WO2016157735A1 - 非水電解質二次電池 - Google Patents
非水電解質二次電池 Download PDFInfo
- Publication number
- WO2016157735A1 WO2016157735A1 PCT/JP2016/001243 JP2016001243W WO2016157735A1 WO 2016157735 A1 WO2016157735 A1 WO 2016157735A1 JP 2016001243 W JP2016001243 W JP 2016001243W WO 2016157735 A1 WO2016157735 A1 WO 2016157735A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- positive electrode
- tungsten
- negative electrode
- carbon material
- secondary battery
- Prior art date
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- 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
-
- 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
- H01M4/626—Metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- 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 non-aqueous electrolyte secondary battery.
- Non-aqueous electrolyte secondary batteries are required to further improve output characteristics and durability, mainly for power supply applications such as electric vehicles (EV), hybrid electric vehicles (HEV), and electric tools.
- EV electric vehicles
- HEV hybrid electric vehicles
- Patent Document 1 describes a technique for improving safety during overcharge by using a positive electrode in which the surface of a positive electrode active material is coated with W, Mo, a Zr compound and a phosphoric acid compound.
- Patent Document 2 describes a technique for improving load characteristics by fixing carbon black on a graphite surface as a conductive agent.
- An object of the present invention is to provide a non-aqueous electrolyte secondary battery with improved output after charge storage more than before.
- the present invention is a non-aqueous electrolyte secondary battery including an electrode body having a structure in which a positive electrode plate and a negative electrode plate are laminated via a separator, wherein the positive electrode plate includes tungsten and a phosphoric acid compound, and the negative electrode
- the plate includes a graphite-based carbon material as an anode active material and an amorphous carbon material fixed to the surface thereof, and tungsten or a tungsten compound is included on the surface of the amorphous carbon material.
- the inventors of the present application have found that when a graphite carbon material and an amorphous carbon material fixed on the surface thereof are used as the negative electrode active material, tungsten is uniformly formed on the surface of the amorphous carbon material.
- tungsten is uniformly formed on the surface of the amorphous carbon material.
- the phosphate compound is lithium phosphate.
- the positive electrode plate contains at least one of tungsten in the positive electrode active material and a tungsten compound in the positive electrode mixture layer.
- the tungsten compound is WO 3.
- the amorphous carbon material is carbon black.
- the output after charge storage can be improved more than before.
- the basic configuration of the nonaqueous electrolyte secondary battery of the present embodiment is the same as the conventional one, and has a wound electrode body in which a positive electrode plate and a negative electrode plate are wound through a separator. The outermost peripheral surface of is covered with a separator.
- the positive electrode plate is formed on both surfaces of a positive electrode core made of aluminum or an aluminum alloy on both surfaces with a positive electrode core exposed portion in which the core is exposed in a strip shape along the longitudinal direction at one end in the width direction.
- a positive electrode mixture layer is formed on the substrate.
- the negative electrode plate is formed on both surfaces of the negative electrode core made of copper or copper alloy on both surfaces of the negative electrode core exposed portion in which the core is exposed in a strip shape along the longitudinal direction at one end in the width direction. As shown, a negative electrode mixture layer is formed.
- the positive electrode plate and the negative electrode plate are wound through a separator and formed into a flat shape to produce a flat wound electrode body. At this time, a positive electrode core exposed portion wound around one end of the flat wound electrode body is formed, and a negative electrode core exposed portion wound around the other end is formed.
- the wound positive electrode core exposed portion is electrically connected to the positive electrode terminal via the positive electrode current collector.
- the wound negative electrode core exposed portion is electrically connected to the negative electrode terminal via the negative electrode current collector.
- the positive electrode current collector and the positive electrode terminal are preferably made of aluminum or an aluminum alloy.
- the negative electrode current collector and the negative electrode terminal are preferably made of copper or a copper alloy.
- the positive terminal is fixed to the sealing body via an insulating member, and the negative terminal is also fixed to the sealing body via an insulating member.
- the flat wound electrode body is housed in the rectangular exterior body while being covered with a resin insulating sheet.
- the sealing body is brought into contact with the opening of the metal rectangular outer casing, and the contact portion between the sealing body and the rectangular outer casing is laser-welded.
- the sealing body has an electrolyte solution injection port, and a non-aqueous electrolyte solution is injected from the electrolyte solution injection port, and then the electrolyte solution injection port is sealed with a blind rivet or the like.
- a non-aqueous electrolyte secondary battery is an example, and other configurations, for example, a non-aqueous electrolyte secondary battery in which a non-aqueous electrolyte and a wound electrode body are inserted into a laminate outer package may be used. .
- a positive electrode is comprised by positive electrode collectors, such as metal foil, and the positive mix layer formed on the positive electrode collector, for example.
- the positive electrode current collector a metal foil that is stable in the potential range of the positive electrode such as aluminum, a film in which the metal is disposed on the surface layer, or the like can be used.
- the positive electrode mixture layer preferably contains a phosphoric acid compound in addition to a lithium transition metal oxide that is a positive electrode active material, and further contains a conductive agent and a binder.
- the positive electrode is coated with a positive electrode mixture slurry containing a positive electrode active material, a binder, etc. on the positive electrode current collector, dried, and then rolled to form a positive electrode mixture layer on both sides of the current collector. It can be manufactured by forming.
- the positive electrode active material a material containing a lithium transition metal oxide is used, and a material containing a phosphoric acid compound (Li 3 PO 4 or the like) in the positive electrode mixture layer is used. It is preferable that the lithium transition metal oxide contains tungsten. Further, it is preferable that a tungsten compound is contained in the positive electrode mixture layer. More preferably, the lithium transition metal oxide contains tungsten, and further, a tungsten compound is contained in the positive electrode mixture layer.
- the lithium transition metal oxide preferably contains cobalt (Co) and manganese (Mn) in addition to Ni, and contains aluminum (Al) in addition to Ni or Co or in place of Mn. It is also suitable to contain.
- the proportion of Ni in the M is preferably 30 mol% or more.
- Ni is particularly preferably contained in the state of Ni 3+ .
- the lithium transition metal oxide containing Ni 3+ include nickel cobalt lithium manganate having a molar ratio of Ni> Mn, and the molar ratio of Ni, Co, and Mn is, for example, 3: 5: 2, 4: 3. : 3, 5: 2: 3, 5: 3: 2, 6: 2: 2, 7: 1: 2, 7: 2: 1, 8: 1: 1.
- the molar ratio of Ni, Co, and Al is, for example, 80: 15: 5, 85: 12: 3, and 90: 7: 3.
- Examples of elements other than Ni, Co, and Mn include transition metal elements such as zirconium (Zr), alkali metal elements, alkaline earth metal elements, and 12th to 14th group elements.
- transition metal elements such as zirconium (Zr), alkali metal elements, alkaline earth metal elements, and 12th to 14th group elements.
- Examples include molybdenum (Mo), tantalum (Ta), tin (Sn), sodium (Na), potassium (K), barium (Ba), strontium (Sr), calcium (Ca), and the like.
- Zr has a function of stabilizing the crystal structure of a lithium transition metal oxide, for example.
- Lithium transition metal oxide is, for example, secondary particles formed by aggregation of primary particles (not separated into primary particles by ultrasonic dispersion or the like).
- the particle size of the lithium transition metal oxide is not particularly limited, but is preferably a volume average particle size of 0.1 ⁇ m to 20 ⁇ m measured by a laser diffraction method. When the particle size of the lithium transition metal oxide is within the above range, it becomes easy to achieve both good ionic conductivity and electronic conductivity of the positive electrode mixture layer. Moreover, it is preferable that the specific surface area measured by BET method of a lithium transition metal oxide is large from viewpoints, such as the retainability of electrolyte solution, a diffusivity.
- the content of W in the lithium transition metal oxide is preferably 0.05 mol% or more and 10 mol% or less, more preferably 0.1 mol% or more and 5 mol% or less, with respect to the metal element excluding Li of the lithium transition metal oxide. 0.2 mol% or more and 3 mol% or less is particularly preferable.
- W is a mixture of a composite oxide containing, for example, Ni, Co, Mn, etc., a lithium compound such as lithium hydroxide, and a tungsten compound such as W or tungsten oxide when synthesizing a lithium transition metal oxide. It can be made to contain in the said oxide by baking. W is preferably dissolved in the lithium transition metal oxide. At the time of synthesizing the lithium transition metal oxide, W can be dissolved in the lithium transition metal oxide by mixing and firing a composite oxide containing Ni, Co, Mn, and the like and W. In addition, W may be precipitated at the interface of the primary particles or the surface of the secondary particles in an oxide or metal state.
- the content of the phosphoric acid compound and the tungsten oxide in the positive electrode mixture layer is preferably 0.01 wt% or more and 5 wt% or less, more preferably 0.05 wt% or more and 4 wt% or less with respect to the total weight of the positive electrode active material. 0.1 wt% or more and 3 wt% or less is particularly preferable.
- the particle diameters of the phosphoric acid compound and the tungsten oxide are preferably smaller than the particle diameter of the positive electrode active material, for example, 25% or less of the average particle diameter of the positive electrode active material.
- Examples of the phosphoric acid compound mixed in the positive electrode mixture layer include a group consisting of lithium phosphate, lithium dihydrogen phosphate, cobalt phosphate, nickel phosphate, manganese phosphate, potassium phosphate, and ammonium dihydrogen phosphate. There may be mentioned at least one selected. Of these, it is particularly preferable to use lithium phosphate.
- the tungsten compound to be mixed in the positive electrode mixture layer is not particularly limited, but tungsten oxide is preferable, and WO 3 in which the oxidation number of tungsten is the most stable hexavalent is preferable.
- the phosphoric acid compound and the tungsten oxide can be mechanically mixed with the positive electrode active material, for example, and adhered to the surface of the active material particles.
- the phosphoric acid compound and the tungsten oxide may be added to mix them with the positive electrode mixture layer.
- the phosphoric acid compound and the tungsten oxide are added to the positive electrode mixture layer using the former method. Thereby, the phosphoric acid compound and the tungsten oxide can be efficiently present in the vicinity of the surface of the active material particles.
- the presence of the phosphoric acid compound in the positive electrode mixture layer makes it possible to adjust the reaction rate at which a part of tungsten elutes and to form a surface film in a good shape on the negative electrode.
- the conductive agent is used to increase the electrical conductivity of the positive electrode mixture layer.
- the conductive agent include carbon materials such as carbon black, acetylene black, ketjen black, and graphite. These may be used alone or in combination of two or more.
- the binder is used to maintain a good contact state between the positive electrode active material and the conductive agent and to increase the binding property of the positive electrode active material and the like to the surface of the positive electrode current collector.
- the binder include fluorine resins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimide resins, acrylic resins, and polyolefin resins.
- these resins, carboxymethyl cellulose (CMC) or a salt thereof (CMC-Na, CMC-K, CMC-NH 4 etc., may be a partially neutralized salt), polyethylene oxide (PEO), etc. May be used in combination. These may be used alone or in combination of two or more.
- a negative electrode is comprised by the negative electrode collector which consists of metal foil etc., for example, and the negative mix layer formed on the said collector.
- the negative electrode current collector a metal foil that is stable in the potential range of a negative electrode such as copper, a film in which the metal is disposed on the surface layer, or the like can be used.
- the negative electrode mixture layer preferably contains a binder in addition to the negative electrode active material.
- a negative electrode mixture slurry containing a negative electrode active material and a binder is applied to the negative electrode current collector, the coating film is dried, and then rolled to form a negative electrode mixture layer on both sides of the current collector It can produce by doing.
- the negative electrode active material includes graphite-based carbon materials such as natural graphite and artificial graphite, which can reversibly occlude / release lithium ions, and amorphous carbon materials.
- ⁇ ⁇ Graphite-based carbon material is a carbon material with a developed graphite crystal structure, and examples thereof include natural graphite and artificial graphite. These may have a scale shape or may be subjected to a spheronization process to be processed into a spherical shape.
- Artificial graphite is produced by subjecting petroleum, coal pitch, coke, etc. as raw materials to heat treatment at 2000 to 3000 ° C. or higher in an Atchison furnace or graphite heater furnace.
- the distance between d (002) planes by X-ray diffraction is preferably 0.338 nm or less, and the crystal thickness (Lc (002)) in the c-axis direction is preferably 30 to 1000 nm.
- the amorphous carbon material here is a carbon material in which the graphite crystal structure is not developed, and is an amorphous or microcrystalline carbon in a turbulent structure state. More specifically, X-ray diffraction This means that the d (002) plane interval by is 0.342 nm or more. Examples include hard carbon (non-graphitizable carbon), soft carbon (graphitizable carbon), carbon black, carbon fiber, activated carbon, and the like. These production methods are not particularly limited. For example, it can be obtained by carbonizing a resin or a resin composition, and a thermoplastic resin such as a phenol-based thermosetting resin or polyacrylonitrile, a petroleum-based or coal-based tar or pitch can be used.
- a thermoplastic resin such as a phenol-based thermosetting resin or polyacrylonitrile, a petroleum-based or coal-based tar or pitch can be used.
- carbon black is obtained by thermally decomposing hydrocarbon as a raw material
- examples of the thermal decomposition method include a thermal method and an acetylene decomposition method.
- examples of the incomplete combustion method include a contact method, a lamp / pine smoke method, a gas furnace method, and an oil furnace method.
- Specific examples of carbon black produced by these production methods include acetylene black, ketjen black, thermal black, furnace black, and the like.
- the surface of these amorphous carbon materials may be further coated with another amorphous or amorphous carbon.
- the amorphous carbon material is preferably present in a state of being fixed to the surface of the graphite-based carbon material.
- the term “fixed” refers to a state in which they are chemically / physically bonded. Even if the negative electrode active material of the present invention is stirred in water or an organic solvent, the graphite-based carbon material and the amorphous carbon are mixed. It means that the material is not released.
- the ratio of the graphite-based carbon material to the amorphous carbon material is not particularly limited, but it is preferable that the ratio of the amorphous carbon material having excellent Li occlusion is large, and the ratio of the amorphous carbon material is 0. 0% in the active material. 5 wt% or more, more preferably 2 wt% or more. However, if the amorphous carbon material becomes excessive, it becomes impossible to uniformly adhere to the graphite surface, so it is preferable to set the upper limit in consideration of this point.
- a method for fixing amorphous carbon to a graphite-based carbon material a method in which petroleum-based or coal-based tar or pitch is added to an amorphous carbon material and mixed with the graphite-based carbon material, followed by heat treatment, or graphite particles Mechano-fusion method that coats by applying compressive shear stress between solid and amorphous carbon, solid phase method that coats by sputtering method, etc., graphite is dissolved by dissolving amorphous carbon in a solvent such as toluene Then, there is a liquid phase method in which heat treatment is performed.
- the primary particle diameter of amorphous carbon is preferably small from the viewpoint of the diffusion distance of Li, and the specific surface area is preferably large because the reaction surface area for the Li storage reaction is large. However, if it is too large, excessive reaction occurs on the surface, leading to an increase in resistance. Therefore, the specific surface area of amorphous carbon is preferably 5 m 2 / g or more and 200 m 2 / g or less. In order to reduce the excessive specific surface area, the primary particle diameter is preferably 20 nm to 1000 nm, more preferably 40 nm to 100 nm, and it is preferably not a hollow structure in which cavities exist in the particles.
- Fluorine resin, PAN, polyimide resin, acrylic resin, polyolefin resin, etc. can be used as the binder as in the case of the positive electrode.
- PAN polyimide resin
- acrylic resin polyolefin resin
- PAN polyimide resin
- acrylic resin polyolefin resin
- PVA polyvinyl alcohol
- a porous sheet having ion permeability and insulating properties is used.
- the porous sheet include a microporous thin film, a woven fabric, and a nonwoven fabric.
- olefinic resins such as polyethylene and polypropylene, cellulose and the like are suitable.
- the separator may be a laminate having a cellulose fiber layer and a thermoplastic resin fiber layer such as an olefin resin.
- the electrolyte is a nonaqueous electrolyte containing, for example, a nonaqueous solvent and an electrolyte salt dissolved in the nonaqueous solvent.
- the nonaqueous electrolyte is not limited to a liquid electrolyte (nonaqueous electrolyte solution), and may be a solid electrolyte using a gel polymer or the like.
- the non-aqueous solvent for example, esters, ethers, nitriles, amides such as dimethylformamide, a mixed solvent of two or more of these, and the like can be used.
- a sulfone group-containing compound such as propane sultone may also be used.
- the non-aqueous solvent may contain a halogen-substituted product in which at least a part of hydrogen in these solvents is substituted with a halogen atom such as fluorine.
- esters examples include chain carboxylic acid ester.
- the chain carboxylic acid ester is not particularly limited, but is preferably a chain carboxylic acid ester having 3 to 5 carbon atoms. Specific examples include methyl propionate, ethyl propionate, methyl acetate, ethyl acetate, propyl acetate and the like.
- esters other than the chain carboxylic acid ester
- examples of the esters include cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, vinylene carbonate (VC), dimethyl carbonate (DMC), ethyl Chain carbonates such as ethyl carbonate (EMC), diethyl carbonate (DEC), methyl propyl carbonate, ethyl propyl carbonate, methyl isopropyl carbonate, and cyclic carboxylic acid esters such as ⁇ -butyrolactone (GBL) and ⁇ -valerolactone (GVL) Etc.
- cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, vinylene carbonate (VC), dimethyl carbonate (DMC), ethyl Chain carbonates such as ethyl carbonate (EMC), diethyl carbonate (DEC), methyl propyl carbonate, ethyl
- ethers examples include 1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, propylene oxide, 1,2-butylene oxide, 1,3-dioxane, 1,4 -Cyclic ethers such as dioxane, 1,3,5-trioxane, furan, 2-methylfuran, 1,8-cineol, crown ether, 1,2-dimethoxyethane, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether , Dihexyl ether, ethyl vinyl ether, butyl vinyl ether, methyl phenyl ether, ethyl phenyl ether, butyl phenyl ether, pentyl phenyl ether, methoxy toluene, benzyl ethyl ether, diphenyl ether, diphen
- nitriles examples include acetonitrile, propionitrile, butyronitrile, valeronitrile, n-heptanenitrile, succinonitrile, glutaronitrile, adiponitrile, pimeonitrile, 1,2,3-propanetricarbonitrile, 1,3 , 5-pentanetricarbonitrile and the like.
- halogen-substituted product examples include fluorinated cyclic carbonates such as fluoroethylene carbonate (FEC), fluorinated chain carbonates, and fluorinated chain carboxylates such as methyl fluoropropionate (FMP).
- FEC fluoroethylene carbonate
- FMP fluorinated chain carboxylates
- FEC fluoroethylene carbonate
- FMP fluorinated chain carboxylates
- the electrolyte salt is preferably a lithium salt.
- the lithium salt LiBF 4, LiClO 4, LiPF 6, LiAsF 6, LiSbF 6, LiAlCl 4, LiSCN, LiCF 3 SO 3, LiC (C 2 F 5 SO 2), LiCF 3 CO 2, Li (P (C 2 O 4 ) F 4 ), Li (P (C 2 O 4 ) F 2 ), LiPF 6-x (C n F 2n + 1 ) x (1 ⁇ x ⁇ 6, n is 1 or 2), LiB 10 Cl 10 , LiCl, LiBr, LiI, chloroborane lithium, lower aliphatic lithium carboxylate, Li 2 B 4 O 7 , Li (B (C 2 O 4 ) 2 ) [lithium-bisoxalate borate (LiBOB)], li (B (C 2 O 4 ) F 2) boric acid salts such as, LiN (FSO 2) 2, LiN (C l F 2l + 1 SO 2) (C m F 2m + 1
- lithium salts may be used alone or in combination of two or more.
- at least a fluorine-containing lithium salt from the viewpoints of ion conductivity, electrochemical stability, and the like, and for example, LiPF 6 is preferably used.
- a fluorine-containing lithium salt and a lithium salt for example, LiBOB
- the concentration of the lithium salt is preferably 0.8 to 1.8 mol per liter of the nonaqueous solvent. In particular, 1.2 to 1.5 mol is more preferable for high output.
- tungsten contained in the positive electrode elutes during charging of the nonaqueous electrolyte secondary battery, migrates to the negative electrode, and deposits on the surface of the negative electrode.
- fine and uniform tungsten or tungsten compound is deposited on the surface of the negative electrode active material, more specifically, on the amorphous carbon material on the surface of the negative electrode active material.
- the negative electrode contains a graphite-based carbon material, an amorphous carbon material, and tungsten or a tungsten compound.
- Nickel cobalt manganese composite hydroxide obtained by mixing and coprecipitating NiSO 4 , CoSO 4 , and MnSO 4 in an aqueous solution was fired to prepare a nickel cobalt manganese composite oxide.
- the molar ratio of the composite oxide, lithium hydroxide, and tungsten oxide (WO 3 ), lithium, nickel cobalt manganese, which is a transition metal main component, and tungsten is 1.15: 1: 0.005.
- the mixture was mixed using a rough mortar.
- the mixture was fired in an air atmosphere and then pulverized to obtain a lithium transition metal oxide (positive electrode active material) containing tungsten.
- the positive electrode active material, WO 3 is mixed with 0.5 wt% of the active material, and Li 3 PO 4 is mixed with 1 wt% of the active material.
- These mixtures, carbon black, and polyvinylidene fluoride (PVDF) Were mixed in a weight ratio of 91: 7: 2.
- NMP N-methyl-2-pyrrolidone
- the positive electrode mixture slurry was applied on the aluminum foil as the positive electrode current collector, and the coating film was dried to form a positive electrode mixture layer on the aluminum foil.
- the current collector on which the mixture layer was formed was cut into a predetermined size, rolled and attached with an aluminum tab to obtain a positive electrode.
- the negative electrode mixture layer was formed by applying this negative electrode mixture slurry to a current collector made of copper foil. Then, it dried and removed the water
- Ethylene carbonate (EC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC) were mixed at a volume ratio of 3: 3: 4.
- LiPF 6 was dissolved in the mixed solvent to a concentration of 1.2 mol / L to prepare a nonaqueous electrolytic solution.
- the wound electrode body For producing the wound electrode body, one positive electrode, one negative electrode, and one separator made of a polyethylene microporous film were used. First, the positive electrode and the negative electrode were opposed to each other with a separator interposed therebetween. Next, it was wound in a spiral shape using a cylindrical core. At this time, both the positive electrode current collecting tab and the negative electrode current collecting tab were arranged so as to be positioned on the outermost peripheral side in the respective electrodes. Thereafter, the winding core was pulled out to produce a wound electrode body.
- non-aqueous electrolyte and the wound electrode body thus prepared were inserted into an aluminum laminate outer package in a glove box under an argon atmosphere, and a laminate-type non-aqueous electrolyte secondary battery was produced and tested. This was designated as cell A1.
- Test cell A2 was produced in the same manner as in Experimental Example 1 except that WO 3 was not added during the production of the positive electrode.
- Test cell A3 was produced in the same manner as in Experimental Example 1 except that no tungsten oxide was mixed during the production of the positive electrode active material.
- Test cell B1 was produced in the same manner as in Experimental Example 1 except that the amorphous carbon material was not formed when the negative electrode was produced.
- Test cell B2 was produced in the same manner as in Experimental Example 1 except that Li 3 PO 4 was not mixed during the production of the positive electrode.
- Test cell B3 was prepared in the same manner as in Experimental Example 1 except that Li 3 PO 4 was not mixed during the production of the positive electrode and no amorphous carbon material was formed during the production of the negative electrode.
- Test cell B4 was produced in the same manner as in Experimental Example 2 except that the amorphous carbon material was not formed when the negative electrode was produced.
- Test cell B5 was produced in the same manner as in Experimental Example 3, except that the amorphous carbon material was not formed during the production of the negative electrode.
- Test cell B6 was produced in the same manner as in Experimental Example 3 except that Li 3 PO 4 was not mixed during the production of the positive electrode.
- Test cell B7 was produced in the same manner as in Experimental Example 3, except that Li 3 PO 4 was not mixed during the production of the positive electrode and no amorphous carbon material was formed during the production of the negative electrode.
- Test cell B8 was produced in the same manner as in Experimental Example 3, except that WO 3 was not added at the time of producing the positive electrode.
- Test cell B9 was produced in the same manner as in Experimental Example 3 except that WO 3 and Li 3 PO 4 were not mixed during the production of the positive electrode.
- the battery was charged to SOC 70% at a charging current of 1.2 mA / cm 2 and left at room temperature (25 ° C.) for 1 day (aging). Thereafter, the battery was charged with a charging current of 1.2 mA / cm 2 to a voltage of 4.1 V, and further charged with 4.1 V until the charging current reached 0.06 mA / cm 2 . After the rest, initial charging / discharging was performed by discharging to 2.5 V at a current of 1.2 mA / cm 2 .
- the battery after the above charging and discharging cycle charged to the voltage 4.1V at a charging current 1.2 mA / cm 2, was charged to further charge current 4.1V is 0.06 mA / cm 2 Then, it preserve
- the battery after storage was discharged at a current of 1.2 mA / cm 2 to 2.5 V, and then charged to 50% of the discharge capacity obtained by performing one cycle of the above charge / discharge cycle.
- test cells A1 to A3 of Experimental Examples 1 to 3 including positive electrode containing tungsten, Li 3 PO 4 mixed, and an amorphous carbon material fixed to the surface of the negative electrode active material
- an excellent resistance reduction can be achieved as compared with the test cells B1 to B9 of 4 to 12. This is because an appropriate amount of tungsten was eluted from the positive electrode to the negative electrode surface, and a good film was formed on the surface of the amorphous carbon material to reduce the reaction resistance at the active material-electrolyte interface.
- Test Cell B2 of Experimental Example 5 and Test Cell B6 of Experimental Example 6 since Li 3 PO 4 was not added, the amount of tungsten eluted was small, and tungsten or tungsten compound was uniform on the amorphous carbon material. It was considered that the resistance could not be sufficiently reduced because a non-uniform film was formed without being dispersed.
- the presence of tungsten and a phosphoric acid compound in the positive electrode causes tungsten to elute on the negative electrode surface after charging, and forms a good film containing tungsten or a tungsten compound on the surface of the amorphous carbon material.
- the reaction resistance at the electrolyte interface can be reduced, and higher output characteristics can be maintained even after storage after charging.
- Experimental Example 1 Aging was carried out by allowing to stand at room temperature for 1 day as described above.
- Experimental Example 13 Initial charge / discharge was performed without aging to obtain a test cell C1.
- Experimental Example 14 Aging was performed by leaving at 60 ° C. for 1 day to obtain a test cell C2.
- Table 2 shows the value obtained by normalizing the amount of W in the negative electrode mixture with the amount of inert Li together with the value showing the IV resistance after storage when the test cell B9 of Experimental Example 12 is used as a reference.
- the resistance of the coating was evaluated by standardizing the amount of W using the amount of inert Li in the negative electrode mixture.
- the amount of inactive Li was calculated from the difference between the total amount of Li obtained and the amount of active Li, and the amount of W was normalized.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
正極は、例えば金属箔等の正極集電体と、正極集電体上に形成された正極合剤層とで構成される。正極集電体には、アルミニウムなどの正極の電位範囲で安定な金属の箔、当該金属を表層に配置したフィルム等を用いることができる。正極合剤層は、正極活物質であるリチウム遷移金属酸化物の他に、リン酸化合物を含み、さらに導電剤、及び結着剤を含むことが好適である。正極は、例えば正極集電体上に正極活物質、結着剤等を含む正極合剤スラリーを塗布し、塗膜を乾燥させた後、圧延して正極合剤層を集電体の両面に形成することにより作製できる。
負極は、例えば金属箔等からなる負極集電体と、当該集電体上に形成された負極合剤層で構成される。負極集電体には、銅等の負極の電位範囲で安定な金属の箔、当該金属を表層に配置したフィルム等を用いることができる。負極合剤層は、負極活物質の他に、結着剤を含むことが好ましい。負極は、例えば負極集電体に負極活物質、結着剤などを含む負極合剤スラリーを塗布し、塗膜を乾燥させた後、圧延して負極合剤層を集電体の両面に形成することにより作製できる。
セパレータには、イオン透過性及び絶縁性を有する多孔性シートが用いられる。多孔性シートの具体例としては、微多孔薄膜、織布、不織布等が挙げられる。セパレータの材質としては、ポリエチレン、ポリプロピレン等のオレフィン系樹脂、セルロースなどが好適である。セパレータは、セルロース繊維層及びオレフィン系樹脂等の熱可塑性樹脂繊維層を有する積層体であってもよい。
電解質は、例えば非水溶媒と、非水溶媒に溶解した電解質塩とを含む非水電解質である。非水電解質は、液体電解質(非水電解液)に限定されず、ゲル状ポリマー等を用いた固体電解質であってもよい。非水溶媒には、例えばエステル類、エーテル類、ニトリル類、ジメチルホルムアミド等のアミド類、及びこれらの2種以上の混合溶媒等を用いることができる。また、プロパンスルトン等のスルホン基含有化合物を用いてもよい。非水溶媒は、これら溶媒の水素の少なくとも一部をフッ素等のハロゲン原子で置換したハロゲン置換体を含有していてもよい。
[正極活物質の作製]
NiSO4、CoSO4、及びMnSO4を水溶液中で混合し、共沈させることで得たニッケルコバルトマンガン複合水酸化物を焼成して、ニッケルコバルトマンガン複合酸化物を作製した。次に、当該複合酸化物と水酸化リチウムとタングステン酸化物(WO3)とを、リチウムと、遷移金属主体であるニッケルコバルトマンガンと、タングステンのモル比が1.15:1:0.005になるように、らいかい乳鉢を用いて混合した。この混合物を空気雰囲気中にて焼成した後、粉砕することにより、タングステンが含有したリチウム遷移金属酸化物(正極活物質)を得た。得られた正極活物質をICPで元素分析したところ、遷移金属全体に対する各元素のモル比はNi:Co:Mn:W=47:27:26:0.5であった。
上記の正極活物質と、WO3を活物質に対して0.5wt%、Li3PO4を活物質に対して1wt%混合し、これらの混合物と、カーボンブラックと、ポリフッ化ビニリデン(PVDF)とを、91:7:2の重量比で混合した。当該混合物に分散媒としてN-メチル-2-ピロリドン(NMP)を添加して混練し、正極合剤スラリーを調製した。次に、正極集電体であるアルミニウム箔上に正極合剤スラリーを塗布し、塗膜を乾燥させて、アルミニウム箔に正極合剤層を形成した。上記の合剤層を形成した集電体を所定のサイズに切り出し、圧延してアルミニウムタブを取り付け、正極とした。
天然黒鉛と、ピッチと、カーボンブラックを質量比が91:5:4になるよう混合し、黒鉛粒子の表面をピッチとカーボンブラックで被覆した。次に、得られた混合物を1500℃の不活性ガス雰囲気で24時間焼成し、焼成物を解砕・粉砕して負極活物質を調製した。作製した負極活物質と、増粘剤としてのカルボキシメチルセルロース(CMC)と、結着剤としてのスチレンブタジエンゴム(SBR)とを、それぞれ質量比で98:1:1となるように秤量し、これらを水に分散させて負極合剤スラリーを調製した。この負極合剤スラリーを銅箔からなる集電体に塗布することにより、負極合剤層を形成した。その後、乾燥して水分を除去し、圧延ローラーを用いて所定の厚さまで圧延し、所定のサイズに裁断してニッケルタブを取り付け、負極とした。
エチレンカーボネート(EC)と、エチルメチルカーボネート(EMC)と、ジメチルカーボネート(DMC)を3:3:4の体積比で混合した。当該混合溶媒にLiPF6を1.2mol/Lの濃度となるように溶解させて非水電解液を調製した。
巻回電極体の作製には、上記の正極を1枚、上記の負極を1枚、ポリエチレン製微多孔膜からなるセパレータを1枚用いた。まず、正極と負極とをセパレータを介して互いに絶縁した状態で対向させた。次に、円柱状の巻芯を用いて渦巻き状に巻回した。この際、正極集電タブ及び負極集電タブは、共にそれぞれの電極内における最外周側に位置するように配置した。その後、巻芯を引き抜いて巻回電極体を作製した。
正極作製時にWO3を添加しなかった以外は実験例1と同様にして試験セルA2を作製した。
正極活物質作製時にタングステン酸化物を混合しなかった以外は実験例1と同様にして試験セルA3を作製した。
負極作製時に非晶質炭素材料を形成しなかった以外は実験例1と同様にして試験セルB1を作製した。
正極作製時にLi3PO4を混合しなかった以外は実験例1と同様にして試験セルB2を作製した。
正極作製時にLi3PO4を混合せず、負極作製時に非晶質炭素材を形成しなかった以外は実験例1と同様にして試験セルB3を作製した。
負極作製時に非晶質炭素材を形成しなかった以外は実験例2と同様にして試験セルB4を作製した。
負極作製時に非晶質炭素材を形成しなかった以外は実験例3と同様にして試験セルB5を作製した。
正極作製時にLi3PO4を混合しなかった以外は実験例3と同様にして試験セルB6を作製した。
正極作製時にLi3PO4を混合せず、負極作製時に非晶質炭素材を形成しなかった以外は実験例3と同様にして試験セルB7を作製した。
正極作製時にWO3を添加しなかった以外は実験例3と同様にして試験セルB8を作製した。
正極作製時にWO3及びLi3PO4を混合しなかった以外は実験例3と同様にして試験セルB9を作製した。
充電電流1.2mA/cm2でSOC70%まで充電し、常温(25℃)で1日放置した(エージング)。その後、充電電流1.2mA/cm2で電圧4.1Vまで充電し、更に4.1Vで充電電流が0.06mA/cm2になるまで充電した。休止後、電流1.2mA/cm2で2.5Vまで放電することで初期充放電とした。その後、充電電流1.2mA/cm2で電圧4.1Vまで充電し、更に4.1Vで充電電流が0.06mA/cm2になるまで充電し、休止後、電流1.2mA/cm2で2.5Vまで放電する充放電サイクルを5サイクル行った。
具体的には、
実験例1:上記のように常温で1日放置してエージングを行った。
実験例13:エージングせずに初期充放電を行い、試験セルC1とした。
実験例14:60℃で1日放置してエージングを行い、試験セルC2とした。
試験後の負極極板をイオン交換水に浸漬し、発生した水素ガス量から活性Li量を算出した。さらに、試料合剤に王水を加えて加熱した後、濾別して得られた溶液をICPにより元素分析することで、合剤に含まれる全Li量、及びW量を測定した。
Claims (7)
- 正極板と負極板がセパレータを介して積層された構造を有する電極体を備えた非水電解質二次電池であって、
前記正極板は、タングステン及びリン酸化合物を含有し、
前記負極板は、負極活物質として黒鉛系炭素材及びその表面に固着された非晶質炭素材を含み、
前記非晶質炭素材表面に、タングステンまたはタングステン化合物を含む、非水電解質二次電池。 - 前記正極板は、正極活物質にタングステンを含有するか、正極合剤層内にタングステン化合物を含有するか、の少なくとも一方である、請求項1に記載の非水電解質二次電池。
- 前記リン酸化合物は、リン酸リチウムである、請求項1~2のいずれかに記載の非水電解質二次電池。
- 前記タングステン化合物は、WO3である、請求項2に記載の非水電解質二次電池。
- 前記非晶質炭素材は、カーボンブラックである、請求項1~4のいずれかに記載の非水電解質二次電池。
- 前記タングステンまたはタングステン化合物は、充電により正極から溶出して負極活物質表面に析出した、請求項1~5のいずれかに記載の非水電解質二次電池。
- 前記非晶質炭素材表面のタングステンまたはタングステン化合物中におけるタングステンの、不活性リチウムに対する比率は、2.07以下である、請求項1~6のいずれかに記載の非水電解質二次電池。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201680013543.4A CN107431239B (zh) | 2015-03-30 | 2016-03-08 | 非水电解质二次电池 |
US15/554,982 US10529978B2 (en) | 2015-03-30 | 2016-03-08 | Nonaqueous electrolyte secondary battery |
JP2017509223A JP6728134B2 (ja) | 2015-03-30 | 2016-03-08 | 非水電解質二次電池 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015-069705 | 2015-03-30 | ||
JP2015069705 | 2015-03-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016157735A1 true WO2016157735A1 (ja) | 2016-10-06 |
Family
ID=57004134
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2016/001243 WO2016157735A1 (ja) | 2015-03-30 | 2016-03-08 | 非水電解質二次電池 |
Country Status (4)
Country | Link |
---|---|
US (1) | US10529978B2 (ja) |
JP (1) | JP6728134B2 (ja) |
CN (1) | CN107431239B (ja) |
WO (1) | WO2016157735A1 (ja) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018030176A1 (ja) * | 2016-08-09 | 2018-02-15 | パナソニックIpマネジメント株式会社 | 非水電解質二次電池 |
WO2018173521A1 (ja) * | 2017-03-22 | 2018-09-27 | パナソニックIpマネジメント株式会社 | 二次電池用負極およびその製造方法並びに二次電池 |
JP2019050155A (ja) * | 2017-09-11 | 2019-03-28 | トヨタ自動車株式会社 | 非水電解液二次電池 |
JPWO2018179936A1 (ja) * | 2017-03-31 | 2020-02-27 | パナソニック株式会社 | 非水電解質二次電池用正極活物質及びその製造方法 |
KR20200028979A (ko) * | 2017-07-14 | 2020-03-17 | 바스프 에스이 | 전극 활물질의 제조 방법 |
WO2020241105A1 (ja) * | 2019-05-30 | 2020-12-03 | パナソニックIpマネジメント株式会社 | 二次電池用の負極活物質、及び二次電池 |
JP2021061212A (ja) * | 2019-10-09 | 2021-04-15 | 三菱マテリアル株式会社 | 負極材料、電池、負極材料の製造方法、及び電池の製造方法 |
WO2023224070A1 (ja) * | 2022-05-20 | 2023-11-23 | 株式会社Gsユアサ | 非水電解質蓄電素子 |
WO2024029333A1 (ja) * | 2022-08-01 | 2024-02-08 | 株式会社Gsユアサ | 非水電解質蓄電素子 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010040383A (ja) * | 2008-08-06 | 2010-02-18 | Sony Corp | 正極活物質の製造方法および正極活物質 |
JP2012038534A (ja) * | 2010-08-06 | 2012-02-23 | Hitachi Ltd | リチウム二次電池用正極材料,リチウム二次電池及びそれを用いた二次電池モジュール |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003346804A (ja) * | 2002-05-28 | 2003-12-05 | Sony Corp | 負極材料、非水電解質電池及び負極材料の製造方法 |
US8080335B2 (en) * | 2006-06-09 | 2011-12-20 | Canon Kabushiki Kaisha | Powder material, electrode structure using the powder material, and energy storage device having the electrode structure |
JP2008108689A (ja) | 2006-09-29 | 2008-05-08 | Sanyo Electric Co Ltd | 非水電解質二次電池 |
CN101013751A (zh) * | 2007-02-12 | 2007-08-08 | 王海波 | 一种稀土掺杂的球形锂离子电池正极材料及其制造方法 |
JP2010231958A (ja) * | 2009-03-26 | 2010-10-14 | Sanyo Electric Co Ltd | 非水電解質二次電池 |
JP5589751B2 (ja) * | 2010-03-02 | 2014-09-17 | ソニー株式会社 | 非水電解質電池および非水電解質 |
WO2014128903A1 (ja) * | 2013-02-22 | 2014-08-28 | 株式会社 日立製作所 | リチウムイオン二次電池 |
US10297826B2 (en) * | 2015-02-27 | 2019-05-21 | Sanyo Electric Co., Ltd. | Nonaqueous electrolyte secondary battery |
-
2016
- 2016-03-08 US US15/554,982 patent/US10529978B2/en active Active
- 2016-03-08 JP JP2017509223A patent/JP6728134B2/ja active Active
- 2016-03-08 CN CN201680013543.4A patent/CN107431239B/zh active Active
- 2016-03-08 WO PCT/JP2016/001243 patent/WO2016157735A1/ja active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010040383A (ja) * | 2008-08-06 | 2010-02-18 | Sony Corp | 正極活物質の製造方法および正極活物質 |
JP2012038534A (ja) * | 2010-08-06 | 2012-02-23 | Hitachi Ltd | リチウム二次電池用正極材料,リチウム二次電池及びそれを用いた二次電池モジュール |
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11024837B2 (en) | 2016-08-09 | 2021-06-01 | Panasonic Intellectual Property Management Co., Ltd. | Nonaqueous electrolyte secondary battery |
JPWO2018030176A1 (ja) * | 2016-08-09 | 2019-06-06 | パナソニックIpマネジメント株式会社 | 非水電解質二次電池 |
WO2018030176A1 (ja) * | 2016-08-09 | 2018-02-15 | パナソニックIpマネジメント株式会社 | 非水電解質二次電池 |
WO2018173521A1 (ja) * | 2017-03-22 | 2018-09-27 | パナソニックIpマネジメント株式会社 | 二次電池用負極およびその製造方法並びに二次電池 |
US11870053B2 (en) | 2017-03-22 | 2024-01-09 | Panasonic Intellectual Property Management Co., Ltd. | Secondary-battery negative electrode and manufacturing method thereof, and secondary battery |
CN110392949A (zh) * | 2017-03-22 | 2019-10-29 | 松下知识产权经营株式会社 | 二次电池用负极及其制造方法以及二次电池 |
JPWO2018173521A1 (ja) * | 2017-03-22 | 2020-02-06 | パナソニックIpマネジメント株式会社 | 二次電池用負極およびその製造方法並びに二次電池 |
CN110392949B (zh) * | 2017-03-22 | 2022-08-12 | 松下知识产权经营株式会社 | 二次电池用负极及其制造方法以及二次电池 |
JP7113248B2 (ja) | 2017-03-22 | 2022-08-05 | パナソニックIpマネジメント株式会社 | 二次電池用負極およびその製造方法並びに二次電池 |
JPWO2018179936A1 (ja) * | 2017-03-31 | 2020-02-27 | パナソニック株式会社 | 非水電解質二次電池用正極活物質及びその製造方法 |
US11658295B2 (en) | 2017-03-31 | 2023-05-23 | Panasonic Holdings Corporation | Positive electrode active material for non-aqueous electrolyte secondary battery and method for producing same |
KR102539250B1 (ko) | 2017-07-14 | 2023-06-01 | 바스프 에스이 | 전극 활물질의 제조 방법 |
JP2020528637A (ja) * | 2017-07-14 | 2020-09-24 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | 電極活物質の製造方法 |
JP7191489B2 (ja) | 2017-07-14 | 2022-12-19 | ビーエーエスエフ ソシエタス・ヨーロピア | 電極活物質の製造方法 |
KR20200028979A (ko) * | 2017-07-14 | 2020-03-17 | 바스프 에스이 | 전극 활물질의 제조 방법 |
JP2019050155A (ja) * | 2017-09-11 | 2019-03-28 | トヨタ自動車株式会社 | 非水電解液二次電池 |
WO2020241105A1 (ja) * | 2019-05-30 | 2020-12-03 | パナソニックIpマネジメント株式会社 | 二次電池用の負極活物質、及び二次電池 |
JP7474951B2 (ja) | 2019-05-30 | 2024-04-26 | パナソニックIpマネジメント株式会社 | 二次電池用の負極活物質、及び二次電池 |
JP7088156B2 (ja) | 2019-10-09 | 2022-06-21 | 三菱マテリアル株式会社 | 負極材料の製造方法、及び電池の製造方法 |
JP2022079612A (ja) * | 2019-10-09 | 2022-05-26 | 三菱マテリアル株式会社 | 負極材料、電池、負極材料の製造方法、及び電池の製造方法 |
WO2021070830A1 (ja) * | 2019-10-09 | 2021-04-15 | 三菱マテリアル株式会社 | 負極材料、電池、負極材料の製造方法、及び電池の製造方法 |
JP2021061212A (ja) * | 2019-10-09 | 2021-04-15 | 三菱マテリアル株式会社 | 負極材料、電池、負極材料の製造方法、及び電池の製造方法 |
JP7513049B2 (ja) | 2019-10-09 | 2024-07-09 | 三菱マテリアル株式会社 | 負極材料、リチウムイオン二次電池、負極材料の製造方法、及びリチウムイオン二次電池の製造方法 |
WO2023224070A1 (ja) * | 2022-05-20 | 2023-11-23 | 株式会社Gsユアサ | 非水電解質蓄電素子 |
WO2024029333A1 (ja) * | 2022-08-01 | 2024-02-08 | 株式会社Gsユアサ | 非水電解質蓄電素子 |
Also Published As
Publication number | Publication date |
---|---|
CN107431239B (zh) | 2020-05-08 |
JP6728134B2 (ja) | 2020-07-22 |
JPWO2016157735A1 (ja) | 2018-01-25 |
US10529978B2 (en) | 2020-01-07 |
US20180108939A1 (en) | 2018-04-19 |
CN107431239A (zh) | 2017-12-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6728134B2 (ja) | 非水電解質二次電池 | |
CN107112499B (zh) | 非水电解质二次电池用负极和非水电解质二次电池 | |
JP6588079B2 (ja) | 非水電解質二次電池 | |
KR101334609B1 (ko) | 음극 활물질 및 이를 이용한 이차전지 | |
JP6072271B2 (ja) | リチウム二次電池用電解液及びそれを含むリチウム二次電池 | |
JP5359490B2 (ja) | リチウムイオン二次電池 | |
JP6576007B2 (ja) | リチウム二次電池用電解液及びそれを含むリチウム二次電池 | |
JP6408631B2 (ja) | リチウム二次電池 | |
JP6811404B2 (ja) | 非水電解質二次電池 | |
JP6104245B2 (ja) | リチウムイオン二次電池 | |
JP6749692B2 (ja) | リチウム二次電池、電池モジュール、電池パック、及び電池パックを含むデバイス | |
KR101334615B1 (ko) | 음극 활물질 및 이를 이용한 이차전지 | |
US20180337424A1 (en) | Negative-electrode active material for non-aqueous secondary battery and non-aqueous secondary battery | |
JP6484995B2 (ja) | リチウムイオン二次電池 | |
JP2013134921A (ja) | 非水電解質二次電池用電極および非水電解質二次電池 | |
KR102520421B1 (ko) | 부극 | |
CN112673503A (zh) | 非水电解质蓄电元件和蓄电装置 | |
US10559846B2 (en) | Negative-electrode active material for non-aqueous secondary battery and non-aqueous secondary battery | |
JP6154467B2 (ja) | リチウム二次電池 | |
JP6181762B2 (ja) | リチウム二次電池用電解液及びそれを含むリチウム二次電池 | |
US10497967B2 (en) | Negative-electrode active material for non-aqueous secondary battery and non-aqueous secondary battery | |
JP6680531B2 (ja) | 負極活物質の製造方法及びリチウムイオン二次電池の製造方法 | |
WO2019066065A1 (ja) | 電極及び蓄電素子 | |
KR20230115234A (ko) | 리튬 이차전지용 전해액 및 이를 포함하는 리튬 이차전지 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16771629 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2017509223 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15554982 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 16771629 Country of ref document: EP Kind code of ref document: A1 |