WO2013137273A1 - 非水電解質二次電池および電池パック - Google Patents
非水電解質二次電池および電池パック Download PDFInfo
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- WO2013137273A1 WO2013137273A1 PCT/JP2013/056860 JP2013056860W WO2013137273A1 WO 2013137273 A1 WO2013137273 A1 WO 2013137273A1 JP 2013056860 W JP2013056860 W JP 2013056860W WO 2013137273 A1 WO2013137273 A1 WO 2013137273A1
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- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/044—Activating, forming or electrochemical attack of the supporting material
- H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
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- 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
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- 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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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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- H01M10/44—Methods for charging or discharging
- H01M10/446—Initial charging measures
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- 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
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- 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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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
- H01M10/486—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte for measuring temperature
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- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H01M2200/00—Safety devices for primary or secondary batteries
- H01M2200/10—Temperature sensitive devices
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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
- 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
- Embodiments of the present invention relate to a non-aqueous electrolyte secondary battery and a battery pack having the non-aqueous electrolyte secondary battery.
- a non-aqueous electrolyte secondary battery including a titanium composite oxide in which a lithium occlusion / release reaction proceeds at a potential higher than 0.5 V with respect to Li / Li + at a negative electrode is a non-aqueous electrolyte secondary battery using a carbon material as a negative electrode.
- the volume change of the active material accompanying charging / discharging is small and the operating potential at the time of charging / discharging is high.
- a non-aqueous electrolyte secondary battery including a titanium composite oxide in the negative electrode has a high operating potential
- a coating that inhibits side reactions is formed on the surface of the carbon negative electrode.
- SEI solid electrolyte interface
- An object of the present invention is to provide a non-aqueous electrolyte secondary battery excellent in charge / discharge cycle and a battery pack having the non-aqueous electrolyte secondary battery.
- the non-aqueous electrolyte secondary battery of the embodiment includes a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and a non-aqueous electrolyte.
- the negative electrode is Li / Li + as an active material. On the other hand, it contains a titanium composite oxide in which a lithium occlusion / release reaction proceeds at a potential higher than 0.5 V, and the non-aqueous electrolyte contains at least one element selected from B and S.
- the negative electrode has a Li / C composition ratio of 0.20 to 0.50 and a Li / Ti composition ratio of 0.5 to 5.0 with respect to the elemental composition of the surface measured by X-ray photoelectron spectroscopy.
- the nonaqueous electrolyte secondary battery of the embodiment includes a titanium composite oxide in which a negative electrode has an active material and a lithium occlusion / release reaction proceeds at a potential higher than 0.5 V vs Li / Li + , and the nonaqueous electrolyte includes B and S.
- the negative electrode has a Li / C composition ratio of 0.20 to 0.50 with respect to the elemental composition of the surface measured by X-ray photoelectron spectroscopy, and a Li / Ti composition ratio of 0 The condition of 0.5 to 5.0 is satisfied, and the charge / discharge cycle characteristics are greatly improved.
- Examples of the X-ray photoelectron spectrometer include, but are not particularly limited to, the AXIS series manufactured by Shimadzu Corporation.
- the Li / C composition ratio is smaller than 0.20, the resistance is too large and it is difficult to obtain the effect of improving the cycle characteristics.
- the Li / C composition ratio is greater than 0.50, the resistance increase with the progress of the cycle is large, and it is difficult to obtain the effect of improving the cycle characteristics.
- the Li / Ti composition ratio is smaller than 0.5, the resistance increase with the progress of the cycle is large, and it is difficult to obtain the effect of improving the cycle characteristics.
- the Li / Ti composition ratio is larger than 5, the resistance is too large and it is difficult to obtain the effect of improving the cycle characteristics.
- the Li / Ti composition ratio is more preferably in the range of 0.6 to 4.5.
- the content of B or S in the nonaqueous electrolyte is preferably in the range of 1 ⁇ 10 ⁇ 5 to 2 wt%.
- the above-described Li / C composition ratio of the negative electrode surface is 0.20 to 0.50 and the Li / Ti composition ratio is 0.5 to 0.5%. It becomes difficult to make it within the range of 5.0.
- the content of B or S is greater than 10 wt%, the resistance of the electrolyte solution itself increases, the Li / C composition ratio is less than 0.20, or the Li / Ti composition ratio is greater than 5.0. There is a tendency to increase, and it becomes difficult to obtain the effect of improving the cycle characteristics.
- Examples of the titanium composite oxide in which the lithium occlusion / release reaction proceeds at a potential higher than 0.5 V vs Li / Li + which is a negative electrode active material include, for example, lithium titanate represented by the chemical formula Li 4 + x Ti 5 O 12. It is done.
- the negative electrode active material preferably has an average particle diameter in the range of 0.05 to 2 ⁇ m and a specific surface area in the range of 2 to 25 m 2 / g. If the average particle size is smaller than 0.05 ⁇ m, the crystallinity of the active material itself is lowered, and if it is larger than 2 ⁇ m, the lithium ion diffusion distance in the active material becomes too large, so that it is difficult to obtain the effect of improving the cycle characteristics.
- the specific surface area is smaller than 2 m 2 / g, the resistance of the battery itself is increased.
- the specific surface area is larger than 25 m 2 / g, the increase in resistance with the progress of the cycle is increased, and it is difficult to obtain the effect of improving the cycle characteristics.
- the average particle diameter of the negative electrode active material is synonymous with the 50% frequency diameter. This is measured by, for example, a laser diffraction / scattering type / particle size / particle size distribution measuring apparatus.
- An example of the apparatus is a Nikkiso Microtrack.
- the specific surface area of the negative electrode active material is measured by a specific surface area / pore distribution measuring device using a gas adsorption phenomenon.
- the apparatus include an automatic specific surface area / pore distribution measuring apparatus (BELSORP-mini) manufactured by Nippon Bell.
- the positive electrode has a current collector and a positive electrode layer (positive electrode active material layer) supported on one or both sides of the current collector and containing a positive electrode active material, a conductive agent, and a binder.
- a positive electrode active material layer for example, a conductive agent and a binder are added to a powdered positive electrode active material, suspended in an appropriate solvent, and the suspension (slurry) is applied to a current collector, dried and pressed. It is produced by forming a strip electrode.
- the positive electrode active material includes manganese dioxide (MnO 2 ), iron oxide, copper oxide, nickel oxide, Li a MnO 2 , lithium cobalt composite oxide (Li a CoM h O 2 , where M is Al, Cr, Mg and At least one element or two or more elements selected from the group consisting of Fe, 0 ⁇ h ⁇ 0.1, a lithium manganese cobalt composite oxide (eg, LiMn 1- gh Co g M h O 2 , wherein M is at least one element selected from the group consisting of Al, Cr, Mg, and Fe, 0 ⁇ g ⁇ 0.5, lithium manganese nickel composite oxide (for example, LiMn j Ni j M 1 ⁇ 2j O 2, wherein M is at least one or more element selected Co, Cr, Al, from the group consisting of Mg and Fe, 1/3 ⁇ j ⁇ 1/2, LiMn / 3 Ni 1/3 Co 1/3 O 2 , LiMn 1/2 Ni 1/2 O 2), spinel type lithium-mangan
- a and b are preferably 0 ⁇ a ⁇ 1.2 and 0 ⁇ b ⁇ 1.
- Other positive electrode active materials include conductive polymer materials such as polyaniline and polypyrrole, disulfide polymer materials, organic materials such as sulfur (S) and carbon fluoride, and inorganic materials.
- More preferable positive electrode active materials are lithium cobalt composite oxide, lithium manganese nickel composite oxide, spinel type lithium manganese composite oxide, spinel type lithium manganese nickel composite oxide, lithium manganese cobalt composite oxide, and lithium iron phosphate. .
- the average particle diameter of the positive electrode active material is desirably 1 ⁇ m or more and 20 ⁇ m or less.
- the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), and fluorine-based rubber.
- the positive electrode active material layer may contain a conductive agent.
- the conductive agent include carbonaceous materials such as acetylene black, carbon black, and graphite.
- the mixing ratio of the positive electrode active material, the conductive agent, and the binder is preferably 73 to 95% by weight of the positive electrode active material, 3 to 20% by weight of the conductive agent, and 2 to 7% by weight of the binder.
- the positive electrode current collector is preferably formed of aluminum foil or aluminum alloy foil.
- the aluminum foil and the aluminum alloy foil desirably have an average crystal grain size of 50 ⁇ m or less, more preferably 30 ⁇ m or less, and still more preferably 5 ⁇ m or less.
- the average crystal grain size is 50 ⁇ m or less, the strength of the aluminum foil or aluminum alloy foil can be dramatically increased, the positive electrode can be densified with a high press pressure, and the battery capacity is increased. be able to.
- the average crystal grain size of the aluminum foil and the aluminum alloy foil changes under complex influences from a plurality of factors such as material structure, impurities, processing conditions, heat treatment history, and annealing conditions.
- the crystal grain size can be adjusted by combining the above factors in the production process of the current collector.
- the thickness of the aluminum foil and the aluminum alloy foil is preferably 20 ⁇ m or less, and more preferably 15 ⁇ m or less.
- the purity of the aluminum foil is preferably 99% by mass or more.
- As the aluminum alloy an alloy containing elements such as magnesium, zinc and silicon is preferable.
- the content of transition metals such as iron, copper, nickel and chromium is preferably 1% by mass or less.
- Negative electrode The negative electrode includes a current collector and a negative electrode layer (negative electrode active material layer) that is supported on one or both surfaces of the current collector and includes a negative electrode active material, a conductive agent, and a binder.
- a negative electrode active material layer that is supported on one or both surfaces of the current collector and includes a negative electrode active material, a conductive agent, and a binder.
- a conductive agent and a binder are added to a powdered negative electrode active material, these are suspended in an appropriate solvent, and this suspension (slurry) is applied to a current collector, dried and pressed. It is produced by forming a strip electrode.
- the negative electrode current collector is preferably formed of, for example, copper foil, aluminum foil, or aluminum alloy foil.
- the aluminum foil or aluminum alloy foil constituting the negative electrode current collector desirably has an average crystal grain size of 50 ⁇ m or less, more preferably 30 ⁇ m or less, and still more preferably 5 ⁇ m or less.
- the average crystal grain size can be determined by the method described above. When the average crystal grain size is 50 ⁇ m or less, the strength of the aluminum foil or aluminum alloy foil can be dramatically increased. For this reason, it is possible to increase the negative electrode capacity by increasing the pressure during pressing to increase the density of the negative electrode active material layer. Further, it is possible to prevent the current collector from being dissolved and corroded in an overdischarge cycle under a high temperature environment (40 ° C. or higher). For this reason, an increase in negative electrode impedance can be suppressed. Furthermore, output characteristics, quick charge, and charge / discharge cycle characteristics can also be improved.
- the average crystal grain size of aluminum foil or aluminum alloy foil changes under complex influences from several factors such as material structure, impurities, processing conditions, heat treatment history, and annealing conditions.
- the crystal grain size can be adjusted by combining the above factors in the production process of the current collector.
- the thickness of the aluminum foil or aluminum alloy foil is desirably 20 ⁇ m or less, more preferably 15 ⁇ m or less.
- the aluminum foil preferably has a purity of 99% by mass or more.
- the aluminum alloy is preferably an alloy containing elements such as magnesium, zinc, and silicon. Transition metals such as iron, copper, nickel and chromium contained as alloy components are preferably 1% by mass or less.
- the negative electrode active material includes a titanium composite oxide in which a lithium storage / release reaction proceeds at a potential higher than 0.5 V vs Li / Li + .
- a titanium composite oxide in which the occlusion and release reaction of lithium proceeds at a potential higher than 0.5 V vs Li / Li + is, for example, Li 4 + x Ti 5 O 12 Spinel type lithium titanate, ramsteride type Li 2 + x Ti 3 O 7 (x varies in the range of ⁇ 1 ⁇ x ⁇ 3 by charge / discharge reaction), Ti and P, V, Sn, Cu , Metal composite oxides containing at least one element selected from the group consisting of Ni and Fe.
- Examples of the metal composite oxide containing at least one element selected from the group consisting of Ti and P, V, Sn, Cu, Ni, and Fe include TiO 2 —P 2 O 5 , TiO 2 —V 2. O 5 , TiO 2 —P 2 O 5 —SnO 2 , TiO 2 —P 2 O 5 —MO (M is at least one element selected from the group consisting of Cu, Ni and Fe).
- This metal complex oxide has a low crystallinity and preferably has a microstructure in which a crystal phase and an amorphous phase coexist or exist alone. Such a microstructured metal composite oxide can greatly improve the cycle performance.
- These metal composite oxides change to lithium titanium composite oxides when lithium is inserted by charging. Among lithium titanium composite oxides, spinel type lithium titanate is preferable because of its excellent cycle characteristics.
- the negative electrode active material may contain other active materials, and examples thereof include carbonaceous materials and metal compounds.
- Examples of the carbonaceous material include natural graphite, artificial graphite, coke, vapor grown carbon fiber, mesophase pitch carbon fiber, spherical carbon, and resin-fired carbon. More preferable carbonaceous materials include vapor grown carbon fiber, mesophase pitch carbon fiber, and spherical carbon.
- the carbonaceous material preferably has a (002) plane spacing d002 of 0.34 nm or less by X-ray diffraction.
- metal compound metal sulfide or metal nitride can be used.
- metal sulfide titanium sulfide such as TiS 2
- molybdenum sulfide such as MoS 2
- iron sulfide such as FeS, FeS 2
- Li x FeS 2 can be used.
- metal nitride for example, lithium cobalt nitride (for example, Li s Co t N, 0 ⁇ s ⁇ 4, 0 ⁇ t ⁇ 0.5) can be used.
- binder examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), fluorine rubber, and styrene butadiene rubber.
- the blending ratio of the negative electrode active material, the conductive agent and the binder is preferably in the range of 73 to 96% by weight of the negative electrode active material, 2 to 20% by weight of the conductive agent, and 2 to 7% by weight of the binder.
- Nonaqueous electrolyte includes a nonaqueous solvent and an electrolyte salt dissolved in the nonaqueous solvent.
- the polymer may be contained in the non-aqueous solvent.
- electrolyte salt examples include LiPF 6 , LiBF 4 , Li (CF 3 SO 2 ) 2 N (bistrifluoromethanesulfonylamidolithium; commonly known as LiTFSI), LiCF 3 SO 3 (commonly known as LiTFS), and Li (C 2 F 5 SO 2 ).
- LiBETI bis pentafluoroethanesulfonyl amide lithium; called LiBETI
- LiClO 4 LiAsF 6 , LiSbF 6, bisoxalato Lato lithium borate (LiB (C 2 O 4) 2 ( known as LiBOB))
- LiBOB bisoxalato Lato lithium borate
- difluoro tri-fluoro-2
- lithium salts such as -oxide-2-trifluoro-methylpropionate (2-)-0,0) lithium borate (LiBF 2 OCOOC (CF 3 ) 2 ) (commonly called LiBF 2 (HHIB))
- HHIB lithium borate
- These electrolyte salts may be used alone or in combination of two or more.
- LiPF 6 and LiBF 4 are preferable.
- the electrolyte salt concentration is preferably 1 to 3 mol / L. Such regulation of the electrolyte concentration makes it possible to further improve the performance when a high load current is passed while suppressing the influence of an increase in viscosity due to an increase in the electrolyte salt concentration.
- the non-aqueous solvent is not particularly limited.
- PC propylene carbonate
- EC ethylene carbonate
- DME 1,2-dimethoxyethane
- GBL ⁇ -butyrolactone
- THF tetrahydrofuran
- 2-MeHF 2 -Use methyltetrahydrofuran
- 1,3-dioxolane 1,3-dioxolane
- sulfolane 1,3-dioxolane
- sulfolane acetonitrile (AN)
- DEC diethyl carbonate
- DMC dimethyl carbonate
- MEC methyl ethyl carbonate
- DPC dipropyl carbonate
- solvents may be used alone or in combination of two or more.
- An additive may be added to this non-aqueous electrolyte.
- an additive is not specifically limited, Vinylene carbonate (VC), vinylene acetate (VA), vinylene butyrate, vinylene hexanate, vinylene crotonate, catechol carbonate, etc. are mentioned.
- the concentration of the additive is preferably in the range of 0.1% by weight to 3% by weight with respect to 100% by weight of the nonaqueous electrolyte. A more preferable range is 0.5% by weight or more and 1% by weight or less.
- the non-aqueous electrolyte of the embodiment includes B or S.
- the compound containing B include lithium tetrafluoroborate (LiBF 4 ), lithium bis (oxalato) lithium borate (LiBOB), lithium difluoro (oxalato) borate (LiBF 2 C 2 O 4 ), and bis (malonato) boric acid.
- Lithium, lithium bis (succinate) borate, and difluoro (trifluoro-2-oxide-2-trifluoro-methylpropionate (2-)-0,0) lithium borate are preferred.
- Compounds containing S include ethylene sulfite, propylene sulfite, 1,2-ethane sultone, 1,3-propane sultone, 1,4-butane sultone, 1,5-pentane sultone, 1,3-propene sultone, 1,4 -Butylene sultone is preferred.
- the separator is not particularly limited as long as it has insulating properties, and a porous film or a nonwoven fabric made of a polymer such as polyolefin, cellulose, polyethylene terephthalate, and vinylon can be used.
- a porous film or a nonwoven fabric made of a polymer such as polyolefin, cellulose, polyethylene terephthalate, and vinylon can be used.
- One type of separator material may be used, or two or more types may be used in combination.
- Exterior member As the exterior member, a laminate film having a thickness of 0.5 mm or less or a metal container having a thickness of 1 mm or less is used.
- the metal container is more preferably 0.5 mm or less in thickness.
- Examples of the shape of the exterior member that is, the battery shape, include a flat type (thin type), a square type, a cylindrical type, a coin type, and a button type.
- the battery can be applied to, for example, a small-sized application loaded on a portable electronic device or the like, and a large-sized application loaded on a two-wheel to four-wheeled vehicle or the like.
- the laminate film a multilayer film in which a metal layer is interposed between resin layers is used.
- the metal layer is preferably an aluminum foil or an aluminum alloy foil for weight reduction.
- a polymer material such as polypropylene (PP), polyethylene (PE), nylon, polyethylene terephthalate (PET) can be used.
- the laminate film can be formed into the shape of an exterior member by sealing by heat sealing.
- Metal containers are made of aluminum or aluminum alloy.
- the aluminum alloy an alloy containing elements such as magnesium, zinc and silicon is preferable.
- transition metals such as iron, copper, nickel and chromium are contained in the alloy, the amount is preferably 100 ppm or less.
- Example A-1 ⁇ Preparation of positive electrode> LiNi 0.6 Co 0.2 Mn 0.2 O 2 was prepared as a positive electrode active material, graphite and acetylene black as a conductive agent, and PVdF as a binder.
- NMP N-methylpyrrolidone
- This slurry was applied to both sides of a current collector made of aluminum foil having a thickness of 15 ⁇ m, dried, and press-molded to produce a positive electrode having a positive electrode active material layer on both sides of the current collector.
- the positive electrode active material layer on one side has a thickness of 50 ⁇ m and a density of 3.30 g / cm 3 .
- ⁇ Production of negative electrode> Li 4 Ti 5 O 12 having an average particle size of 0.9 ⁇ m and a specific surface area of 8 m 2 / g as a negative electrode active material, graphite as a conductive agent, and PVdF as a binder were prepared.
- NMP N-methylpyrrolidone
- the slurry was applied to both sides of a 15 ⁇ m thick aluminum foil current collector, dried, and press-molded to produce a negative electrode having a negative electrode active material layer on both sides of the current collector.
- the negative electrode active material layer on one side has a thickness of 65 ⁇ m and a density of 2.40 g / cm 3 .
- a non-aqueous electrolyte secondary battery having the structure shown in FIG. 1 was produced.
- a container 10 having a bottomed rectangular cylindrical body made of aluminum having a thickness of 0.3 mm, and a positive electrode terminal 13 and an aluminum terminal in which a negative electrode terminal 12 is inserted by caulking through an insulating resin 14.
- a lid 11 was prepared. After impregnating a separator 2 made of a cellulose nonwoven fabric with a thickness of 15 ⁇ m with a non-aqueous electrolyte, the positive electrode 3 is covered with the separator 2, and the negative electrode 1 is stacked so as to face the positive electrode 3 with the separator 2 interposed therebetween.
- a spiral electrode group having lead tabs extending from the positive electrode 3 and the negative electrode 1 was produced. This electrode group was pressed into a flat shape.
- the positive electrode lead tab 5 of the electrode group formed into a flat shape is connected to one end of the positive electrode terminal 13 of the lid body 11, the negative electrode lead tab 4 is connected to one end of the negative electrode terminal 12, and the electrode group is passed through the opening of the container together with the lid body 11.
- the lid 11 was welded to the opening of the container 10 after being inserted into the inside. Through these steps, a nonaqueous electrolyte secondary battery having the structure shown in FIG. 1 and having a thickness of 3.0 mm, a width of 35 mm, and a height of 62 mm was manufactured.
- the obtained nonaqueous electrolyte secondary battery was charged to 2.8 V at a current value of 0.2 C in a 25 ° C. environment, discharged to 0.5 V at a current value of 0.2 C, and then left for 24 hours in a 70 ° C. environment. Aging was performed. This battery was charged to 2.4 V in a 25 ° C. environment. The battery was disassembled and the surface element composition of the negative electrode extracted was measured by X-ray photoelectron spectroscopy. As a result, the Li / C composition ratio was 0.33, and the Li / Ti composition ratio was 1.2.
- the battery disassembly method will be described. Place the charged battery in a glove box under an argon atmosphere, scrape the sealing (welding) part of the sealing plate and outer package with a file to peel off the sealing plate and outer package, and generate the power generation site (positive electrode / separator / negative electrode) Take out the laminate consisting of The lead portion is removed so as not to short-circuit the power generation site, and the laminate is decomposed into a positive electrode, a separator, and a negative electrode.
- the obtained negative electrode is washed with, for example, methyl ethyl carbonate solvent to remove the Li salt on the negative electrode surface and then dried to obtain an analytical sample. Further, the obtained negative electrode is put into a solvent to dissolve the binder, the negative electrode active material layer is peeled from the current collector, and the peeled material is filtered to extract the negative electrode active material.
- Examples A-2 to 3, B-1 to 7, C-1 to 7, D-1 to 2 A battery was prepared in the same manner as in Example A-1, except that the negative electrode active material, the electrolyte composition, and the aging conditions after charging were changed as shown in Tables 1 and 2.
- the aging conditions are changed.
- the additive is changed.
- the Li salt is changed.
- the negative electrode active material is changed.
- Example A-1 A non-aqueous electrolyte secondary battery similar to that in Example A-1 was prepared, and the obtained non-aqueous electrolyte secondary battery was charged to 2.8 V at a current value of 0.2 C in a 25 ° C. environment. The current was discharged to 1.5V. This battery was charged to 2.4 V in a 25 ° C. environment. The battery was disassembled and the surface element composition of the negative electrode extracted was measured by X-ray photoelectron spectroscopy. As a result, the Li / C composition ratio was 0.73, and the Li / Ti composition ratio was 0.4.
- a charge / discharge cycle test was performed in which the obtained battery was charged to 2.6 V at 2 C and discharged to 2.2 V at 2 C in a 60 ° C. environment.
- the battery capacity after 50000 cycles was 92% for the battery of Example A-1, compared with 58% for the battery of Comparative Example A-1.
- Comparative Example A-2 Comparative Example D-1, 2
- a battery was prepared in the same manner as in Example A-1, except that the negative electrode active material and the aging conditions after charging were changed as shown in Tables 1 and 2.
- the aging conditions are changed.
- the negative electrode active material is changed.
- each of Examples A-1 to 3, B-1 to 7, C-1 to 7, and D-1 to 2 has a cycle capacity maintenance rate of 70% or more, and a charge / discharge cycle. Improved properties were observed.
- the battery pack has one or more non-aqueous electrolyte secondary batteries (unit cells) described above.
- unit cells non-aqueous electrolyte secondary batteries
- each unit cell is electrically connected in series or in parallel.
- FIGS. 1-10 Such a battery pack will be described with reference to FIGS.
- a plurality of unit cells 21 composed of flat type nonaqueous electrolyte secondary batteries are laminated so that the negative electrode terminal 12 and the positive electrode terminal 13 extending to the outside are aligned in the same direction, and are fastened with an adhesive tape 22 and assembled.
- a battery 23 is configured. These unit cells 21 are electrically connected to each other in series as shown in FIG.
- the printed wiring board 24 is disposed to face the side surface of the unit cell 21 from which the negative electrode terminal 12 and the positive electrode terminal 13 extend. As shown in FIG. 3, a thermistor 25, a protection circuit 26, and a terminal 27 for energizing external devices are mounted on the printed wiring board 24. An insulating plate (not shown) is attached to the surface of the protection circuit board 24 facing the assembled battery 23 in order to avoid unnecessary connection with the wiring of the assembled battery 23.
- the positive electrode side lead 28 is connected to the positive electrode terminal 13 located in the lowermost layer of the assembled battery 23, and the tip thereof is inserted into the positive electrode side connector 29 of the printed wiring board 24 and electrically connected thereto.
- the negative electrode side lead 30 is connected to the negative electrode terminal 12 positioned at the uppermost layer of the assembled battery 23, and the tip thereof is inserted into the negative electrode side connector 31 of the printed wiring board 24 and electrically connected thereto.
- These connectors 29 and 31 are connected to the protection circuit 26 through wirings 32 and 33 formed on the printed wiring board 24.
- the thermistor 25 detects the temperature of the unit cell 21, and the detection signal is transmitted to the protection circuit 26.
- the protection circuit 26 can cut off the plus side wiring 34a and the minus side wiring 34b between the protection circuit 26 and the energization terminal 27 to the external device under a predetermined condition.
- the predetermined condition is, for example, when the temperature detected by the thermistor 25 is equal to or higher than a predetermined temperature.
- the predetermined condition is when the overcharge, overdischarge, overcurrent, etc. of the cell 21 are detected. This detection of overcharge or the like is performed for each single cell 21 or the entire single cell 21.
- the battery voltage may be detected, or the positive electrode potential or the negative electrode potential may be detected.
- a lithium electrode used as a reference electrode is inserted into each unit cell 21.
- a wiring 35 for voltage detection is connected to each single cell 21, and a detection signal is transmitted to the protection circuit 26 through these wirings 35.
- Protective sheets 36 made of rubber or resin are disposed on the three side surfaces of the assembled battery 23 excluding the side surfaces from which the positive electrode terminal 13 and the negative electrode terminal 12 protrude.
- the assembled battery 23 is stored in a storage container 37 together with each protective sheet 36 and the printed wiring board 24. That is, the protective sheet 36 is disposed on each of the inner side surface in the long side direction and the inner side surface in the short side direction of the storage container 37, and the printed wiring board 24 is disposed on the inner side surface on the opposite side in the short side direction.
- the assembled battery 23 is located in a space surrounded by the protective sheet 36 and the printed wiring board 24.
- the lid 38 is attached to the upper surface of the storage container 37.
- a heat shrink tape may be used for fixing the assembled battery 23.
- protective sheets are arranged on both side surfaces of the assembled battery, the heat shrinkable tube is circulated, and then the heat shrinkable tube is thermally contracted to bind the assembled battery.
- FIGS. 2 and 3 show a configuration in which the unit cells 21 are connected in series, but in order to increase the battery capacity, they may be connected in parallel.
- the assembled battery packs can be connected in series or in parallel.
- the mode of the battery pack is appropriately changed depending on the application.
- those in which cycle characteristics with large current characteristics are desired are preferable.
- Specific examples include a power source for a digital camera, a vehicle for a two- to four-wheel hybrid electric vehicle, a two- to four-wheel electric vehicle, an assist bicycle, and the like.
- the vehicle-mounted one is suitable.
- the negative electrode active material Li 4 Ti 5 O 12 used in the series of Example A, the series of Example B, and the series of Example C had an average operating potential of 1.55V.
- the negative electrode active material TiO 2 used in Example D-1 and Comparative Example D-1 had an average operating potential of 1.50V.
- the average working potential of TiO 2 (B) used in Example D-2 and Comparative Example D-2 was 1.60V.
- Comparative Example A-1 Comparative Example D-1 and Comparative Example D-2
- the produced nonaqueous electrolyte secondary battery was charged to 2.8 V at a current value of 0.2 C in a 25 ° C. environment, and 0
- the battery was discharged to 2.4 V with a current value of 2 C. That is, aging was not performed in these comparative examples. Therefore, the cycle capacity retention rate was lower than that of the nonaqueous electrolyte secondary battery of the example.
- Comparative Example A-2 the produced nonaqueous electrolyte secondary battery was charged to 2.8 V at a current value of 0.2 C in a 25 ° C. environment, and discharged to 2.4 V at a current value of 0.2 C. Aging was performed by leaving it in an 80 ° C. environment for 12 hours. In Comparative Example A-2, since the aging was performed without performing sufficient discharge, the cycle capacity retention rate was lower than that of the nonaqueous electrolyte secondary battery of the example.
- the nonaqueous electrolytes included in the nonaqueous electrolyte secondary batteries of the above examples and comparative examples have a content of at least one element selected from B and S in the range of 1 ⁇ 10 ⁇ 5 to 10 wt%. is there. For this reason, in the nonaqueous electrolyte secondary batteries of the above examples and comparative examples, it is considered that there is little difference in cycle characteristics due to the resistance of the nonaqueous electrolyte.
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Abstract
Description
正極は、集電体と、この集電体の片面または両面に担持され、正極活物質、導電剤および結着剤を含む正極層(正極活物質層)とを有する。この正極は、例えば粉末状の正極活物質に導電剤および結着剤を添加し、これらを適当な溶媒に懸濁させ、この懸濁物(スラリー)を集電体に塗布、乾燥、プレスして帯状電極にすることにより作製される。
アルミニウム箔およびアルミニウム合金箔の平均結晶粒径は、材料組織、不純物、加工条件、熱処理履歴、および焼鈍条件など複数の因子から複雑な影響を受けて変化する。結晶粒径は、集電体の製造工程の中で、前記諸因子を組合せて調整することが可能である。
負極は、集電体と、この集電体の片面または両面に担持され、負極活物質、導電剤および結着剤を含む負極層(負極活物質層)とを有する。この負極は、例えば粉末状の負極活物質に導電剤および結着剤を添加し、これらを適当な溶媒に懸濁させ、この懸濁物(スラリー)を集電体に塗布、乾燥、プレスして帯状電極にすることにより作製される。
非水電解質は、非水溶媒と、この非水溶媒に溶解される電解質塩を含む。非水溶媒中にポリマーを含んでいてもよい。
セパレータは、絶縁性を有するものであれば特に限定されないが、ポリオレフィン、セルロース、ポリエチレンテレフタレート、およびビニロンのようなポリマーからなる多孔質フィルム又は不織布を用いることができる。セパレータの材料は1種類であってもよく、2種類以上を組合せて用いてもよい。
外装部材は、厚さ0.5mm以下のラミネートフィルム又は厚さ1mm以下の金属製容器が用いられる。金属製容器は、厚さ0.5mm以下であることがより好ましい。
<正極の作製>
正極活物質としてLiNi0.6Co0.2Mn0.2O2、導電剤としてグラファイトおよびアセチレンブラック、結着剤としてPVdFを用意した。正極活物質85重量部、アセチレンブラック5重量部、グラファイト5重量部およびPVdF5重量部の混合物をN-メチルピロリドン(NMP)に分散させてスラリーを調製した。このスラリーを厚さ15μmのアルミニウム箔からなる集電体の両面に塗布、乾燥し、さらにプレス成形して、集電体の両面に正極活物質層を有する正極を作製した。片面の正極活物質層は厚さが50μmで密度が3.30g/cm3である。
負極活物質として平均粒径が0.9μmで比表面積が8m2/gのLi4Ti5O12、導電剤としてグラファイト、結着剤としてPVdFを用意した。負極活物質90重量部、グラファイト5重量部およびPVdF5重量部の混合物をN-メチルピロリドン(NMP)に分散させてスラリーを調製した。このスラリーを厚さ15μmのアルミニウム箔の集電体の両面に塗布、乾燥し、さらにプレス成形して、集電体の両面に負極活物質層を有する負極を作製した。片面の負極活物質層は厚さが65μmで密度が2.40g/cm3である。
プロピレンカーボネート(PC)とジエチルカーボネート(DEC)とを体積比1:2の割合で混合した混合溶媒に、12wt%のLiPF6、3wt%のLiBF4、および1wt%のプロパンスルトンを混合して非水電解質を調製した。
図1に示す構造を有する非水電解質二次電池を製造した。厚さ0.3mmのアルミニウムからなる有底矩形状筒体の容器10と、正極端子13が挿着されるとともに負極端子12が絶縁性の樹脂14を介してかしめにより挿着されたアルミニウム製の蓋体11を用意した。非水電解質を厚さ15μmのセルロース製不織布からなるセパレータ2に含浸させた後、このセパレータ2で正極3を覆い、セパレータ2を介して正極3と対向するように負極1を重ね、渦巻状に捲回して、正極3および負極1からそれぞれ延出したリードタブを有する渦巻状の電極群を作製した。この電極群をプレスして扁平状に成形した。扁平状に成形した電極群の正極リードタブ5を蓋体11の正極端子13の一端に接続し、負極リードタブ4を負極端子12の一端に接続し、電極群を蓋体11とともに容器の開口部を通してその内部に挿入し、蓋体11を容器10の開口部に溶接した。これらの工程により、図1に示す構造を有する、厚さ3.0mm、幅35mm、高さ62mmの非水電解質二次電池を製造した。
負極活物質、電解液組成、充電後のエージング条件を、表1および表2に示したように変化させた以外は実施例A-1と同様の電池を作製した。
実施例Aのシリーズではエージング条件を変化させている。
実施例Bのシリーズでは添加剤を変化させている。
実施例CのシリーズではLi塩を変化させている。
実施例Dのシリーズでは負極活物質を変化させている。
実施例A-1と同様の非水電解質二次電池を作製し、得られた非水電解質二次電池を25℃環境において0.2Cの電流値で2.8Vまで充電し、0.2Cの電流値で1.5Vまで放電した。この電池を25℃環境において2.4Vまで充電した。この電池を解体し、抜き出した負極についてX線光電子分光によって表面元素組成を測定した。その結果、Li/C組成比が0.73、Li/Tiの組成比が0.4であった。
負極活物質、充電後のエージング条件を、表1および表2に示したように変化させた以外は実施例A-1と同様の電池を作製した。
比較例Aのシリーズではエージング条件を変化させている。
比較例Dのシリーズでは負極活物質を変化させている。
Claims (7)
- 正極と、負極と、前記正極と前記負極との間に配置されたセパレータと、非水電解質とを具備する非水電解質二次電池において、
前記負極は活物質として、Li/Li+に対して0.5Vより高い電位でリチウムの吸蔵放出反応が進行するチタン複合酸化物を含み、
前記非水電解質はBおよびSから選択される少なくとも1種の元素を含み、
前記負極はX線光電子分光によって測定される表面の元素組成についてLi/C組成比が0.20~0.50であり、Li/Ti組成比が0.5~5.0であることを特徴とする非水電解質二次電池。 - 前記非水電解質中の前記少なくとも1種の元素の含有率が1×10-5~10wt%であることを特徴とする請求項1に記載の非水電解質二次電池。
- 0.5V vs Li/Li+より高い電位でリチウムの吸蔵放出反応が進行する前記チタン複合酸化物は、化学式Li4+xTi5O12(-1≦x≦3)で表されるチタン酸リチウムであり、前記チタン酸リチウムの平均粒径が0.05~2μmであり、前記チタン酸リチウムの比表面積が2~25m2/gであることを特徴とする請求項1または2に記載の非水電解質二次電池。
- 前記非水電解質は、4フッ化ホウ酸リチウム(LiBF4)、ビス(オキサラト)ホウ酸リチウム(LiBOB)、ジフルオロ(オキサラト)ホウ酸リチウム(LiBF2C2O4)、ビス(マロナト)ホウ酸リチウム、ビス(スクシナート)ホウ酸リチウム、およびジフルオロ(トリフルオロ-2-オキシド-2-トリフルオロ-メチルプロピオナト(2-)-0,0)ホウ酸リチウムからなる群より選択される少なくとも1種を含むことを特徴とする請求項1ないし3のいずれか1項に記載の非水電解質二次電池。
- 前記非水電解質は、エチレンサルファイト、プロピレンサルファイト、1,2-エタンスルトン、1,3-プロパンスルトン、1,4-ブタンスルトン、1,5-ペンタンスルトン、1,3-プロペンスルトン、1,4-ブチレンスルトンからなる群より選択される少なくとも1種を含むことを特徴とする請求項1ないし4のいずれか1項に記載の非水電解質二次電池。
- 前記非水電解質は、30~90wt%のプロピレンカーボネートを含むことを特徴とする請求項1ないし5のいずれか1項に記載の非水電解質二次電池。
- 請求項1ないし6のいずれか1項に記載の非水電解質二次電池を有することを特徴とする電池パック。
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2013
- 2013-03-12 JP JP2014504939A patent/JPWO2013137273A1/ja active Pending
- 2013-03-12 CN CN201380002500.2A patent/CN103718370B/zh active Active
- 2013-03-12 WO PCT/JP2013/056860 patent/WO2013137273A1/ja active Application Filing
- 2013-03-12 EP EP13761007.7A patent/EP2827431A4/en not_active Withdrawn
-
2014
- 2014-01-27 US US14/164,511 patent/US20140141323A1/en not_active Abandoned
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JP2003163029A (ja) * | 2001-11-27 | 2003-06-06 | Matsushita Electric Ind Co Ltd | 非水電解質二次電池 |
JP2007053083A (ja) | 2005-07-21 | 2007-03-01 | Matsushita Electric Ind Co Ltd | 非水電解質二次電池及びその製造方法 |
JP2007042440A (ja) * | 2005-08-03 | 2007-02-15 | Sanyo Electric Co Ltd | リチウム二次電池 |
JP2008091327A (ja) | 2006-09-05 | 2008-04-17 | Gs Yuasa Corporation:Kk | 非水電解質電池及びその製造方法 |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015187964A (ja) * | 2014-03-13 | 2015-10-29 | 株式会社Gsユアサ | 非水電解液蓄電素子及びそれを備えた蓄電装置 |
CN106537654A (zh) * | 2014-07-14 | 2017-03-22 | 丰田自动车株式会社 | 制造非水二次电池的方法 |
JP2016035902A (ja) * | 2014-07-31 | 2016-03-17 | 株式会社東芝 | 非水電解質電池及び電池パック |
JP2016035901A (ja) * | 2014-07-31 | 2016-03-17 | 株式会社東芝 | 非水電解質電池、非水電解質電池の製造方法及び電池パック |
JP2018049836A (ja) * | 2014-09-10 | 2018-03-29 | 株式会社東芝 | 負極 |
US10355273B2 (en) | 2014-09-10 | 2019-07-16 | Kabushiki Kaisha Toshiba | Nonaqueous electrolyte battery |
US10910643B2 (en) | 2014-09-10 | 2021-02-02 | Kabushiki Kaisha Toshiba | Nonaqueous electrolyte battery |
WO2022054415A1 (ja) * | 2020-09-10 | 2022-03-17 | 株式会社村田製作所 | リチウムイオン二次電池 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2013137273A1 (ja) | 2015-08-03 |
EP2827431A4 (en) | 2015-11-18 |
US20140141323A1 (en) | 2014-05-22 |
CN103718370B (zh) | 2016-06-15 |
CN103718370A (zh) | 2014-04-09 |
EP2827431A1 (en) | 2015-01-21 |
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