WO2013150937A1 - リチウムイオン二次電池 - Google Patents
リチウムイオン二次電池 Download PDFInfo
- Publication number
- WO2013150937A1 WO2013150937A1 PCT/JP2013/058978 JP2013058978W WO2013150937A1 WO 2013150937 A1 WO2013150937 A1 WO 2013150937A1 JP 2013058978 W JP2013058978 W JP 2013058978W WO 2013150937 A1 WO2013150937 A1 WO 2013150937A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- active material
- positive electrode
- electrode active
- ion secondary
- lithium ion
- 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
- 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
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a lithium ion secondary battery having excellent cycle characteristics and a long life.
- Lithium ion secondary batteries can be used for portable electronic devices and personal computers, as well as power sources for electric vehicles (EV), hybrid vehicles (HEV), plug-in hybrid vehicles (PHV), etc. Widely used in systems, large-capacity charge / discharge batteries for power supply in the event of a large-scale disaster, and super-large charge / discharge batteries used in substations that form a power grid called a smart grid. Life expectancy of lithium-ion secondary batteries for portable electronic devices is 1-3 years, while large lithium-ion secondary batteries are required to have a long life of 10-20 years. Furthermore, the super large lithium ion secondary battery is required to have a life span of at least 25 to 30 years.
- the basic structure of a lithium ion secondary battery is that a positive electrode active material layer containing a positive electrode active material and a negative electrode active material layer containing a negative electrode active material, each formed on a current collector, are interposed via a separator.
- each of the positive electrode active material and the negative electrode active material contains lithium ions. Charging and discharging cycles are performed by reversibly storing and releasing.
- Patent Document 1 A lithium ion secondary battery (Patent Document 1) has been reported.
- a cyclic sulfonic acid ester containing at least two sulfonyl groups is contained in the electrolyte, and a surface film (Solid electrolyte interphase: SEI film) that suppresses deterioration due to charge and discharge is formed on the negative electrode surface, and is included in the positive electrode Lithium-ion secondary battery (Patent Document 2) that suppresses manganese elution from the manganese oxide, suppresses manganese adhesion on the negative electrode surface, and improves charge / discharge cycle characteristics, and positive electrode using lithium manganese spinel
- a thin passive film is formed on the positive electrode and the electrolyte interface by preliminarily heat-treating, and by suppressing Mn elution, Coulomb efficiency and high temperature cycle characteristics and storage characteristics are improved.
- Patent Document 3 The improved lithium ion secondary battery (Patent Document 3) and the cyclic sulfonic acid ester contained in the electrolytic solution are charged and thereafter Decomposing the positive electrode to form a sulfur-containing protective coating by Jingu, a secondary battery having an improved rapid charge and discharge cycle life at high temperature (Patent Document 4) have been reported.
- Patent Document 4 a secondary battery having an improved rapid charge and discharge cycle life at high temperature
- Patent Document 5 A lithium ion secondary battery (Patent Document 5) has been reported.
- the positive electrode using a lithium-manganese composite oxide as an active material has a problem of distortion of the crystal due to change in the valence of manganese in the crystal due to the release and insertion of lithium ions during charge and discharge, and further, manganese ions from the crystal. It has been pointed out that the positive electrode is deteriorated due to the loss of the crystal structure due to elution. In particular, in high temperature environments, elution of manganese ions is promoted by repeated charge and discharge, and the battery capacity tends to decrease. The eluted manganese is deposited on the surface of the negative electrode active material and the separator, and lithium In some cases, the movement of ions is hindered and cycle characteristics are reduced.
- Patent Documents 1-4 disclose a technique for suppressing transition metal elution from the positive electrode
- Patent Documents 3 and 4 disclose a technique for suppressing transition metal elution by forming an SEI film on the positive electrode. ing.
- the lithium ion secondary battery described in Patent Document 3 it is difficult to control the formation of the film because the electrolytic solution is decomposed by heat treatment to form the positive electrode SEI film.
- a positive electrode active material, initial charge conditions, aging conditions, etc. are set and a protective film containing sulfur is formed.
- the reaction rate of oxidative decomposition is not sufficient, and depending on the type of the sulfur-containing compound, a sufficient protective film may not be formed.
- the technology for forming a high-quality SEI film on the positive electrode is not yet sufficient, and what additive is used as an additive to be added to the electrolytic solution and how the additive is added. There is a technical problem in whether to decompose to form a positive electrode SEI film.
- additives for forming a good SEI film on the negative electrode have been mainly used so far, and this role does not change even when the SEI film is formed on the positive electrode. For this reason, as an ideal additive, a high-quality SEI film can be simultaneously formed on the positive electrode and the negative electrode with one kind of additive.
- a positive electrode additive together with a negative electrode additive as an additive, it is necessary to select a positive electrode additive that does not hinder the action of the negative electrode additive.
- the additive can form a SEI film with a high reaction rate (decomposition rate). This is because film formation does not occur unless the reaction rate of the additive is high.
- the reaction rate of the additive depends on the reaction method and conditions, but preferably has a high reaction rate (decomposition rate) under normal operating conditions (operating voltage, operating temperature).
- a lithium ion secondary battery using a lithium manganese-based oxide as a positive electrode active material can easily form an SEI film on the positive electrode surface as well as the negative electrode surface, which suppresses repeated charge / discharge deterioration.
- the present inventors can react with a sulfonic acid ester contained in an electrolytic solution at the time of initial charge and discharge, and are extremely efficient.
- the knowledge that a SEI film can be formed on the positive electrode surface was obtained.
- the present inventors have found that this SEI film does not inhibit lithium ion permeation, inhibits manganese ion permeation, and can remarkably suppress elution of manganese from the lithium manganese oxide of the positive electrode active material.
- the present invention relates to a lithium ion secondary battery having a positive electrode active material layer containing a lithium manganese oxide as a positive electrode active material, a negative electrode active material layer containing a negative electrode active material, and an electrolytic solution soaking them.
- the present invention relates to a lithium ion secondary battery, wherein the positive electrode active material layer includes carbon nanotubes, and the electrolytic solution includes a sulfonate ester.
- the lithium ion secondary battery of the present invention is a lithium ion secondary battery using a lithium manganese oxide as a positive electrode active material.
- the SEI film that suppresses deterioration in repeated charge and discharge is applied not only to the negative electrode surface but also to the positive electrode. It is easily formed on the surface, in particular, suppresses a decrease in capacity when used in a high temperature environment, improves charge / discharge cycle characteristics, and has a long life.
- the lithium ion secondary battery of the present invention includes a positive electrode active material layer containing a lithium manganese composite oxide as a positive electrode active material, a negative electrode active material layer containing a negative electrode active material, and an electrolytic solution for immersing them.
- the positive electrode can have a structure in which a positive electrode active material is integrated with a positive electrode binder and is bound on a positive electrode current collector as a positive electrode active material layer.
- the positive electrode active material releases lithium ions into the electrolyte during charging and occludes lithium ions from the electrolyte during discharge, and contains a lithium manganese oxide.
- the lithium manganese oxide may have any of a layered structure, a spinel structure, an olivine structure, and the like. Specifically, mention may be made of LiMnO 2, LiMn 2 O 4, LiNiMnO 2, LiNiCoMnO 2, LiMnMgO 4, Li 2 MnO3, LiCoMnO2, LiMnPO 4 , and the like.
- a lithium-based oxide not containing manganese may be mixed as long as the function of the lithium manganese-based oxide is not impaired.
- Specific examples of the positive electrode active material include LiCoO 2 , LiNiO 2 , or those obtained by replacing a part of these transition metals with other metals; LiNi 1/3 Co 1/3 Mn 1/3 O 2, etc. be able to.
- the content of the lithium-based oxide not containing manganese in the positive electrode active material can be 0 to 45% by mass.
- the average particle diameter of the lithium manganese oxide can be set to 1 to 30 ⁇ m, for example.
- the positive electrode active material layer containing the positive electrode active material contains carbon nanotubes.
- the carbon nanotube has a function of a catalyst that promotes a film formation reaction of a sulfonic acid ester contained in an electrolyte solution described later.
- the carbon nanotubes may have a single-layer or coaxial multilayer structure in which a planar graphene sheet having a six-membered ring of carbon is formed in a cylindrical shape, but a multilayered one is preferable. Further, both ends of the cylindrical carbon nanotube may be open, but are preferably closed with a hemispherical fullerene containing a carbon 5-membered ring or 7-membered ring.
- the diameter of the outermost cylinder of the carbon nanotube is preferably 0.5 nm or more and 50 nm or less, for example.
- the carbon nanotube does not include fibrous carbon or carbon fiber.
- the fibrous carbon has a diameter of 150 to 500 nm, and the carbon fiber has a diameter of 5 to 10 ⁇ m and does not have a cylindrical structure.
- the carbon nanotubes preferably have an average D / G ratio obtained by Raman spectroscopy of 0.2 or more and 0.95 or less.
- an appropriate SEI film can be formed in the initial charge and discharge, and the life of the battery can be greatly extended. If the average D / G ratio is 0.95 or less, the crystallinity of the surface of the carbon nanotube is high, an excellent catalytic function, and a stable SEI film is easily formed on the positive electrode surface. If so, a dense SEI film having high density and stability can be easily formed on the positive electrode, and the charge / discharge cycle characteristics of the battery can be improved.
- the average D / G ratio by Raman spectroscopy is more preferably 0.25 or more and 0.8 or less, and further preferably 0.3 or more and 0.6 or less.
- Raman spectroscopy is one of the methods often used to evaluate the crystallinity of the surface of a carbon material.
- a G band around 1580 to 1600 cm ⁇ 1
- a D band around 1360 cm ⁇ 1
- the ratio ID / IG ratio (referred to as D / G ratio) of the peak intensity IG of the G band corresponding to the vibration mode in the circumferential surface of the carbon nanotube and the peak intensity ID of the D band derived from the defect in the circumferential surface.
- D / G ratio The ratio ID / IG ratio
- the temperature can be controlled mainly by the heat treatment temperature.
- the D / G ratio is small at a relatively high heat treatment temperature, and the D / G ratio is large at a low heat treatment temperature.
- the average D / G ratio by the Raman spectroscopic measurement a value obtained by the following measurement method can be adopted.
- Arbitrary 50 ⁇ m ⁇ 50 ⁇ m of the projected image of the positive electrode active material layer is used as the measurement surface, the measurement spot size of Raman spectroscopy is set to ⁇ 1 ⁇ m, and the measurement surface is mapped and measured (676 locations) by shifting by 1 ⁇ m.
- the D / G ratio is calculated and the average value is taken as the average D / G ratio.
- the carbon nanotube does not exist (the part where the carbon nanotube does not cover the positive electrode), and the Raman peak due to the carbon nanotube is not measured, but the spot is excluded from the average calculation.
- the carbon nanotubes having a D / G ratio of 0.2 or more and 0.95 or less as measured by Raman spectroscopy preferably cover a range of 40% or more and 90% or less of the surface area of the positive electrode active material layer.
- Carbon nanotubes having a D / G ratio of 0.2 or more and 0.95 or less are particularly effective in promoting SEI film formation on the surface of the positive electrode active material, and such carbon nanotubes coat the surface of the positive electrode active material layer. Ratio (also referred to as coverage) is in the above range, the SEI film can be effectively formed on the positive electrode active material, and the manganese elution suppression effect from the positive electrode active material is remarkably obtained. It is done.
- the coverage is more preferably 60% or more, still more preferably 70% or more. Further, if the coverage is 90% or less, it is possible to suppress the filling of the space between the positive electrode active materials with the carbon nanotubes, and the penetration of the electrolyte solution between the positive electrode active materials becomes insufficient, and lithium ions are occluded. Inhibition of release can be suppressed, and in the manufacturing process, it can be suppressed that it takes a long time to inject the electrolytic solution into the positive electrode active material layer.
- the method for measuring the surface area of the positive electrode active material layer coated with carbon nanotubes having a D / G ratio of 0.2 or more and 0.95 or less is the same as the measurement of the average D / G ratio.
- the D / G ratio for each spot on the measurement surface is obtained, the number of spots having a D / G ratio of 0.2 or more and 0.95 or less is divided by the number of all measured spots, and the coverage is expressed as a percentage.
- the coverage with which the carbon nanotubes cover the positive electrode active material layer can be controlled by the type of carbon nanotubes and the amount added.
- the coverage of the positive electrode active material layer of carbon nanotubes converges to a value determined by the D / G ratio distribution of the carbon nanotubes. Therefore, in order to increase the coverage, the entire surface of the positive electrode active material layer may be covered with a carbon nanotube material having a narrow distribution width with a D / G ratio of 0.2 or more and 0.95 or less.
- the coverage can be controlled mainly by changing the distribution of the D / G ratio of the carbon nanotubes and the amount added.
- the aspect ratio of the carbon nanotube is preferably 100 or more and 900 or less.
- the aspect ratio of the carbon nanotube is the ratio of the length to the diameter of the carbon nanotube. If the aspect ratio of the carbon nanotube is 100 or more, it becomes easy to coat the positive electrode active material of the carbon nanotube, and the positive electrode active material can be electrically connected to each other, and if it is 900 or less, workability in the coating process of the positive electrode active material. In addition, it is possible to suppress a decrease in the viscosity, suppress a decrease in dispersibility, and suppress an increase in viscosity at the time of slurry preparation.
- the aspect ratio of the carbon nanotube is more preferably 150 or more and 700 or less, still more preferably 200 or more and 500 or less.
- the specific surface area of the carbon nanotube is preferably 40 m 2 / g or more and 2000 m 2 / g or less. In general, there is a relationship between the diameter and the specific surface area of the carbon nanotube that the specific surface area increases as the diameter decreases. If the specific surface area is 2000 m 2 / g or less, the carbon nanotube reacts with the electrolytic solution to generate gas, and the effect of suppressing the formation of the SEI film is high. On the other hand, when the specific surface area is 40 m 2 / g or more, the surface of the positive electrode active material can be efficiently coated.
- Such carbon nanotubes compared ratio has been conventionally used surface area and Ketjen Black 800m 2 / g ⁇ 1300m 2 / g, acetylene black and carbon black 40m 2 / g ⁇ 100m 2 / g,
- the positive electrode active material layer is efficiently coated and has good characteristics as a conductive additive.
- Examples of the content of such carbon nanotubes in the positive electrode active material layer include 0.1 to 5% by mass.
- the positive electrode active material layer may contain plate-like graphite as a conductive material together with carbon nanotubes.
- the positive electrode active material layer contains carbon nanotubes and plate-like graphite, an appropriate gap can be formed between the spherical or massive positive electrode active materials. For this reason, not only the flow path of the electrolytic solution is easily formed in the positive electrode active material layer, but also the movement of lithium ions is facilitated, and the carbon nanotube has a function of holding the electrolytic solution therein, Electrolyte depletion can also be suppressed, and a rapid increase in resistance due to electrolyte depletion is also suppressed. This is in contrast to an electrode structure in which fine particles such as carbon black fill gaps between active materials.
- the content of the plate-like graphite in the positive electrode active material layer include 0.5 to 5% by mass.
- binder for forming the positive electrode active material layer on the positive electrode current collector by integrating the positive electrode active material and the carbon nanotube are polyvinylidene fluoride (PVDF), styrene butadiene rubber (SBR), and an acrylic polymer. , Polyimide, polyamideimide and the like. As a solvent for such an organic binder, N-methyl-2pyrrolidone (NMP) is preferable.
- NMP N-methyl-2pyrrolidone
- a thickening agent such as carboxymethyl cellulose (CMC) may be used in an aqueous binder such as SBR.
- the content of the binder is preferably 1% by mass to 10% by mass and more preferably 2% by mass to 6% by mass with respect to the positive electrode active material. If the content of the binder is in the above range, sufficient binding force can be obtained, and an effect of suppressing an increase in charge transfer resistance when lithium ions permeate and suppressing a decrease in battery capacity is high.
- the positive electrode current collector supports a positive electrode active material layer in which a positive electrode active material, carbon nanotubes, and other conductive materials, if necessary, are integrated with a binder, and enables conduction with external terminals. Any aluminum foil or the like can be used.
- the negative electrode may have a structure in which a negative electrode active material is integrated with a negative electrode binder and bound on a negative electrode current collector as a negative electrode active material layer.
- Any negative electrode active material may be used as long as it absorbs lithium ions from the electrolyte during charging and releases lithium ions into the electrolyte during discharging.
- crystalline artificial graphitized material obtained by heat treatment of natural graphite, coal, petroleum pitch, etc. at high temperature
- amorphous carbon obtained by heat treatment of coal, petroleum pitch coke, acetylene pitch coke, etc.
- a carbon material such as can be used.
- silicon materials such as silicon and silicon oxide, and metals that can form alloys with lithium, such as aluminum, lead, tin, indium, bismuth, silver, barium, calcium, mercury, palladium, platinum, tellurium, zinc Lanthanum and metal oxides such as aluminum oxide, tin oxide, indium oxide, zinc oxide, and lithium oxide can be used, and these can be used alone or in combination of two or more. It is preferable that the metal oxide be used together with the metal contained in the metal oxide, because lithium ions are occluded and released at different potentials during charging and discharging, and a rapid volume change of the negative electrode active material layer can be suppressed.
- the shape of the negative electrode active material is spherical or massive. This is because, when such a shape is used, the orientation of the crystal is directed in various directions even after the rolling process at the time of electrode preparation, so that lithium ions move smoothly between the electrodes, and between active materials. This is because it is easy to form a gap through which the electrolyte solution permeates, and is excellent in high output characteristics.
- the size of the negative electrode active material the larger the volume change associated with charge / discharge, the smaller the diameter, which is preferable because the volume change of the negative electrode active material layer due to the volume change of these particles can be suppressed.
- the average particle diameter of the carbon material can be set to 1 to 40 ⁇ m, for example.
- the binder for integrally forming the negative electrode active material as a negative electrode active material layer on the negative electrode current collector the same materials as those exemplified as the binder used for the positive electrode active material can be used. Further, the negative electrode active material layer may contain a conductive material such as carbon black as necessary.
- the negative electrode current collector is not particularly limited as long as it has conductivity that supports the negative electrode active material layer in which the negative electrode active material is integrated with the binder and enables conduction with the external terminal, and uses copper foil or the like. be able to.
- the electrolytic solution is obtained by dissolving an electrolyte in a non-aqueous organic solvent that can dissolve lithium ions by immersing the positive electrode and the negative electrode in order to allow lithium ions to be occluded and released in the positive electrode and the negative electrode during charging and discharging.
- the solvent of the electrolytic solution is stable at the operating potential of the battery and has a low viscosity so that the electrode can be immersed in the usage environment of the battery.
- cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC); dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate ( MEC), linear carbonates such as dipropyl carbonate (DPC); polar organic solvents such as ⁇ -butyrolactone, N, N′-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, m-cresol, and the like. These can be used alone or in combination of two or more.
- the negative electrode active material may contain a fluorinated ether compound.
- the fluorinated ether compound has high affinity with silicon and improves cycle characteristics, particularly capacity retention.
- Examples of the electrolyte contained in the electrolytic solution include lithium, alkali metal cations such as potassium and sodium, ClO 4 ⁇ , BF 4 ⁇ , PF 6 ⁇ , CF 3 SO 3 ⁇ and (CF 3 SO 2 ) 2 N ⁇ . , (C 2 F 5 SO 2 ) 2 N ⁇ , (CF 3 SO 2 ) 3 C ⁇ , (C 2 F 5 SO 2 ) 3 C ⁇ , and the like. . These salts may be used alone or in combination of two or more. Alternatively, a gel electrolyte in which an electrolytic solution is contained in a polymer gel may be used.
- the concentration of the electrolyte in the electrolytic solution is preferably 0.01 mol / L or more and 3 mol / L or less, more preferably 0.5 mol / L or more and 1.5 mol / L or less.
- concentration is within this range, safety can be improved, and a battery having high reliability and contributing to reduction of environmental load can be obtained.
- the above electrolytic solution contains a sulfonic acid ester.
- the sulfonic acid ester is reduced and decomposed prior to the solvent with charge and discharge, and forms a SEI film that enables a desolvation reaction between the negative electrode active material and lithium ions on the surface of the negative electrode active material. Can be prevented from coming into contact with the surface of the negative electrode active material, and decomposition of the electrolytic solution can be suppressed. Furthermore, volume change of the negative electrode active material can be suppressed, and loss of the negative electrode active material from the negative electrode active material layer can be suppressed.
- the sulfonic acid ester is reduced and decomposed by initial charge and discharge, and an SEI film is also formed on the surface of the positive electrode active material.
- the SEI film formed on the surface of the positive electrode active material in the presence of the carbon nanotube is not only efficiently formed to a desired thickness, but also a film formed by simple thermal decomposition, although it has not been clearly demonstrated. It is essentially different in density, conductive properties, and the like, and suppresses elution of manganese from the positive electrode active material.
- These SEI coatings are easily formed under the normal driving conditions of the battery, and appropriate coatings are formed in the initial charge and aging processes, thus significantly improving the charge / discharge cycle characteristics of the battery and the high temperature environment. The service life can be extended even when used in
- sulfonic acid ester examples include cyclic monosulfonic acid esters such as 1, 3-propane sultone, 1, 4-butane sultone. Moreover, the cyclic sulfonic acid ester represented by Formula (1) can be mentioned.
- Q represents an oxygen atom, a methylene group, or a single bond
- A represents a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, a carbonyl group, or a sulfinyl group
- B represents a substituted group. Or an unsubstituted alkylene group or an oxygen atom is shown.
- the substituent in the alkylene group having 1 to 6 carbon atoms represented by A in the formula an alkyl group, a fluorine atom, an oxy group and the like are preferable.
- the alkyl group include a methyl group and an ethyl group.
- Examples of the fluorine-substituted alkylene group include a fluoroalkylene group and a perfluoroalkylene group in which all hydrogen atoms are substituted with fluorine atoms.
- the oxy group may be present not only at the end of the carbon chain of the alkylene group but also at the middle part of the carbon chain.
- the substituent in the alkylene group represented by B in the formula an alkyl group, a fluorine atom, an oxy group and the like are preferable.
- the same alkylene group as A can be exemplified.
- cyclic sulfonate ester represented by the formula (1) include those represented by the following formulas (101) to (123).
- examples of the sulfonic acid ester include a chain sulfonic acid ester represented by the formula (2).
- X represents an alkylene group having 1 to 6 carbon atoms
- R represents an alkyl group having 1 to 6 carbon atoms
- two Rs represent the same group but are different from each other. Also good.
- the above sulfonic acid esters can be used alone or in combination of two or more.
- the sulfonic acid ester is preferably contained in a range of 0.1% by mass to 6.0% by mass with respect to the total mass of the solvent and the sulfonic acid ester. If the sulfonic acid ester is 0.1% by mass or more, the effect of forming a sufficient SEI film on the surface of the positive electrode active material is high, and if it is 6.0% by mass or less, the SEI film formed on the negative electrode active material is The effect of suppressing the increase in the charge transfer resistance of lithium ions and extending the life of the battery is high.
- the lithium ion secondary battery of the present invention may be one in which a positive electrode active material layer and a negative electrode active material layer are arranged to face each other with a separator interposed between them and housed in an exterior body.
- the separator may be any one as long as it suppresses conduction between the positive electrode and the negative electrode, does not inhibit the permeation of lithium ions, and has durability with respect to the electrolytic solution.
- Specific examples of the material that can be used include polyolefin microporous membranes such as polypropylene and polyethylene, cellulose, polyethylene terephthalate, polyimide, and polyvinylidene fluoride. These can be used as porous films, woven fabrics, non-woven fabrics and the like.
- the outer package those having a strength capable of stably holding the positive electrode, the negative electrode, the separator, and the electrolyte, electrochemically stable to these substances, and watertight are preferable.
- a laminate film coated with stainless steel, nickel-plated iron, aluminum, silica, and alumina can be used.
- a resin used for the laminate film polyethylene, polypropylene, polyethylene terephthalate, or the like is used. Can do. These may be a structure of one layer or two or more layers.
- the lithium ion secondary battery may be any of the cylindrical type, flat wound rectangular type, laminated rectangular type, coin type, flat wound laminated type, and laminated laminated type.
- FIG. 1 shows the configuration of an example of the lithium ion secondary battery.
- the lithium ion secondary battery shown in FIG. 1 shows a state in which an SEI film is formed by charging and discharging.
- a negative electrode 10 having a negative electrode active material layer 10a containing a negative electrode active material 11 integrated on a negative electrode current collector 12 with a binder, and a positive electrode active integrated on a positive electrode current collector 4 with a binder.
- the positive electrode 1 having the positive electrode active material layer 1 a containing the substance 3, the carbon nanotube 2, and the plate-like graphite 8 is alternately arranged opposite to each other via the separator 9 made of a porous film that avoids these contacts. Is housed in a laminate outer package (not shown).
- the negative electrode active material 11 is covered with a SEI film 11a
- the positive electrode active material 3 is covered with a SEI film 3a.
- the exterior body is filled with the electrolytic solution 5 and penetrates into the negative electrode active material layer and the positive electrode active material layer, and the negative electrode and the positive electrode are respectively connected to a portion of the current collector where the active material layer is not formed.
- a negative electrode terminal (not shown) and a positive electrode terminal (not shown) are drawn to the outside of the exterior body, and are connected to an external power source or a device to be used via the terminals at the time of charge / discharge.
- a positive electrode active material layer is prepared using a positive electrode active material, carbon nanotubes, and, if necessary, a positive electrode active material layer material containing a conductive material and a binder.
- the method for producing the positive electrode active material layer include a coating method such as a doctor blade method and a die coater method, a CVD method, and a sputtering method.
- a thin film may be formed by a method such as vapor deposition or sputtering to form a positive electrode current collector.
- a negative electrode active material layer is formed on a negative electrode current collector using a negative electrode active material layer material containing a negative electrode active material and a binder. Terminals are connected to the ends of the respective current collectors, stacked via separators, accommodated in the exterior body, injected with electrolyte, and then the terminals are drawn out of the exterior body to seal the exterior body.
- An initial charge is performed under conditions such as the operating voltage of the battery, room temperature to 50 ° C., and left for a predetermined time to perform aging, whereby an SEI film can be formed on the active material surface.
- Table 1 shows the average D / G ratio of the carbon nanotubes A to F, carbon black, and plate-like graphite conductor used in the examples.
- histograms of the D / G ratios of the carbon nanotubes C, D, and E are shown in FIGS. 2a, b, and c.
- the frequency distribution of the D / G ratio obtained from the Raman measurement at each spot in the 50 ⁇ m ⁇ 50 ⁇ m region on the surface of the positive electrode active material layer was plotted.
- Carbon nanotubes C and D showed a distribution with a narrow D / G ratio
- carbon nanotube E showed a distribution with a wide D / G ratio.
- All the carbon nanotubes had an average diameter of about 10 nm, an aspect ratio of about 150, and a specific surface area of about 200 m 2 / g. Moreover, the average diameter of the primary particles of carbon black used as a comparative example was 60 nm, the aspect ratio was 1.1, and the specific surface area was 60 m 2 / g.
- Example 1 [Production of battery]
- a positive electrode active material 4% by mass of polyvinylidene fluoride (PVDF) as a binder, 0.6% by mass of carbon nanotube C, and the remainder other than these are lithium manganese spinel (LiMn 2 O 4 ) powder having an average particle diameter of 10 ⁇ m and stirred.
- PVDF polyvinylidene fluoride
- LiMn 2 O 4 lithium manganese spinel
- a negative electrode slurry was prepared by dispersing. A negative electrode slurry was uniformly applied to a negative electrode current collector of copper foil having a thickness of 10 ⁇ m using a coater, NMP was evaporated and dried, and then the density was adjusted by a roll press to prepare a negative electrode active material layer. The mass of the negative electrode active material layer per unit area was 20 mg / cm 2 .
- the electrolytic solution is represented by the formula (101) with respect to a solution obtained by dissolving 1 mol / L LiPF 6 as an electrolyte in a solvent containing ethylene carbonate (EC) and diethyl carbonate (DEC) at a volume ratio of 35:65.
- EC ethylene carbonate
- DEC diethyl carbonate
- a cyclic sulfonic acid ester (indicated by S1 in Table 2) was added to prepare 2.0% by mass.
- the obtained positive electrode was cut into 4.0 cm ⁇ 2.4 cm, and the negative electrode was cut into 4.5 cm ⁇ 2.8 cm.
- the positive electrode side of 4.0 cm ⁇ 1.0 cm and the negative electrode side of 4.5 cm ⁇ 1.0 cm are connected to the terminal, and the active material layer is formed without applying the positive electrode slurry and the negative electrode slurry, respectively.
- a portion of the current collector that was not provided was provided.
- a positive electrode terminal made of aluminum having a width of 7 mm, a length of 8 cm, and a thickness of 0.1 mm was welded to a portion where the positive electrode active material layer was not formed.
- a negative electrode terminal made of nickel having the same shape as the positive electrode terminal was welded to a portion where the negative electrode active material layer was not formed.
- the both sides of the positive electrode were covered with a 5 cm ⁇ 3 cm polypropylene separator, and the negative electrode active material layer was arranged on the positive electrode active material layer so as to face the positive electrode active material layer, thereby preparing an electrode laminate.
- the electrode laminate is sandwiched between two aluminum laminate films of 7 cm ⁇ 5 cm, the three sides excluding one long side are heat sealed with a width of 8 mm, the electrolyte is injected, and the remaining side is heated. Sealed to prepare a battery of a small laminate cell.
- a battery is manufactured in the same manner except that the carbon nanotube F is used instead of the carbon nanotube C.
- the charge transfer resistance component is weak from the impedance shown in FIG. Two peaks were observed, suggesting the presence of the SEI film not only on the negative electrode but also on the positive electrode.
- Example 2-25 A battery was prepared in the same manner as in Example 1 except that the positive electrode active material, the carbon nanotube, the addition amount thereof, and the sulfonate ester shown in Tables 2 to 4 were used, and the coverage of the carbon nanotube in the positive electrode active material layer, The capacity retention rate was measured. The results are shown in Tables 2-4.
- Mn spinel LiMn 2 O 4 Mn layered: LiMnO 2 Mn olivine: LiMnPO 4 Ni layer: LiNi 0.8 Co 0.2 O 2
- S1 Cyclic sulfonate ester represented by formula (101)
- S2 Cyclic sulfonate ester represented by formula (102)
- PS Propane sultone
- Example 15 Cyclic sulfonate ester represented by formula (104)
- S4 Cyclic sulfonate ester represented by formula (107)
- S5 Cyclic sulfonate ester represented by formula (122)
- the positive electrode active material was Mn
- the positive electrode active material in the positive electrode active material layer was 70% by mass Mn spinel, 22% by mass Ni layer, and 2.0% by mass of plate-like graphite was added. did. Since plate-like graphite is also added, the coverage of the positive electrode active material layer surface by Raman spectroscopy is not measured.
- Example 1-10 A battery was prepared in the same manner as in Example 1 except that the positive electrode active material, carbon nanotube or carbon black or plate-like graphite, addition amount thereof, and sulfonate ester shown in Table 5 were used. The nanotube coverage and capacity retention were measured. The results are shown in Tables 2-4.
- Example 1 to Example 25 in a positive electrode including a lithium manganese-based oxide, a battery using an additive containing a carbon nanotube and further containing a sulfonate ester has a high temperature of 55 ° C. It was found that there was little capacity degradation in the environment and it had good charge / discharge cycle characteristics. This is because, by using an additive containing carbon nanotubes and a sulfonate ester, a high-quality SEI film is formed on the surface of the positive electrode active material even in the initial charge performed under the same conditions as the battery driving conditions. It seems that manganese elution was suppressed.
- the present invention can be used in all industrial fields that require a power source and industrial fields related to the transport, storage and supply of electrical energy. Specifically, it can be used as a power source for mobile devices such as a mobile phone and a notebook computer, a power source for driving a vehicle, and the like.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
Description
1a 正極活物質層
2 カーボンナノチューブ
3 正極活物質
3a、11a SEI皮膜
4 正極集電体
5 電解液
8 板状黒鉛
9 セパレーター
10 負極
10a 負極活物質層
11 負極活物質
12 負極集電体
正極は、正極活物質が正極結着剤により一体化され正極活物質層として正極集電体上に結着された構造を有するものとすることができる。
負極は、負極活物質が負極結着剤により一体化され負極活物質層として負極集電体上に結着された構造を有するものとすることができる。
電解液は、充放電時に正極、負極においてリチウムイオンの吸蔵放出を可能とするため、正極と負極を漬浸してリチウムイオンを溶解可能な非水系の有機溶媒に、電解質を溶解したものである。
本発明のリチウムイオン二次電池は、正極活物質層と負極活物質層がセパレーターを介して対向配置され、外装体に収納されたものであってよい。
[電池の作製]
正極活物質として、結着剤としてポリフッ化ビニリデン(PVDF)4質量%、カーボンナノチューブC0.6質量%、これら以外の残部は平均粒子径10μmのリチウムマンガンスピネル(LiMn2O4)粉末とし、攪拌混合に優れたトリミックスを用いてNMP中に均一に分散させて正極スラリーを調製した。厚さ20μmのアルミニウム箔の正極集電体にコーターを用いて正極スラリーを均一に塗布し、NMPを蒸発させて乾燥後、裏面も同様にコーティングし、乾燥後ロールプレスにて密度を調整し、集電体の両面に正極活物質層を作製した。単位面積当たりの正極活物質層の質量は、50mg/cm2であった。
55℃の恒温槽中で1000回の充放電サイクル試験を行い、その容量維持率を測定し、寿命を評価した。充電は、1Cの定電流充電を上限電圧4.2Vまで行い、続いて4.2Vで定電圧充電を行い、総充電時間を2.5時間行った。 放電は、1Cで定電流放電を2.5Vまで行った。 尚、充放電サイクルを55℃という極めて高い温度で行ったが、これは、マンガン溶出による特性劣化を早期に見極めることができるからである。充放電サイクル試験後の容量を測定し、充放電サイクル試験前の容量に対する割合を算出した。結果を表2に示す。
表2~4に示す正極活物質、カーボンナノチューブ、その添加量、スルホン酸エステルを用いたこと以外は、実施例1と同様に、電池を作製し、正極活物質層のカーボンナノチューブの被覆率、容量維持率を測定した。結果を表2~4に示す。
Mnスピネル:LiMn2O4
Mn層状:LiMnO2
Mnオリビン:LiMnPO4
Ni層状:LiNi0.8Co0.2O2
S1:式(101)で示される環状スルホン酸エステル
S2:式(102)で示される環状スルホン酸エステル
PS:プロパンスルトン
SL:式(4)で示すスルホン酸エステル
S4:式(107)で示される環状スルホン酸エステル
S5:式(122)で示される環状スルホン酸エステル
実施例15において、正極活物質は、Mnスピネル70質量%、Ni層状24質量%とし、実施例16において、正極活物質層中の正極活物質は、Mnスピネル70質量%、Ni層状22質量%とし、板状黒鉛2.0質量%添加した。尚、板状黒鉛も添加しているので、ラマン分光による正極活物質層表面の被覆率は測定していない。
表5に示す正極活物質、カーボンナノチューブ又はカーボンブラック若しくは板状黒鉛、その添加量、スルホン酸エステルを用いたこと以外は、実施例1と同様に、電池を作製し、正極活物質層のカーボンナノチューブの被覆率、容量維持率を測定した。結果を表2~4に示す。
VS:ビニレンカーボネート
尚、カーボンナノチューブを添加していないものは、ラマン分光による正極活物質層表面の被覆率は測定していない。
Claims (7)
- 正極活物質としてリチウムマンガン系酸化物を含む正極活物質層と、負極活物質を含む負極活物質層と、これらを漬浸する電解液とを有するリチウムイオン二次電池において、
正極活物質層が、カーボンナノチューブを含み、
電解液が、スルホン酸エステルを含有することを特徴とするリチウムイオン二次電池。 - カーボンナノチューブが、ラマン分光測定による平均D/G比が0.2以上、0.95以下である請求項1記載のリチウムイオン二次電池。
- 正極活物質層の表面が、ラマン分光測定によるD/G比が0.2以上、0.95以下であるカーボンナノチューブで、表面積の40%以上、90%以下の範囲が被覆されている請求項1から3のいずれか記載のリチウムイオン二次電池。
- カーボンナノチューブのアスペクト比が100以上、900以下である請求項1から4のいずれか記載のリチウムイオン二次電池。
- カーボンナノチューブの比表面積が40m2/g以上、2000m2/g以下である請求項1から5のいずれか記載のリチウムイオン二次電池。
- 正極活物質層が、板状の黒鉛を含有し、板状の黒鉛がリチウムマンガン系酸化物の表面に接している請求項1から6のいずれか記載のリチウムイオン二次電池。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014509118A JP6156939B2 (ja) | 2012-04-05 | 2013-03-27 | リチウムイオン二次電池 |
US14/383,816 US10340550B2 (en) | 2012-04-05 | 2013-03-27 | Lithium ion secondary cell |
CN201380018467.2A CN104247135B (zh) | 2012-04-05 | 2013-03-27 | 锂离子二次电池 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012086289 | 2012-04-05 | ||
JP2012-086289 | 2012-04-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013150937A1 true WO2013150937A1 (ja) | 2013-10-10 |
Family
ID=49300427
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/058978 WO2013150937A1 (ja) | 2012-04-05 | 2013-03-27 | リチウムイオン二次電池 |
Country Status (4)
Country | Link |
---|---|
US (1) | US10340550B2 (ja) |
JP (1) | JP6156939B2 (ja) |
CN (1) | CN104247135B (ja) |
WO (1) | WO2013150937A1 (ja) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015095423A (ja) * | 2013-11-14 | 2015-05-18 | Fdk株式会社 | リチウム二次電池用電極材料およびリチウム二次電池 |
JP2015229607A (ja) * | 2014-06-04 | 2015-12-21 | 日立化成株式会社 | マグネシウムアルミニウム酸化物複合体 |
JP2016134218A (ja) * | 2015-01-16 | 2016-07-25 | 日本電気株式会社 | リチウムイオン二次電池 |
CN106030863A (zh) * | 2014-02-20 | 2016-10-12 | Nec能源元器件株式会社 | 锂离子二次电池用正极和使用其的锂离子二次电池 |
JPWO2016063813A1 (ja) * | 2014-10-21 | 2017-08-03 | 日本電気株式会社 | 二次電池用電極およびこれを用いた二次電池 |
JP2018529197A (ja) * | 2015-09-16 | 2018-10-04 | ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツングRobert Bosch Gmbh | バッテリーセルの正極用の活物質、正極、およびバッテリーセル |
JP2018529198A (ja) * | 2015-09-16 | 2018-10-04 | ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツングRobert Bosch Gmbh | バッテリーセルの正極用の活物質、正極、およびバッテリーセル |
JP2018174107A (ja) * | 2017-03-31 | 2018-11-08 | Tdk株式会社 | 正極、及びリチウムイオン二次電池 |
KR20190043955A (ko) * | 2017-10-19 | 2019-04-29 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 전극 및 이를 포함하는 리튬 이차 전지 |
JP2019526886A (ja) * | 2017-02-22 | 2019-09-19 | トヨタ モーター ヨーロッパ | リチウムイオン電池の高温エージングプロセス |
JP2020047437A (ja) * | 2018-09-18 | 2020-03-26 | 株式会社東芝 | 電極、二次電池、電池パック、及び車両 |
JP2020513653A (ja) * | 2016-11-24 | 2020-05-14 | ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツングRobert Bosch Gmbh | 電池セルの正極用の活物質、正極および電池セル |
JP2020184490A (ja) * | 2019-05-09 | 2020-11-12 | プライムアースEvエナジー株式会社 | リチウムイオン二次電池用正極ペースト、正極の製造方法、及び正極 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3276732B1 (en) * | 2015-03-24 | 2020-07-08 | Nec Corporation | Lithium-ion secondary cell and method for manufacturing same |
EP3353844B1 (en) | 2015-03-27 | 2022-05-11 | Mason K. Harrup | All-inorganic solvents for electrolytes |
KR102101006B1 (ko) * | 2015-12-10 | 2020-04-14 | 주식회사 엘지화학 | 이차전지용 양극 및 이를 포함하는 이차전지 |
WO2018051667A1 (ja) * | 2016-09-14 | 2018-03-22 | 日本電気株式会社 | リチウムイオン二次電池 |
US10707531B1 (en) | 2016-09-27 | 2020-07-07 | New Dominion Enterprises Inc. | All-inorganic solvents for electrolytes |
WO2019093836A1 (ko) * | 2017-11-09 | 2019-05-16 | 주식회사 엘지화학 | 원통형 젤리롤에 사용되는 스트립형 전극 및 그를 포함하는 리튬 이차전지 |
JP6933589B2 (ja) * | 2018-02-22 | 2021-09-08 | 日産自動車株式会社 | 負極活物質のプレドープ方法、負極の製造方法、及び蓄電デバイスの製造方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003077476A (ja) * | 2001-09-03 | 2003-03-14 | Matsushita Electric Ind Co Ltd | リチウムイオン二次電池 |
JP2004281368A (ja) * | 2002-08-29 | 2004-10-07 | Nec Corp | 二次電池用電解液およびそれを用いた二次電池 |
JP2005149750A (ja) * | 2003-11-11 | 2005-06-09 | Nec Corp | 非水電解質二次電池 |
JP2011192543A (ja) * | 2010-03-15 | 2011-09-29 | Hitachi Maxell Energy Ltd | リチウムイオン二次電池 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6218048B1 (en) | 1998-04-07 | 2001-04-17 | Fmc Corporation | Method of preliminarily heat treating positive electrodes of secondary lithium and lithium-ion Batteries and resulting positive electrodes and batteries |
JP3024636B2 (ja) | 1998-08-27 | 2000-03-21 | 日本電気株式会社 | 非水電解液二次電池 |
US6733925B2 (en) * | 2000-02-08 | 2004-05-11 | Shin-Kobe Electric Machinery Co., Ltd. | Non-aqueous electrolytic solution secondary battery with electrodes having a specific thickness and porosity |
AU2003301357A1 (en) * | 2002-10-17 | 2004-05-04 | Tel-Aviv University Future Technology Development L.P. | Thin-film cathode for 3-dimensional microbattery and method for preparing such cathode |
JP4836415B2 (ja) | 2004-06-18 | 2011-12-14 | 株式会社東芝 | 非水電解質二次電池 |
EP2034542B1 (en) * | 2006-06-27 | 2015-06-03 | Kao Corporation | Composite positive electrode material for lithium ion battery and battery using the same |
CN101207190A (zh) | 2006-12-22 | 2008-06-25 | 比亚迪股份有限公司 | 一种锂离子二次电池正极及包括该正极的锂离子二次电池 |
JP5287520B2 (ja) | 2008-09-02 | 2013-09-11 | 住友化学株式会社 | 電極活物質、電極および非水電解質二次電池 |
JP5372568B2 (ja) * | 2009-03-27 | 2013-12-18 | 富士重工業株式会社 | 蓄電デバイスおよびその製造方法 |
US20110171371A1 (en) * | 2010-01-13 | 2011-07-14 | CNano Technology Limited | Enhanced Electrode Composition for Li ion Battery |
CN102742064B (zh) | 2010-02-10 | 2015-11-25 | Nec能源元器件株式会社 | 非水性电解质溶液,和具有所述非水性电解质溶液的锂离子二次电池 |
WO2013038494A1 (ja) * | 2011-09-13 | 2013-03-21 | 株式会社日立製作所 | リチウムイオン二次電池用電極、その製造方法およびリチウムイオン二次電池 |
KR20130108816A (ko) * | 2012-03-26 | 2013-10-07 | 삼성에스디아이 주식회사 | 이차 전지 |
-
2013
- 2013-03-27 JP JP2014509118A patent/JP6156939B2/ja active Active
- 2013-03-27 US US14/383,816 patent/US10340550B2/en active Active
- 2013-03-27 CN CN201380018467.2A patent/CN104247135B/zh active Active
- 2013-03-27 WO PCT/JP2013/058978 patent/WO2013150937A1/ja active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003077476A (ja) * | 2001-09-03 | 2003-03-14 | Matsushita Electric Ind Co Ltd | リチウムイオン二次電池 |
JP2004281368A (ja) * | 2002-08-29 | 2004-10-07 | Nec Corp | 二次電池用電解液およびそれを用いた二次電池 |
JP2005149750A (ja) * | 2003-11-11 | 2005-06-09 | Nec Corp | 非水電解質二次電池 |
JP2011192543A (ja) * | 2010-03-15 | 2011-09-29 | Hitachi Maxell Energy Ltd | リチウムイオン二次電池 |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015095423A (ja) * | 2013-11-14 | 2015-05-18 | Fdk株式会社 | リチウム二次電池用電極材料およびリチウム二次電池 |
US20160351902A1 (en) * | 2014-02-20 | 2016-12-01 | Nec Energy Devices, Ltd. | Positive electrode for lithium ion secondary battery and lithium ion secondary battery using same |
CN106030863A (zh) * | 2014-02-20 | 2016-10-12 | Nec能源元器件株式会社 | 锂离子二次电池用正极和使用其的锂离子二次电池 |
JP2015229607A (ja) * | 2014-06-04 | 2015-12-21 | 日立化成株式会社 | マグネシウムアルミニウム酸化物複合体 |
US10320026B2 (en) * | 2014-10-21 | 2019-06-11 | Nec Corporation | Electrode for secondary battery and secondary battery using same |
JPWO2016063813A1 (ja) * | 2014-10-21 | 2017-08-03 | 日本電気株式会社 | 二次電池用電極およびこれを用いた二次電池 |
JP2016134218A (ja) * | 2015-01-16 | 2016-07-25 | 日本電気株式会社 | リチウムイオン二次電池 |
JP2018529197A (ja) * | 2015-09-16 | 2018-10-04 | ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツングRobert Bosch Gmbh | バッテリーセルの正極用の活物質、正極、およびバッテリーセル |
JP2018529198A (ja) * | 2015-09-16 | 2018-10-04 | ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツングRobert Bosch Gmbh | バッテリーセルの正極用の活物質、正極、およびバッテリーセル |
US10790502B2 (en) | 2015-09-16 | 2020-09-29 | Robert Bosch Gmbh | Active material for a positive electrode of a battery cell, positive electrode, and battery cell |
US10763502B2 (en) | 2015-09-16 | 2020-09-01 | Robert Bosch Gmbh | Active material for a positive electrode of a battery cell, positive electrode, and battery cell |
JP2020513653A (ja) * | 2016-11-24 | 2020-05-14 | ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツングRobert Bosch Gmbh | 電池セルの正極用の活物質、正極および電池セル |
US11024898B2 (en) | 2017-02-22 | 2021-06-01 | Toyota Motor Europe | Lithium-ion battery high temperature aging process |
JP2019526886A (ja) * | 2017-02-22 | 2019-09-19 | トヨタ モーター ヨーロッパ | リチウムイオン電池の高温エージングプロセス |
JP2018174107A (ja) * | 2017-03-31 | 2018-11-08 | Tdk株式会社 | 正極、及びリチウムイオン二次電池 |
KR20190043955A (ko) * | 2017-10-19 | 2019-04-29 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 전극 및 이를 포함하는 리튬 이차 전지 |
KR102519116B1 (ko) | 2017-10-19 | 2023-04-05 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 전극 및 이를 포함하는 리튬 이차 전지 |
KR20230048494A (ko) * | 2017-10-19 | 2023-04-11 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 전극 및 이를 포함하는 리튬 이차 전지 |
KR102614017B1 (ko) | 2017-10-19 | 2023-12-13 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 전극 및 이를 포함하는 리튬 이차 전지 |
JP2020047437A (ja) * | 2018-09-18 | 2020-03-26 | 株式会社東芝 | 電極、二次電池、電池パック、及び車両 |
JP7210198B2 (ja) | 2018-09-18 | 2023-01-23 | 株式会社東芝 | 電極、二次電池、電池パック、及び車両 |
JP2020184490A (ja) * | 2019-05-09 | 2020-11-12 | プライムアースEvエナジー株式会社 | リチウムイオン二次電池用正極ペースト、正極の製造方法、及び正極 |
JP7029755B2 (ja) | 2019-05-09 | 2022-03-04 | プライムアースEvエナジー株式会社 | リチウムイオン二次電池用正極ペースト、正極の製造方法、及び正極 |
Also Published As
Publication number | Publication date |
---|---|
CN104247135A (zh) | 2014-12-24 |
JP6156939B2 (ja) | 2017-07-05 |
JPWO2013150937A1 (ja) | 2015-12-17 |
US20150104701A1 (en) | 2015-04-16 |
US10340550B2 (en) | 2019-07-02 |
CN104247135B (zh) | 2016-09-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6156939B2 (ja) | リチウムイオン二次電池 | |
US10897040B2 (en) | Anode having double-protection layer formed thereon for lithium secondary battery, and lithium secondary battery comprising same | |
JP5640546B2 (ja) | 非水系電解液二次電池用セパレータ及び非水系電解液二次電池 | |
JP2022538962A (ja) | 再充電可能なバッテリーセル | |
JP6685940B2 (ja) | リチウムイオン二次電池用負極及びリチウムイオン二次電池 | |
JP7281570B2 (ja) | 非水電解液二次電池およびその製造方法 | |
CZ2016618A3 (cs) | Soli multivalentních kovů pro lithium-iontové články, které mají elektrodové aktivní materiály, které zahrnují kyslík | |
JPWO2018180017A1 (ja) | 電池用電極及びリチウムイオン二次電池 | |
JP2012043629A (ja) | 非水系電解液二次電池用セパレータ及び非水系電解液二次電池 | |
CN109417167A (zh) | 用于锂离子电池的包覆钛酸锂 | |
JP2011192561A (ja) | 非水電解液二次電池の製造方法 | |
JP2016184484A (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 | |
JP2016139548A (ja) | リチウムイオン電池 | |
JP2008198408A (ja) | 非水電解質二次電池 | |
CN109935905B (zh) | 电解液和锂离子电池 | |
US11349125B2 (en) | Spacer included electrodes structure and its application for high energy density and fast chargeable lithium ion batteries | |
JP2016134218A (ja) | リチウムイオン二次電池 | |
TWI600195B (zh) | 非水電解質二次電池及使用其之組電池 | |
JP2018097935A (ja) | 炭素質材料、リチウム二次電池および炭素質材料の製造方法 | |
JPWO2017057134A1 (ja) | リチウムイオン二次電池用正極及びリチウムイオン二次電池 | |
JP2017183048A (ja) | 正極活物質、及びそれを用いた正極並びにリチウムイオン二次電池 | |
JP2016081707A (ja) | 負極及びそれを用いたリチウムイオン二次電池 | |
CN111029580B (zh) | 二次电池用电极和二次电池 | |
JP6120068B2 (ja) | 非水電解液二次電池の製造方法 | |
WO2024150390A1 (ja) | リチウムイオン二次電池用負極材、リチウムイオン二次電池用負極及びリチウムイオン二次電池 |
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: 13772353 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14383816 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 2014509118 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 13772353 Country of ref document: EP Kind code of ref document: A1 |