WO2013140791A1 - 非水電解質電池 - Google Patents
非水電解質電池 Download PDFInfo
- Publication number
- WO2013140791A1 WO2013140791A1 PCT/JP2013/001871 JP2013001871W WO2013140791A1 WO 2013140791 A1 WO2013140791 A1 WO 2013140791A1 JP 2013001871 W JP2013001871 W JP 2013001871W WO 2013140791 A1 WO2013140791 A1 WO 2013140791A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- positive electrode
- negative electrode
- battery
- active material
- nonaqueous electrolyte
- Prior art date
Links
Images
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
- H01M4/36—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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
Definitions
- the present invention relates to a nonaqueous electrolyte battery using a positive electrode containing vanadium pentoxide and a negative electrode containing silicon.
- Non-aqueous electrolyte batteries represented by lithium ion batteries are widely used as main power sources and memory backup power sources for various electronic devices.
- the demand for non-aqueous electrolyte batteries has been increasing year by year.
- miniaturization and weight reduction of devices are progressing, high functionality of devices and increase in memory capacity are required. Therefore, in applications such as a main power source and a backup power source, the battery is required to be small and have a high capacity. In these applications, it is also important to ensure excellent reliability over a long period of time.
- a positive electrode active material of a nonaqueous electrolyte battery manganese dioxide, fluorinated graphite or the like is used in a primary battery, and sulfides such as TiS 2 and MoS 2 are used in a secondary battery; manganese dioxide, vanadium pentoxide (V 2). O 5) oxide and the like; lithium cobalt oxide, lithium nickel oxide, lithium-containing transition metal composite oxide such as lithium manganate are being considered. Vanadium pentoxide can occlude and release lithium ions and has a high theoretical capacity.
- a non-aqueous electrolyte battery in which a positive electrode using vanadium pentoxide and a lithium negative electrode are combined has a small self-discharge, and thus is used for backup applications.
- Patent Document 1 uses a positive electrode containing vanadium pentoxide and aluminum powder and a negative electrode containing niobium pentoxide doped with lithium in a lithium secondary battery used for backup use, a mobile power source, and the like. Proposed.
- the battery In backup applications, etc., the battery is very frequently exposed to the charged state, and is easily overcharged. If the overcharge state continues, battery characteristics are likely to deteriorate. Therefore, in such an application, a high continuous charge characteristic that suppresses a decrease in battery characteristics even when continuously charged is required.
- vanadium pentoxide Since vanadium pentoxide has a high charging potential, the positive electrode is exposed to an extremely high potential in an overcharged state. When the positive electrode potential is increased, vanadium pentoxide is oxidized and eluted into the non-aqueous electrolyte, causing a side reaction of the negative electrode, which tends to deteriorate battery characteristics.
- vanadium pentoxide When using a battery that uses vanadium pentoxide as the positive electrode for an application that is likely to be exposed to an overcharged state, such as a backup application, ensuring high continuous charge characteristics It leads to improvement.
- Patent Document 1 aluminum powder is added to a positive electrode containing vanadium pentoxide in order to suppress a decrease in battery capacity when overcharged in a high temperature atmosphere. As a result, it is considered that the continuous charge characteristics can be improved to some extent.
- the porosity is likely to increase as compared with the case where other positive electrode active materials are used. When the porosity of the positive electrode is large, the supply rate of the non-aqueous electrolyte to the positive electrode is very high, while the supply rate to the negative electrode is low.
- negative electrodes using graphite and silicon-containing materials are being studied. Since these negative electrodes have a large amount of occlusion of lithium ions and can greatly reduce the negative electrode potential, they are effective in obtaining a high-capacity battery. In particular, silicon-containing materials are attracting attention because they have a larger lithium storage capacity than graphite.
- a negative electrode using a silicon-containing material In a negative electrode using a silicon-containing material, during charging, the negative electrode potential is lowered by occlusion of a large amount of lithium ions, which can be expected to increase the capacity.
- the negative electrode potential is not sufficiently lowered, and the initial capacity of the battery is reduced, thereby reducing the initial static characteristics of the battery.
- a side reaction between the conductive agent, lithium, and the non-aqueous electrolyte included in the negative electrode becomes significant, and the resistance increases. , Battery capacity decreases.
- Patent Document 1 niobium pentoxide doped with lithium is used for the negative electrode.
- the side reaction at the negative electrode as described above involving the conductive agent is particularly remarkable in the negative electrode using a silicon-containing material having a lower reduction potential than that of niobium pentoxide. Incurs a decline.
- a nonaqueous electrolyte battery excellent in initial static characteristics and continuous charge characteristics despite using a positive electrode using vanadium pentoxide and a negative electrode using a silicon-containing material.
- the purpose is to provide.
- One aspect of the present invention includes a pellet-shaped positive electrode, a pellet-shaped negative electrode, a separator interposed between the positive electrode and the negative electrode, and a nonaqueous electrolyte.
- the positive electrode includes a positive electrode active material, aluminum powder, and a conductive agent.
- the positive electrode active material contains vanadium pentoxide
- the positive electrode has a porosity of 35.6 to 45.4% by volume
- the negative electrode contains silicon, a negative electrode active material, a conductive agent And a non-aqueous electrolyte battery containing a binder.
- a nonaqueous electrolyte battery excellent in initial static characteristics and continuous charge characteristics can be obtained despite the use of a positive electrode using vanadium pentoxide and a negative electrode using a silicon-containing material.
- a non-aqueous electrolyte battery including a pellet-shaped positive electrode, a pellet-shaped negative electrode, a separator interposed between the positive electrode and the negative electrode, and a non-aqueous electrolyte.
- the positive electrode includes a positive electrode active material, aluminum powder, a conductive agent, and a binder, and the positive electrode active material includes vanadium pentoxide.
- the negative electrode includes a negative electrode active material containing silicon, a conductive agent, and a binder.
- the porosity of the positive electrode is 35.6 to 45.4% by volume.
- the porosity of the positive electrode tends to be large because the filling property is lower than in the case of other positive electrode active materials.
- the porosity of the positive electrode is large, the supply rate of the nonaqueous electrolyte to the positive electrode becomes extremely high, and therefore the supply rate to the negative electrode is relatively likely to be relatively small.
- the occlusion reaction of lithium ions into the negative electrode proceeds at a very high rate simultaneously with the injection of the non-aqueous electrolyte during battery assembly (initial stage). . That is, in the negative electrode using the negative electrode active material containing silicon, the consumption of the nonaqueous electrolyte in the initial negative electrode becomes very large.
- the negative electrode when continuous charging is performed in a state where the negative electrode potential is not sufficiently lowered, the negative electrode is not charged with a side reaction involving a conductive agent and lithium contained in the negative electrode, rather than a charging reaction of a negative electrode active material containing silicon. Water electrolyte is consumed. Since such a side reaction is an irreversible reaction, the capacity maintenance rate of the battery decreases due to continuous charging.
- the porosity of the pellet-shaped positive electrode is controlled to 45.4% by volume or less. Therefore, even when a positive electrode active material containing vanadium pentoxide is used, the rate at which the nonaqueous electrolyte is absorbed by the positive electrode is moderately slowed, and the supply rate of the nonaqueous electrolyte to the negative electrode is unnecessarily reduced. Can be suppressed.
- the porosity of the positive electrode the slower the absorption of the nonaqueous electrolyte, and the insufficient supply of the nonaqueous electrolyte to the negative electrode is improved.
- the porosity is too small, the battery capacity decreases due to continuous charging.
- the mixture containing the positive electrode components positive electrode mixture
- the components are subjected to a larger load than necessary, so that the particulate components (positive electrode active material, conductive agent, etc.) Etc. collapse, and the conductivity of the positive electrode decreases.
- the side reaction is continuously progressing in the negative electrode containing silicon at the time of continuous charge.
- the positive electrode using vanadium pentoxide and the negative electrode active material containing silicon are obtained by setting the porosity of the pellet-shaped positive electrode to 35.6 to 45.6% by volume. Regardless of the combination with the negative electrode used, an appropriate amount of nonaqueous electrolyte can be retained in both the positive electrode and the negative electrode. For this reason, it is possible to suppress a decrease in static characteristics of the initial battery and to suppress a decrease in capacity during continuous charging. Therefore, even if the nonaqueous electrolyte battery is used for backup, high reliability can be obtained.
- the porosity is 35.6% by volume or more, preferably 35.8% by volume or more, and more preferably 36% by volume or more.
- the porosity of the positive electrode is 45.4% by volume or less, preferably 45.2% by volume or less, and more preferably 45% by volume or less.
- These lower limit values and upper limit values can be arbitrarily combined.
- the porosity may be 35.8-45.4% by volume, or 36-45% by volume.
- the absorption rate of the nonaqueous electrolyte into the positive electrode is remarkably increased, so that a sufficient amount of the nonaqueous electrolyte for the charging reaction cannot be supplied to the negative electrode.
- the negative electrode potential at the time of initial charge cannot be sufficiently reduced, so that the initial static characteristics are deteriorated.
- the state in which the negative electrode potential does not sufficiently decrease continues or continuous charging is performed in this state, a side reaction involving the conductive agent contained in the negative electrode occurs in the negative electrode, and the capacity of the battery decreases. That is, the continuous charge characteristic is deteriorated.
- the porosity of the positive electrode is less than 35.6% by volume, a load is applied to the positive electrode component more than necessary in the process of producing the pellet-shaped positive electrode, so that the particle component (conductive agent or active material) Particles) are crushed or disintegrated. Thereby, the electroconductive path
- the porosity of the positive electrode can be calculated from the mass, volume and true density of the positive electrode.
- the true density of the positive electrode can be calculated from the content and specific gravity of the constituent components of the positive electrode.
- the positive electrode active material is not particularly limited as long as it contains vanadium pentoxide.
- known components used as the positive electrode active material of the nonaqueous electrolyte battery for example, sulfides such as TiS 2 and MoS 2 ; V 6 O 13 , metal oxides such as MnO 2 ; lithium-containing transition metal composite oxides such as lithium cobaltate, lithium nickelate, and lithium manganate may also be included.
- the ratio of vanadium pentoxide in the positive electrode active material is preferably, for example, 70% by mass or more, and may be 80% by mass or more or 90% by mass or more.
- the positive electrode active material may contain only vanadium pentoxide. That is, the ratio of vanadium pentoxide in the positive electrode active material is 100% by mass or less. These lower limit values and upper limit values can be arbitrarily combined. By using a positive electrode active material containing vanadium pentoxide, a flat high voltage can be easily obtained, and a high-capacity battery can be easily realized. In addition, self-discharge is small, and it is easy to improve reliability even when used for backup.
- Vanadium pentoxide is usually in the form of particles.
- the average particle size of vanadium pentoxide is, for example, 1 to 30 ⁇ m, preferably 3 to 20 ⁇ m, and more preferably 5 to 15 ⁇ m.
- the average particle diameter can be determined based on the specific surface area, for example, by calculating the specific surface area by the air permeation method.
- vanadium pentoxide When aluminum powder is used in combination with vanadium pentoxide, it is suppressed that vanadium pentoxide is oxidized and eluted during overcharge. When the oxide of vanadium pentoxide is eluted, a film is formed on the surface of the negative electrode, the charge / discharge reaction is hindered, and the capacity tends to decrease. Although the reason is not clear, it is presumed that by adding aluminum powder to the positive electrode, even if the positive electrode potential becomes excessively high during overcharging, the oxidation of aluminum takes place in preference to the oxidation of vanadium pentoxide. Since the generated oxide of aluminum is stably present in the positive electrode, as a result, it is considered that the decrease in capacity during overcharging is suppressed by adding aluminum powder to the positive electrode.
- the particle size of the aluminum powder is not particularly limited, but is preferably small so that it is easily oxidized during overcharge.
- particles having a particle size of 45 ⁇ m or less in the aluminum powder by the low tap method are preferably 60% by mass or more, and more preferably 70% by mass or more or 80% by mass or more.
- the amount of aluminum powder contained in the positive electrode is, for example, 1 to 20 parts by mass, preferably 1 to 10 parts by mass, and more preferably 1.5 to 8 parts by mass with respect to 100 parts by mass of the positive electrode active material.
- content of aluminum powder is such a range, the fall of the battery capacity at the time of overcharge can be suppressed more effectively.
- the conductive agent contained in the positive electrode is not particularly limited as long as it is a conductor that is stable (for example, does not cause a chemical reaction) within the usable potential range during charging and discharging.
- Specific examples of the conductive agent include graphite such as natural graphite and artificial graphite; carbon black such as acetylene black and ketjen black; conductive fiber such as carbon fiber and metal fiber; and carbon fluoride.
- These electrically conductive agents can be used individually by 1 type or in combination of 2 or more types. From the viewpoint of easily ensuring high conductivity in the positive electrode, it is preferable to use carbon black such as Ketjen Black as a conductive agent.
- the amount of the conductive agent is, for example, 1 to 30 parts by mass, preferably 2 to 20 parts by mass, and more preferably 3 to 10 parts by mass with respect to 100 parts by mass of the positive electrode active material.
- the amount of the conductive agent is within such a range, it is easy to ensure high conductivity in the positive electrode and to easily suppress an increase in initial internal resistance.
- binder contained in the positive electrode examples include polyolefins such as polyethylene and polypropylene; fluorine resins such as polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, and modified products thereof; styrene butadiene rubber And rubber polymers such as modified acrylonitrile rubbers; acrylic polymers such as polyacrylic acid and acrylic acid-methacrylic acid copolymers or salts thereof (sodium salts, ammonium salts, etc.).
- binders can be used individually by 1 type or in combination of 2 or more types.
- a fluororesin such as a tetrafluoroethylene-hexafluoropropylene copolymer is particularly preferable from the viewpoint of easily ensuring the strength of the electrode.
- the amount of the binder is, for example, 0.5 to 10 parts by mass, preferably 1 to 8 parts by mass, and more preferably 1.5 to 7 parts by mass with respect to 100 parts by mass of the positive electrode active material.
- amount of the binder is within such a range, it is easy to ensure high conductivity while ensuring the strength of the positive electrode.
- the positive electrode only needs to contain a positive electrode active material, aluminum powder, a conductive agent, and a binder, and a mixture (mixture) containing these components is prepared, and the mixture is obtained by compression molding into a pellet form. Can do.
- the porosity can be adjusted. Compression molding can be performed, for example, by filling a molding die having a predetermined shape with a mixture and applying pressure. After the mixture is formed into pellets, it may be dried by natural drying or heating under reduced pressure or atmospheric pressure.
- the porosity of a positive electrode can be managed indirectly from the mass and volume of a pellet.
- the pressure applied to the mixture to be formed can be adjusted by adjusting the mass and thickness to obtain a desired porosity.
- the positive electrode pellet can be obtained.
- the positive electrode may include a known current collector as necessary.
- a dispersion medium may be used for the mixture.
- the dispersion medium is not particularly limited, and examples thereof include water, alcohols such as ethanol, ethers such as tetrahydrofuran, amides such as dimethylformamide, N-methyl-2-pyrrolidone, and mixed solvents thereof.
- the binder may be used in the form of a dispersion dispersed in a dispersion medium.
- the negative electrode includes a negative electrode active material (or silicon-containing material) containing silicon, a conductive agent, and a binder.
- silicon-containing materials include silicon alone, silicon alloys, silicon compounds (nitrides, sulfides, oxides, etc.). These silicon-containing materials can be used singly or in combination of two or more. Among these, a silicon simple substance and a silicon alloy are preferable.
- the silicon alloy examples include an alloy of silicon and a transition metal.
- an electrochemically active amorphous silicon phase (amorphous Si phase) and an electrochemically inactive phase can be mixed.
- the inactive phase has a role of relieving the stress of expansion and contraction of the amorphous Si phase that accompanies charge / discharge, and also has a role of imparting conductivity to the negative electrode active material.
- Such an electrochemically inactive phase includes an intermetallic compound of a transition metal element and silicon constituting the alloy.
- the amorphous Si phase may contain microcrystallites, but the crystallite size is so small that it cannot be confirmed by an X-ray diffraction spectrum, for example, 10 nm or less.
- the transition metal elements constituting the silicon alloy include Group 4 elements of the periodic table such as Ti and Zr; Group 6 elements such as Cr, Mo and W; Group 7 elements such as Mn; Group elements; Group 9 elements such as Co; Group 10 elements such as Ni; Group 11 elements such as Cu.
- the intermetallic compound may contain one kind of transition metal element, or may contain two or more kinds in combination. Of these, Ti, Ni, W, Co and the like are preferable.
- preferable silicon alloys include Si—Ti alloy, Si—Ni alloy, Si—W alloy, Si—Co alloy, and the like.
- the negative electrode active material preferably includes a Si—Ti alloy, and particularly preferably includes a Si—titanium alloy including an amorphous Si phase.
- the mass ratio of silicon to the transition metal element is, for example, 40:60 to 80:20, preferably 50:50 to 75:25, and more preferably 55:45 to 70. : 30.
- the mass ratio of silicon and transition metal element is in such a range, in addition to ensuring high battery capacity, it is easy to relieve stress associated with volume change of the active material during charge and discharge, and high conductivity. Is easy to obtain.
- the mass ratio between silicon and the transition metal element can be treated as the same mass ratio between silicon and the transition metal used when forming the alloy.
- the silicon alloy can be produced by a known method such as a mechanical alloying method, a vacuum deposition method, a plating method, a gas phase chemical reaction method, a liquid quenching method, or an ion beam sputtering method.
- the negative electrode active material may be doped with lithium in advance.
- Lithium doping is performed by preparing a pellet-like negative electrode (or negative electrode precursor) containing a negative electrode active material, and then attaching lithium foil or the like, dipping in a non-aqueous electrolyte, and electrochemically shorting. it can.
- the conductive agent contained in the negative electrode can be selected from the same as those exemplified for the positive electrode, and is preferably carbonaceous. Of the conductive agents, it is more preferable to use graphite from the viewpoint of low bulk and high conductivity.
- the amount of the conductive agent is, for example, 15 to 45 parts by weight, preferably 18 to 42 parts by weight, more preferably 20 to 40 parts by weight with respect to 100 parts by weight of the negative electrode active material.
- the conductive agent is in such a range, high conductivity is easily obtained, and a decrease in battery capacity can be more effectively suppressed even during continuous charging.
- the binder contained in the negative electrode can be selected from the same as those exemplified for the positive electrode.
- an acrylic polymer or a salt thereof is preferable.
- the acrylic polymer include a polymer containing at least one selected from acrylic acid and methacrylic acid as a monomer unit.
- Specific examples of such acrylic polymers include acrylics such as polyacrylic acid, polymethacrylic acid, acrylic acid-methacrylic acid copolymer, ethylene-acrylic acid copolymer, and acrylic acid-methyl acrylate copolymer.
- Examples include copolymers of acid and / or methacrylic acid and other copolymerizable monomers (olefins, acrylic esters, methacrylic esters, etc.) or salts thereof (alkali metal salts such as sodium salts; ammonium salts, etc.). It is done.
- polyacrylic acid is preferable.
- the binder may be used alone or in combination of two or more.
- the binder may be used in the form of a dispersion dispersed in a dispersion medium.
- the ratio of the binder is, for example, 1 to 20 parts by mass, preferably 5 to 15 parts by mass with respect to 100 parts by mass of the negative electrode active material.
- the negative electrode only needs to contain a negative electrode active material containing silicon, a binder, and a conductive agent. Similarly to the positive electrode, a mixture (mixture) containing these components is prepared, and the mixture is compressed into a pellet. Can be obtained.
- the negative electrode may include a known current collector as necessary.
- the pellet-shaped positive electrode and the pellet-shaped negative electrode are arranged to face each other with a separator interposed therebetween.
- the separator include a woven fabric and a non-woven fabric, and a microporous film made of polyolefin.
- the resin constituting the woven or non-woven fabric examples include polyolefin such as polypropylene; polyphenylene sulfide; aromatic polyester such as aramid; polyimide resin such as polyimide and polyamideimide; and polyether ether ketone.
- the woven fabric or the nonwoven fabric may contain one of these resins alone or in combination of two or more.
- the polyolefin contained in the microporous film examples include polyethylene, polypropylene, ethylene-propylene copolymer, and the like.
- the shape and size of the separator are not particularly limited as long as the positive electrode and the negative electrode can be insulated.
- a circular separator that is slightly larger than the facing area of the positive electrode and the negative electrode is used.
- the thickness of the separator can be appropriately selected from a range of about 10 to 250 ⁇ m, for example.
- Non-aqueous electrolyte contains a nonaqueous solvent and a lithium salt that dissolves in the nonaqueous solvent.
- the types of the non-aqueous solvent and the lithium salt are not particularly limited, and known ones can be used.
- Cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate
- Chain carbonates such as dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate
- -Cyclic ethers such as dioxane, 1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran; 1,2-dimethoxyethane (DME), 1,2-diethoxyethane, 1,3-dimethoxypropane, diethylene glycol
- chain ethers such as dimethyl ether and tetraglyme
- lactones such as ⁇ -butyrolactone
- sulfoxide compounds such as sulfolane.
- a non-aqueous solvent can be used individually by 1 type or in mixture of 2 or more types.
- the lithium salt is not particularly limited, for example, lithium salt of a fluorine-containing acid imide [LiN (CF 3 SO 2) 2, LiN (C 2 F 5 SO 2) 2, LiN (CF 3 SO 2) (C 4 F 9 SO 2 )], lithium salts of fluorine-containing acids (LiPF 6 , LiBF 4 , LiCF 3 SO 3, etc.), lithium salts of chlorine-containing acids (LiClO 4, etc.), etc. can be used.
- a lithium salt can be used individually by 1 type or in combination of 2 or more types.
- the concentration of the lithium salt in the nonaqueous electrolyte is, for example, 0.5 to 2 mol / L.
- the non-aqueous electrolyte may contain a known additive, for example, a carbonate having a polymerizable unsaturated bond such as vinylene carbonate or vinyl ethylene carbonate; an aromatic compound such as cyclohexylbenzene or diphenyl ether.
- a carbonate having a polymerizable unsaturated bond such as vinylene carbonate or vinyl ethylene carbonate
- an aromatic compound such as cyclohexylbenzene or diphenyl ether.
- the nonaqueous electrolyte may be a solution in which a lithium salt is dissolved in a nonaqueous solvent, or may be a gel in which this solution is held in a polymer material.
- Polymer materials include: fluororesins such as polyvinylidene fluoride and vinylidene fluoride-hexafluoropropylene copolymers; chlorine-containing vinyl resins such as polyvinyl chloride; vinyl cyanide resins such as polyacrylonitrile; acrylic resins such as polyacrylate Polyalkylene oxides such as polyethylene oxide can be used. These polymer materials may be used singly or in combination of two or more.
- a non-aqueous electrolyte battery can be produced, for example, by housing a pellet-shaped positive electrode and a pellet-shaped negative electrode, a separator interposed therebetween, and a non-aqueous electrolyte in a battery case and sealing with a sealing plate.
- a manufacturing method in particular is not restrict
- a coin-type nonaqueous electrolyte battery accommodates a nonaqueous electrolyte by disposing a positive electrode in a battery case (such as an inner bottom surface) and disposing a separator on the positive electrode. Next, in a state where the negative electrode is attached to the inner surface of the sealing plate, the sealing plate is fitted into the opening of the battery case via a gasket and sealed to obtain a coin-type lithium secondary battery.
- FIG. 1 is a schematic sectional view of a coin-type lithium secondary battery according to an embodiment of the present invention.
- the coin-type lithium secondary battery 10 includes a disk pellet-shaped positive electrode 4, a disk pellet-shaped negative electrode 5, a separator 6 interposed between the positive electrode 4 and the negative electrode 5, and a non-aqueous electrolyte (not shown).
- the positive electrode 4 includes a positive electrode active material containing vanadium pentoxide, an aluminum powder, a conductive agent, and a binder, and has a porosity of 35.6 to 45.4% by volume.
- the negative electrode 5 includes a negative electrode active material containing silicon, a conductive agent, and a binder.
- the separator 6 is a resin nonwoven fabric or a microporous film punched into a circle.
- the battery case 1 made of stainless steel is accommodated so that the positive electrode 4 and the negative electrode 5 are insulated by the separator 6, and the positive electrode 4 is in contact with the inner bottom surface of the battery case 1.
- a gasket 3 made of resin (such as polypropylene) that is injection-molded in a ring shape is disposed from the opening to the inner wall.
- the upper end of the opening of the battery case 1 is bent inward by caulking with the gasket 3 interposed between the sealing plate 2 made of stainless steel.
- the battery case 1 and the sealing plate 2 constitute a battery outer package.
- the negative electrode when assembling the battery, can be doped with lithium.
- a negative electrode in the form of a disk pellet containing a negative electrode active material, a conductive agent and a binder (or a negative electrode precursor) with a lithium foil pasted and a positive electrode, with a separator interposed therebetween The battery is accommodated in a battery case so as to be in a state of being allowed to flow, and a nonaqueous electrolyte is further injected.
- the negative electrode precursor in which lithium is doped into the negative electrode active material can be obtained by immersing the negative electrode precursor with the lithium foil attached in a non-aqueous electrolyte and electrochemically shorting the negative electrode precursor.
- Example 1 A coin-type lithium secondary battery A1 as shown in FIG. 1 was produced by the following procedure.
- (1) Production of negative electrode precursor A Ti—Si alloy was produced by mechanical alloying. At that time, Ti and Si were thrown into the vibrating ball mill apparatus at a mass ratio of 35:65, and stainless steel balls with a diameter of 15 mm were thrown into the apparatus. The inside of the apparatus was replaced with argon and maintained at 1 atmosphere. A mechanical alloying operation was performed under these conditions. The vibrating ball mill apparatus was driven under the conditions of an amplitude of 8 mm and a rotation speed of 1200 rpm, and mechanical alloying was performed for 80 hours. The obtained alloy powder was classified, and an alloy powder having a particle size of 50 ⁇ m or less was used as a negative electrode active material.
- a negative electrode mixture was prepared by mixing the obtained negative electrode active material, graphite as a conductive agent, and polyacrylic acid as a binder in a mass ratio of solid content of 100: 30: 10. .
- the obtained negative electrode mixture was molded into a disk-shaped pellet having a diameter of 7.0 mm and a thickness of 0.30 mm, and dried at 160 ° C. for 12 hours to obtain a negative electrode precursor.
- binder an aqueous solution of non-crosslinked polyacrylic acid having a weight average molecular weight of 1,000,000 (manufactured by Toagosei Co., Ltd.) was used.
- conductive agent graphite having an average particle diameter of 10 ⁇ m (manufactured by Nippon Graphite Co., Ltd.) was used.
- positive electrode Vanadium pentoxide as a positive electrode active material (average particle diameter by air permeation method: 8 ⁇ m), ketjen black as a conductive agent, and an aqueous dispersion of a fluororesin as a binder
- the positive electrode mixture was obtained by mixing aluminum powder so that it might become 87: 7: 3: 3 by solid content mass ratio.
- the obtained positive electrode mixture was press-molded into a disk-shaped pellet having a diameter of 6.2 mm and a thickness of 1.09 mm, and dried at 200 ° C. for 10 hours to produce a positive electrode.
- the aluminum powder particles having a particle size of 45 ⁇ m or less by the low tap method with 80% by mass or more were used.
- a coin-type lithium secondary battery shown in FIG. 1 was produced according to the method described above.
- a metallic lithium foil is attached to the surface of the negative electrode precursor obtained in (1), and contacted with a non-aqueous electrolyte in the battery to cause an electrochemical short circuit.
- Lithium was alloyed to produce a negative electrode.
- the outer dimensions of the battery were an outer diameter of 9.5 mm and a height of 2.0 mm.
- the battery produced by the above manufacturing process was designated as battery A1.
- a total of 10 batteries A1 were produced in the same manner as described above.
- a polypropylene nonwoven fabric was used as the separator.
- a polypropylene gasket was used.
- the concentration of the lithium salt in the nonaqueous electrolyte was 1 mol / L.
- the amount of nonaqueous electrolyte injected into the battery was 45 ⁇ l.
- the battery was continuously charged in an atmosphere at 60 ° C., and the discharge capacity after continuous charge was measured in the same manner as in the case of the initial discharge capacity, and the average value was calculated.
- Continuous charging was performed by continuously applying a voltage of 3.7 V for 100 days.
- the ratio (%) of the average value of the discharge capacity of the battery after the continuous charge to the average value of the initial discharge capacity was used as an index of the continuous charge characteristics as the remaining capacity rate (or capacity retention rate) by the continuous charge. The larger the capacity remaining rate, the better the continuous charging characteristics.
- Examples 2 to 3 and Comparative Examples 1 to 4 A positive electrode was produced in the same manner as in Example 1 except that the porosity was adjusted by changing the thickness of the pellet in the production of the positive electrode (2). Batteries A2 to A7 were prepared and evaluated in the same manner as in Example 1 except that the obtained positive electrode was used. In each battery, the thickness of the positive electrode pellet is 1.21 mm (battery A2), 1.19 mm (battery A3), 1.17 mm (battery A4), 1.01 mm (battery A5), and 1.00 mm (battery A6). 0.97 mm (Battery A7).
- Table 1 shows the results of Examples and Comparative Examples.
- the batteries A1, A4, and A5 are examples, and the batteries A2, A3, A6, and A7 are comparative examples.
- the batteries A1, A4, and A5 in which the porosity of the positive electrode is in the range of 35.6 to 45.4% by volume have a very high capacity even after continuous charging at 60 ° C. A residual rate was obtained. These batteries also had a low initial series resistance. This is considered to be due to the suppression of the initial decrease in conductivity in the positive electrode.
- the nonaqueous electrolyte battery according to one embodiment of the present invention is excellent in continuous charge characteristics. Also, the initial static characteristics are excellent. That is, the nonaqueous electrolyte battery can stably obtain excellent battery characteristics. Therefore, the nonaqueous electrolyte battery can be used for various applications such as a small portable device such as a mobile phone or a digital still camera as a main power source or a backup power source.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
(正極)
ペレット状正極において、空隙率は、35.6体積%以上であり、好ましくは35.8体積%以上、さらに好ましくは36体積%以上である。また、正極の空隙率は、45.4体積%以下であり、好ましくは45.2体積%以下であり、さらに好ましくは45体積%以下である。これらの下限値と上限値とは任意に組み合わせることができる。例えば、空隙率は、35.8~45.4体積%、または36~45体積%であってもよい。
なお、正極の空隙率は、正極の質量、体積および真密度から算出できる。正極の真密度は、正極の構成成分の含有量および比重から算出できる。
負極は、ケイ素を含む負極活物質(またはケイ素含有材料)と、導電剤と、結着剤とを含む。
ケイ素含有材料としては、ケイ素単体、ケイ素合金、ケイ素化合物(窒化物、硫化物、酸化物など)などが例示できる。これらのケイ素含有材料は、一種を単独でまたは二種以上を組み合わせて使用できる。これらのうち、ケイ素単体、ケイ素合金が好ましい。
ケイ素合金においては、電気化学的に活性な非晶質ケイ素の相(非晶質Si相)と、電気化学的に不活性な相とを混在させることができる。不活性な相は、充放電に伴う非晶質Si相の膨張や収縮の応力を緩和する役割を有するとともに、負極活物質に導電性を付与する役割も担う。このような電気化学的に不活性な相は、合金を構成する遷移金属元素とケイ素との金属間化合物を含む。なお、非晶質Si相は、微小結晶子を含むこともあるが、結晶子のサイズは、X線回折スペクトルでは確認できないほど小さく、例えば、10nm以下である。
結着剤の割合は、負極活物質100質量部に対して、例えば、1~20質量部、好ましくは5~15質量部である。
ペレット状の正極と、ペレット状の負極とは、両者の間にセパレータを介在させた状態で、対向配置される。
セパレータとしては、例えば、織布または不織布などの他、ポリオレフィン製の微多孔フィルムなどが例示できる。
セパレータの厚みは、例えば、10~250μm程度の範囲から適宜選択できる。
非水電解質は、非水溶媒と、非水溶媒に溶解するリチウム塩とを含有する。非水溶媒およびリチウム塩の種類は、特に制限されず、公知のものが使用できる。
非水溶媒としては、特に制限されないが、例えば、エチレンカーボネート(EC)、プロピレンカーボネート(PC)、ブチレンカーボネートなどの環状カーボネート;ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネートなどの鎖状カーボネート;1,4-ジオキサン、1,3-ジオキソラン、テトラヒドロフラン、2-メチルテトラヒドロフラン、3-メチルテトラヒドロフランなどの環状エーテル;1,2-ジメトキエタン(DME)、1,2-ジエトキシエタン、1,3-ジメトキシプロパン、ジエチレングリコールジメチルエーテル、テトラグライムなどの鎖状エーテル;γ-ブチロラクトンなどのラクトン;スルホランなどのスルホキシド化合物などが挙げられる。非水溶媒は、一種を単独で又は二種以上を混合して使用できる。
コイン形リチウム二次電池10は、円盤ペレット状の正極4、円盤ペレット状の負極5、正極4と負極5との間に介在するセパレータ6と、図示しない非水電解質とを有する。正極4は、五酸化バナジウムを含む正極活物質、アルミニウム粉末、導電剤および結着剤を含み、空隙率が35.6~45.4体積%である。負極5は、ケイ素を含む負極活物質、導電剤および結着剤を含む。
電池ケース1には、開口部から内側壁にかけて、リング状に射出成型された樹脂製(ポリプロピレン製など)のガスケット3が配置されている。電池ケース1の開口上端部は、ステンレス鋼製の封口板2との間にガスケット3を介在させた状態で、かしめ加工により内方に屈曲している。電池ケース1と封口板2とは、電池外装体を構成する。
下記の手順で、図1に示すようなコイン形リチウム二次電池A1を作製した。
(1)負極前駆体の作製
メカニカルアロイング法によってTi-Si合金を作製した。その際、TiとSiを35:65の質量比で振動ボールミル装置に投入し、さらに直径15mmのステンレス鋼製ボールを投入した。装置内部をアルゴンで置換し、1気圧に維持した。この条件下でメカニカルアロイング操作を行った。振動ボールミル装置を、振幅8mm、回転数1200rpmの条件で駆動し、80時間、メカニカルアロイングを行った。得られた合金粉末を分級し、50μm以下の粒径の合金粉末を負極活物質として使用した。
正極活物質としての五酸化バナジウム(空気透過法による平均粒径:8μm)と、導電剤としてのケッチェンブラックと、結着剤としてのフッ素系樹脂の水性ディスパージョンと、アルミニウム粉末とを、固形分質量比率で87:7:3:3となるように混合することにより、正極合剤を得た。得られた正極合剤を、直径6.2mm、厚さ1.09mmの円盤状のペレットに加圧成型し、200℃で10時間乾燥することにより、正極を作製した。なお、アルミニウム粉末としては、ロータップ法による粒径45μm以下の粒子が80質量%以上のものを使用した。
図1に示すコイン形リチウム二次電池を、既述の方法に準じて作製した。
電池の組立において、(1)で得られた負極前駆体の表面に金属リチウム箔を貼り付け、電池内で非水電解質と接触させて電気化学的にショートさせることにより、前駆体中のSiにリチウムを合金化し、これにより、負極を作製した。
なお、セパレータとして、ポリプロピレンの不織布を用いた。また、ポリプロピレン製のガスケットを用いた。非水電解質としては、非水溶媒としての、PC:EC:DME=1:1:1(体積比)の混合溶媒に、リチウム塩LiBF4を溶解して調製したものを使用した。非水電解質中のリチウム塩の濃度は、1mol/Lであった。電池内に注液した非水電解質の量は45μlであった。
得られた電池および電池に使用した正極について、下記(a)~(c)の評価を行った。
(a)正極の空隙率
組み立てた電池を分解して正極を取り出し、洗浄および乾燥し、質量および寸法(体積)を測定した。また、正極の構成成分の比重および含有量に基づいて、正極の真密度を算出した。このようにして得られた正極の質量、寸法および真密度から、正極の空隙率を算出した。
組み立て直後の電池を、45℃で72時間加熱することによりエージング処理した。エージング処理後の電池の直列抵抗(IR)を測定し、10個の電池について平均値を算出した。なお、測定は、抵抗測定器を使用して、正弦波交流法(1kHz)により正極端子(電池の正極ケース)と負極端子(負極封口板)との間の直列抵抗を測定することにより行った。
組み立て直後の電池を、45℃で72時間加熱することによりエージング処理し、次いで、510Ωの抵抗を介して、3.7Vの定電圧で約40時間充電した。充電した電池を、10kΩの抵抗を介して2.0Vまで放電し、このときの放電容量(初期の放電容量)を測定し、10個の電池の平均値を算出した。
正極の作製(2)において、ペレットの厚みを変更することにより空隙率を調整した以外は、実施例1と同様にして正極を作製した。得られた正極を用いる以外は、実施例1と同様にして、電池A2~A7を作製し、評価を行った。なお、各電池において正極ペレットの厚みは、1.21mm(電池A2)、1.19mm(電池A3)、1.17mm(電池A4)、1.01mm(電池A5)、1.00mm(電池A6)、0.97mm(電池A7)とした。
2 封口板
3 ガスケット
4 正極
5 負極
6 セパレータ
10 コイン形リチウム二次電池
Claims (5)
- ペレット状の正極、ペレット状の負極、前記正極と前記負極との間に介在するセパレータ、および非水電解質を含み、
前記正極が、正極活物質、アルミニウム粉末、導電剤および結着剤を含み、前記正極活物質が、五酸化バナジウムを含み、前記正極の空隙率が35.6~45.4体積%であり、
前記負極が、ケイ素を含む負極活物質、導電剤および結着剤を含む、非水電解質電池。 - 前記正極の空隙率が36~45体積%である、請求項1に記載の非水電解質電池。
- 前記正極中に含まれる前記アルミニウム粉末の量が、前記正極活物質100質量部に対して、1~20質量部である、請求項1または2に記載の非水電解質電池。
- 前記負極活物質が、ケイ素単体およびケイ素合金からなる群より選択される少なくとも一種である、請求項1~3のいずれか1項に記載の非水電解質電池。
- 前記負極活物質が、非晶質ケイ素の相を含むケイ素-チタン合金を含む、請求項1~4のいずれか1項に記載の非水電解質電池。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014506039A JP5995014B2 (ja) | 2012-03-22 | 2013-03-19 | 非水電解質二次電池 |
US14/378,930 US9490479B2 (en) | 2012-03-22 | 2013-03-19 | Non-aqueous electrolyte battery |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012065011 | 2012-03-22 | ||
JP2012-065011 | 2012-03-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013140791A1 true WO2013140791A1 (ja) | 2013-09-26 |
Family
ID=49222269
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/001871 WO2013140791A1 (ja) | 2012-03-22 | 2013-03-19 | 非水電解質電池 |
Country Status (3)
Country | Link |
---|---|
US (1) | US9490479B2 (ja) |
JP (1) | JP5995014B2 (ja) |
WO (1) | WO2013140791A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017085900A1 (ja) * | 2015-11-18 | 2017-05-26 | パナソニックIpマネジメント株式会社 | 非水電解質電池 |
KR20180049811A (ko) * | 2016-11-03 | 2018-05-11 | 주식회사 엘지화학 | 리튬이온 이차 전지 |
CN108352557A (zh) * | 2015-11-13 | 2018-07-31 | 松下知识产权经营株式会社 | 非水电解质电池和非水电解质电池用部件 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107852557B (zh) * | 2015-08-10 | 2020-06-23 | 美商楼氏电子有限公司 | 麦克风和用于麦克风的系统 |
TWI666815B (zh) * | 2018-01-26 | 2019-07-21 | 財團法人工業技術研究院 | 水溶液鋰離子電池及用於其中的電極 |
US11820603B2 (en) | 2019-02-11 | 2023-11-21 | Gea Process Engineering Nv | Feeder device for feeding a powder material |
CN112397707A (zh) * | 2020-11-13 | 2021-02-23 | 何叶红 | 一种用于锂离子电池的多孔vo2微球及其制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07226231A (ja) * | 1994-02-09 | 1995-08-22 | Matsushita Electric Ind Co Ltd | リチウム二次電池 |
JP2007157704A (ja) * | 2005-11-09 | 2007-06-21 | Matsushita Electric Ind Co Ltd | コイン型リチウム二次電池用負極とその製造方法、およびコイン型リチウム二次電池 |
JP2009170428A (ja) * | 2009-03-23 | 2009-07-30 | Ube Ind Ltd | 非水二次電池 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3211259B2 (ja) * | 1991-05-02 | 2001-09-25 | ソニー株式会社 | 非水電解液二次電池 |
US5795680A (en) * | 1995-11-30 | 1998-08-18 | Asahi Glass Company Ltd. | Non-aqueous electrolyte type secondary battery |
WO2003100886A1 (en) * | 2002-05-27 | 2003-12-04 | Japan Storage Battery Co., Ltd. | Battery |
JPWO2005036690A1 (ja) * | 2003-10-07 | 2006-12-28 | 株式会社ジーエス・ユアサコーポレーション | 非水電解質二次電池 |
US20100151321A1 (en) | 2005-11-09 | 2010-06-17 | Teruaki Yamamoto | Negative electrode for coin-shaped lithium secondary battery, method for producing the same, and coin-shaped lithium secondary battery |
US20100124702A1 (en) * | 2008-11-17 | 2010-05-20 | Physical Sciences, Inc. | High Energy Composite Cathodes for Lithium Ion Batteries |
-
2013
- 2013-03-19 US US14/378,930 patent/US9490479B2/en active Active
- 2013-03-19 JP JP2014506039A patent/JP5995014B2/ja active Active
- 2013-03-19 WO PCT/JP2013/001871 patent/WO2013140791A1/ja active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07226231A (ja) * | 1994-02-09 | 1995-08-22 | Matsushita Electric Ind Co Ltd | リチウム二次電池 |
JP2007157704A (ja) * | 2005-11-09 | 2007-06-21 | Matsushita Electric Ind Co Ltd | コイン型リチウム二次電池用負極とその製造方法、およびコイン型リチウム二次電池 |
JP2009170428A (ja) * | 2009-03-23 | 2009-07-30 | Ube Ind Ltd | 非水二次電池 |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108352557A (zh) * | 2015-11-13 | 2018-07-31 | 松下知识产权经营株式会社 | 非水电解质电池和非水电解质电池用部件 |
WO2017085900A1 (ja) * | 2015-11-18 | 2017-05-26 | パナソニックIpマネジメント株式会社 | 非水電解質電池 |
JPWO2017085900A1 (ja) * | 2015-11-18 | 2018-04-19 | パナソニックIpマネジメント株式会社 | 非水電解質電池 |
US10587004B2 (en) | 2015-11-18 | 2020-03-10 | Panasonic Intellectual Property Management Co., Ltd. | Nonaqueous electrolyte battery |
KR20180049811A (ko) * | 2016-11-03 | 2018-05-11 | 주식회사 엘지화학 | 리튬이온 이차 전지 |
CN109155431A (zh) * | 2016-11-03 | 2019-01-04 | 株式会社Lg化学 | 锂离子二次电池 |
JP2019515460A (ja) * | 2016-11-03 | 2019-06-06 | エルジー・ケム・リミテッド | リチウムイオン二次電池 |
KR101991896B1 (ko) * | 2016-11-03 | 2019-09-30 | 주식회사 엘지화학 | 리튬이온 이차 전지 |
US10923717B2 (en) | 2016-11-03 | 2021-02-16 | Lg Chem, Ltd. | Lithium ion secondary battery |
CN109155431B (zh) * | 2016-11-03 | 2022-01-25 | 株式会社Lg化学 | 锂离子二次电池 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2013140791A1 (ja) | 2015-08-03 |
US9490479B2 (en) | 2016-11-08 |
JP5995014B2 (ja) | 2016-09-21 |
US20150017540A1 (en) | 2015-01-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5641862B2 (ja) | コイン形リチウム二次電池 | |
JP5995014B2 (ja) | 非水電解質二次電池 | |
KR101568418B1 (ko) | 부극 및 이차 전지 | |
JP5583265B2 (ja) | 端子付電池 | |
KR20060106622A (ko) | 비수성 이차 전지용 음극 | |
JP2004362895A (ja) | 負極材料およびそれを用いた電池 | |
JP2010080407A (ja) | 正極活物質、正極および非水電解質二次電池に関する。 | |
JPH0963590A (ja) | 非水電解質二次電池 | |
JP2010123331A (ja) | 非水電解質二次電池 | |
JP2010009960A (ja) | 正極活物質の製造方法および正極活物質 | |
JP2003229125A (ja) | 非水電解質電池 | |
JP6504507B2 (ja) | リチウム電池 | |
JP2009134970A (ja) | 非水電解質電池 | |
JP2005302382A (ja) | 非水電解液二次電池パック | |
JP4701595B2 (ja) | リチウムイオン二次電池 | |
JP2005293960A (ja) | リチウムイオン二次電池用負極およびリチウムイオン二次電池 | |
JP2002222651A (ja) | 非水電解質二次電池 | |
JP6668848B2 (ja) | リチウムイオン二次電池 | |
JP2007059206A (ja) | 負極および電池 | |
JP4085481B2 (ja) | 電池 | |
JP2002313418A (ja) | 非水電解質及び非水電解質二次電池 | |
JP2004342459A (ja) | 非水電解質電池 | |
CN108352559B (zh) | 非水电解质电池 | |
JP2001006684A (ja) | 非水電解質電池 | |
JP4938923B2 (ja) | 二次電池 |
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: 13764246 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2014506039 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14378930 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: 13764246 Country of ref document: EP Kind code of ref document: A1 |