等方性ピッチ30重量部を加熱ニーダーで混捏し、これを非酸化性雰囲気下1000℃で焼成する。これを平均粒径2μmに粉砕し、リチウムイオンキャパシタ用負極活物質を得た。
平均粒径30nm、BET比表面積254m2/gのカーボンブラック100重量部と軟化点110℃、メタフェーズ量(QI量)13%の光学的等方性ピッチ30重量部を加熱ニーダーで混捏し、これを非酸化性雰囲気下1000℃で焼成する。これを平均粒径2μmに粉砕し、リチウムイオンキャパシタ用負極活物質を得た。
平均粒径30nm、BET比表面積1000m2/gのカーボンブラック100重量部と軟化点110℃、メタフェーズ量(QI量)13%の光学的等方性ピッチ150重量部を加熱ニーダーで混捏し、これを非酸化性雰囲気下1000℃で焼成する。これを平均粒径2μmに粉砕し、リチウムイオンキャパシタ用負極活物質を得た。
平均粒径30nm、BET比表面積1000m2/gのカーボンブラック100重量部と軟化点110℃、メタフェーズ量(QI量)13%の光学的等方性ピッチ200重量部を加熱ニーダーで混捏し、これを非酸化性雰囲気下1000℃で焼成する。これを平均粒径2μmに粉砕し、リチウムイオンキャパシタ用負極活物質を得た。
実施例3で用いた炭化物を再度非酸化雰囲気下2000℃で焼成し、リチウムイオンキャパシタ用負極活物質を得た。
粉砕後の平均粒径を5μmとした以外は実施例2と同様に作製した。
粉砕後の平均粒径を10μmとした以外は実施例2と同様に作製した。
光学的等方性ピッチ60重量部とした以外は実施例1と同様に作製した。
平均粒径34nm、BET比表面積1270m2/gのカーボンブラック100重量部と軟化点110℃、メタフェーズ量(QI量)13%の光学的等方性ピッチ100重量部を加熱ニーダーで混捏し、これを非酸化性雰囲気下1000℃で焼成する。これを平均粒径2μmに粉砕し、リチウムイオンキャパシタ用負極活物質を得た。
平均粒径48nm、BET比表面積39m2/gのカーボンブラック100重量部と軟化点110℃、メタフェーズ量(QI量)13%の光学的等方性ピッチ133重量部を加熱ニーダーで混捏し、これを非酸化性雰囲気下1000℃で焼成する。これを平均粒径2μmに粉砕し、リチウムイオンキャパシタ用負極活物質を得た。
平均粒径48nm、BET比表面積39m2/gのカーボンブラック100重量部と軟化点110℃、メタフェーズ量(QI量)13%の光学的等方性ピッチ54重量部を加熱ニーダーで混捏し、これを非酸化性雰囲気下1000℃で焼成する。これを平均粒径2μmに粉砕し、負極活物質を得た。
平均粒径24nm、BET比表面積117m2/gのカーボンブラック100重量部と軟化点110℃、メタフェーズ量(QI量)13%の光学的等方性ピッチ50重量部を加熱ニーダーで混捏し、これを非酸化性雰囲気下1000℃で焼成する。これを平均粒径12μmに粉砕し、リチウムイオンキャパシタ用負極活物質を得た。
P/V(P0-P)=(1/VmC)+{(C-1)/VmC}(P/P0)(1)
S=kVm ...................................................(2)
P0 :飽和蒸気圧
P:吸着平衡圧
V:吸着平衡圧Pにおける吸着量
Vm:単分子層吸着量
C:吸着熱などに関するパラメーター
S:比表面積
k:窒素単分子占有面積 0.162nm2
t=〔13.99/{0.034-log(P/P0)}〕0.5.........(3)
により求めた。
P0:飽和蒸気圧
P:吸着平衡圧
Claims (5)
- 電子顕微鏡法による平均粒子径が12~300nmのカーボンブラックを炭素前駆体と混捏し、800℃~3200℃で焼成し、粉砕して平均粒径(D50)を1~20μmとしたカーボンブラックと炭素質材料からなる多孔性複合炭素材料であって、BET比表面積が100m2/g以上350m2/g以下であるリチウムイオンキャパシタ用負極活物質。
- 請求項1において、前記カーボンブラックのBET比表面積が200~1500m2/gであるリチウムイオンキャパシタ用負極活物質。
- 請求項1~2のいずれかにおいて、カーボンブラック100重量部に対して、炭素前駆体が30重量部以上200重量部以下であるリチウムイオンキャパシタ用負極活物質。
- 請求項1~3のいずれかにおいて、リチウム金属を対極に用いて、測定温度25℃にて、電流値0.5mA/cm2で電圧値が0.01Vになるまで定電流充電を行った後、電流値が0.01mA/cm2になるまで定電圧充電を行った際の初回の充電容量が700mAh/g以上1600mAh/g以下である、リチウムイオンキャパシタ用負極活物質。
- 電子顕微鏡法による平均粒子径が12~300nmで且つBET比表面積が200~1500m2/gのカーボンブラック100重量部を炭素前駆体30重量部以上200重量部以下と混捏し、この混捏物を800℃~3200℃で焼成、もしくは黒鉛化し、平均粒径(D50)を1~20μmに粉砕し、比表面積を100m2/g以上350m2/g以下に調整するリチウムイオンキャパシタ用負極活物質の製造方法。
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JP5372568B2 (ja) * | 2009-03-27 | 2013-12-18 | 富士重工業株式会社 | 蓄電デバイスおよびその製造方法 |
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JP2006265005A (ja) * | 2005-03-22 | 2006-10-05 | Kagawa Industry Support Foundation | ナノ金属または金属酸化物担持活性炭の高効率製造方法 |
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