WO2015049824A1 - 電池、電解質、電池パック、電子機器、電動車両、蓄電装置および電力システム - Google Patents
電池、電解質、電池パック、電子機器、電動車両、蓄電装置および電力システム Download PDFInfo
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- WO2015049824A1 WO2015049824A1 PCT/JP2014/004163 JP2014004163W WO2015049824A1 WO 2015049824 A1 WO2015049824 A1 WO 2015049824A1 JP 2014004163 W JP2014004163 W JP 2014004163W WO 2015049824 A1 WO2015049824 A1 WO 2015049824A1
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- Prior art keywords
- battery
- particles
- power
- positive electrode
- negative electrode
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- B60L15/00—Methods, circuits, or devices for controlling the traction-motor speed of electrically-propelled vehicles
- B60L15/007—Physical arrangements or structures of drive train converters specially adapted for the propulsion motors of electric vehicles
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B60L15/00—Methods, circuits, or devices for controlling the traction-motor speed of electrically-propelled vehicles
- B60L15/20—Methods, circuits, or devices for controlling the traction-motor speed of electrically-propelled vehicles for control of the vehicle or its driving motor to achieve a desired performance, e.g. speed, torque, programmed variation of speed
- B60L15/2009—Methods, circuits, or devices for controlling the traction-motor speed of electrically-propelled vehicles for control of the vehicle or its driving motor to achieve a desired performance, e.g. speed, torque, programmed variation of speed for braking
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B60L3/00—Electric devices on electrically-propelled vehicles for safety purposes; Monitoring operating variables, e.g. speed, deceleration or energy consumption
- B60L3/0023—Detecting, eliminating, remedying or compensating for drive train abnormalities, e.g. failures within the drive train
- B60L3/0046—Detecting, eliminating, remedying or compensating for drive train abnormalities, e.g. failures within the drive train relating to electric energy storage systems, e.g. batteries or capacitors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L3/00—Electric devices on electrically-propelled vehicles for safety purposes; Monitoring operating variables, e.g. speed, deceleration or energy consumption
- B60L3/04—Cutting off the power supply under fault conditions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L50/00—Electric propulsion with power supplied within the vehicle
- B60L50/10—Electric propulsion with power supplied within the vehicle using propulsion power supplied by engine-driven generators, e.g. generators driven by combustion engines
- B60L50/16—Electric propulsion with power supplied within the vehicle using propulsion power supplied by engine-driven generators, e.g. generators driven by combustion engines with provision for separate direct mechanical propulsion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L50/00—Electric propulsion with power supplied within the vehicle
- B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
- B60L50/60—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells using power supplied by batteries
- B60L50/64—Constructional details of batteries specially adapted for electric vehicles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L53/00—Methods of charging batteries, specially adapted for electric vehicles; Charging stations or on-board charging equipment therefor; Exchange of energy storage elements in electric vehicles
- B60L53/10—Methods of charging batteries, specially adapted for electric vehicles; Charging stations or on-board charging equipment therefor; Exchange of energy storage elements in electric vehicles characterised by the energy transfer between the charging station and the vehicle
- B60L53/14—Conductive energy transfer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
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- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
- H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/64—Electric machine technologies in electromobility
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/7072—Electromobility specific charging systems or methods for batteries, ultracapacitors, supercapacitors or double-layer capacitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02T10/72—Electric energy management in electromobility
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02T90/10—Technologies relating to charging of electric vehicles
- Y02T90/12—Electric charging stations
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02T90/10—Technologies relating to charging of electric vehicles
- Y02T90/14—Plug-in electric vehicles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02T90/10—Technologies relating to charging of electric vehicles
- Y02T90/16—Information or communication technologies improving the operation of electric vehicles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S903/00—Hybrid electric vehicles, HEVS
- Y10S903/902—Prime movers comprising electrical and internal combustion motors
- Y10S903/903—Prime movers comprising electrical and internal combustion motors having energy storing means, e.g. battery, capacitor
- Y10S903/904—Component specially adapted for hev
- Y10S903/907—Electricity storage, e.g. battery, capacitor
Definitions
- This technology relates to batteries, electrolytes, battery packs, electronic devices, electric vehicles, power storage devices, and power systems.
- a lithium ion secondary battery having a large energy density is most suitable as a battery that satisfies such requirements.
- a lithium ion secondary battery for example, a battery using a laminate film as an exterior member has been put into practical use because it is lightweight and has high energy density, and can be manufactured in a very thin shape. .
- an electrolyte solution and a matrix resin that holds the electrolyte solution are applied as an electrolyte, which is known as a polymer battery.
- a polymer battery has greatly improved the degree of freedom of shape by using an aluminum laminate film for the exterior member, but on the other hand, the strength may not be sufficient, and when a strong force is applied due to misuse. Is prone to deformation.
- Batteries are required to suppress deterioration of battery characteristics and improve heat dissipation when the temperature rises.
- an object of the present technology is to provide a battery, an electrolyte, a battery pack, an electronic device, an electric vehicle, a power storage device, and a power system that can suppress deterioration of battery characteristics and improve heat dissipation by improving heat dissipation against internal heat generation. Is to provide.
- the present technology includes an electrode including a positive electrode and a negative electrode, and a particle-containing insulating portion that is provided between the positive electrode and the negative electrode and includes particles and a resin.
- the battery has a flat shape with an aspect ratio of 2/1 or more.
- the present technology includes particles, an electrolytic solution, and a resin, and the particles are substances that cause a dehydration endothermic reaction and have an oblate shape with an aspect ratio of 2/1 or more.
- the battery pack, electronic device, electric vehicle, power storage device, and power system of the present technology include the above-described battery.
- the present technology it is possible to suppress the deterioration of the battery characteristics, and to improve the heat dissipation property against the internal heat generation, thereby improving the safety.
- FIG. 1 is a schematic cross-sectional view showing an example of the nonaqueous electrolyte of the present technology.
- FIG. 2 is an exploded perspective view showing an example of the nonaqueous electrolyte secondary battery of the present technology.
- FIG. 3 is a cross-sectional view taken along line II of the spirally wound electrode body shown in FIG.
- FIG. 4 is an exploded perspective view showing a configuration of a laminated film type nonaqueous electrolyte battery using a laminated electrode body.
- FIG. 7 is a development view showing the structure of the battery cell of the battery pack shown in FIG. 8 is a cross-sectional view showing the structure of the battery cell of the battery pack shown in FIG.
- FIG. 9 is an exploded perspective view showing a configuration example of a simplified battery pack.
- FIG. 10A is a schematic perspective view showing the appearance of a simple battery pack.
- FIG. 10B is a schematic perspective view showing the appearance of a simple battery pack.
- FIG. 11 is a block diagram illustrating a circuit configuration example of the battery pack according to the embodiment of the present technology.
- FIG. 12 is a schematic diagram showing an example applied to a residential power storage system using the nonaqueous electrolyte battery of the present technology.
- FIG. 13 is a schematic diagram schematically illustrating an example of a configuration of a hybrid vehicle that employs a series hybrid system to which the present technology is applied.
- 14A is an SEM photograph of a cross section of the nonaqueous electrolyte of Example 1.
- FIG. 14B is a SEM photograph of a cross section of the nonaqueous electrolyte of Comparative Example 2.
- FIG. 15A is an SEM photograph in which a partial region of FIG. 14A is enlarged.
- FIG. 15B is an SEM photograph in which a partial region of FIG. 14B is enlarged.
- FIG. 16 shows X-ray diffraction patterns for Sample 1 to Sample 3.
- FIG. 17 is a schematic cross-sectional view showing a configuration example of a separator applied to another embodiment.
- FIG. 1 is a schematic cross-sectional view illustrating a configuration of an example of a nonaqueous electrolyte according to the present technology.
- FIG. 1 shows a schematic configuration example when a nonaqueous electrolyte is used in a battery.
- the positive electrode 33 includes a positive electrode current collector 33A and a positive electrode active material layer 33B formed on both surfaces of the positive electrode current collector 33A.
- the negative electrode 34 includes a negative electrode current collector 34A and a negative electrode active material layer 34B formed on both surfaces of the negative electrode current collector 34A.
- the separator 35 is provided between the positive electrode 33 and the negative electrode 34 in order to separate the positive electrode 33 and the negative electrode 34.
- the nonaqueous electrolyte 36 is disposed so as to be in contact with the positive electrode 33 and the negative electrode 34, for example.
- the nonaqueous electrolyte 36 provided on both sides of the positive electrode 33 in FIG. 1 may be omitted, and the nonaqueous electrolyte 36 may be disposed so as to contact only the negative electrode 34 side. . 1, the nonaqueous electrolyte 36 provided on both sides of the negative electrode 34 may be omitted, and the nonaqueous electrolyte 36 may be disposed so as to be in contact with only the positive electrode 33 side.
- the nonaqueous electrolyte 36 includes a nonaqueous solvent, an electrolyte salt, a resin (matrix resin), and a filler 38.
- a matrix resin is impregnated and held with an electrolytic solution (nonaqueous solvent and electrolyte salt).
- the non-aqueous electrolyte 36 is, for example, a gel-like ionic conductor that contains a filler 38 and is in a gel-like form when the matrix resin is swollen by the electrolytic solution.
- the nonaqueous electrolyte 36 includes a filler 38 and a resin, and is disposed between the positive electrode 33 and the negative electrode 34, and insulates the positive electrode 33 and the negative electrode 34 together with the separator 35. Insulating layer).
- the separator 35 may be omitted.
- the non-aqueous electrolyte 36 is disposed between the positive electrode 33 and the negative electrode 34 and serves as a particle-containing insulating part that insulates the positive electrode 33 and the negative electrode 34 independently.
- Non-aqueous solvent As the non-aqueous solvent, various high dielectric constant solvents and low viscosity solvents can be used.
- the high dielectric constant solvent include those containing ethylene carbonate and propylene carbonate, but are not limited thereto.
- Examples of the high dielectric constant solvent include butylene carbonate, vinylene carbonate, 4-fluoro-1,3-dioxolan-2-one (fluoroethylene carbonate), 4-chloro-1,3-dioxolan-2-one (chloroethylene). Carbonate) and cyclic carbonates such as trifluoromethylethylene carbonate.
- a lactone such as ⁇ -butyrolactone and ⁇ -valerolactone
- a lactam such as N-methylpyrrolidone
- a cyclic carbamic acid such as N-methyloxazolidinone Sulfone compounds such as esters and tetramethylene sulfone
- examples of the low-viscosity solvent include chain carbonates such as dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, and methyl propyl carbonate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, and methyl isobutyrate.
- Chain carboxylic acid esters such as methyl trimethylacetate and ethyl trimethylacetate, chain amides such as N, N-dimethylacetamide, chain carbamines such as methyl N, N-diethylcarbamate and ethyl N, N-diethylcarbamate Examples include acid esters, ethers such as 1,2-dimethoxyethane, tetrahydrofuran, tetrahydropyran, and 1,3-dioxolane.
- said high dielectric constant solvent and low-viscosity solvent can be used individually by 1 type or in mixture of these 2 or more types arbitrarily.
- the content of the nonaqueous solvent is preferably 70% by mass or more and 98% by mass or less with respect to the mass of the electrolytic solution. If it is less than 70% by mass, the viscosity may increase excessively, and if it exceeds 98% by mass, sufficient conductivity may not be obtained.
- Electrolyte salt any electrolyte salt may be used as long as it dissolves or disperses in a non-aqueous solvent, and lithium hexafluorophosphate (LiPF 6 ) can be preferably used, but is not limited thereto. It goes without saying that there is nothing.
- lithium tetrafluoroborate LiBF 4
- lithium hexafluoroarsenate LiAsF 6
- lithium hexafluoro antimonate LiSbF 6
- lithium perchlorate LiClO 4
- four lithium aluminum chloride acid Inorganic lithium salts such as LiAlCl 4 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium bis (trifluoromethanesulfone) imide (LiN (CF 3 SO 2 ) 2 ), lithium bis (pentafluoroethanesulfone) methide
- Lithium salts of perfluoroalkanesulfonic acid derivatives such as (LiC (C 2 F 5 SO 2 ) 2 ) and lithium tris (trifluoromethanesulfone) methide (LiC (CF 3 SO 2 ) 3 )
- Lithium salts of perfluoroalkanesulfonic acid derivatives such as (L
- the seeds can be used alone or in admixture of two or more.
- content of such electrolyte salt shall be 10 to 30 mass% with respect to the mass of electrolyte solution. If it is less than 10% by mass, sufficient conductivity may not be obtained, and if it exceeds 30% by mass, the viscosity may increase excessively.
- the matrix resin is not particularly limited as long as it can impregnate or hold the electrolytic solution (nonaqueous solvent and electrolyte salt) and filler 38.
- the matrix resin a polymer containing vinylidene fluoride, hexafluoropropylene, polytetrafluoroethylene or the like, that is, a homopolymer, a copolymer, and a multi-component copolymer are preferable.
- PVdF polyvinylidene fluoride
- PVdF-HFP polyvinylidene fluoride-hexafluoropropylene copolymer
- PVdF-HEP-CTFE polyvinylidene fluoride-hexafluoropropylene-chlorotrifluoroethylene copolymer
- the content of the matrix resin is preferably 2% by mass or more and 15% by mass or less with respect to the mass of the nonaqueous electrolyte 36.
- the content of the matrix resin is less than 2% by mass, the nonaqueous electrolyte may not be gelled.
- the content of the matrix resin exceeds 15% by mass, there is a possibility that the battery characteristics are affected, such as a decrease in energy density.
- particles such as flat inorganic particles that are substances that generate water by dehydration endothermic reaction (substances that generate a dehydration reaction) and have an aspect ratio of 2/1 or more can be used.
- a substance that generates water by a dehydration endothermic reaction absorbs heat by a dehydration endothermic reaction when the temperature rises, and has an action of suppressing an increase in temperature. Since the particles have a flat shape with an aspect ratio of 2/1 or more, they can exist stably in the battery, do not adversely affect the battery reaction, and have good electrical insulation and thermal conductivity. .
- a flat particle having an aspect ratio of 2/1 or more refers to a particle having a ratio of a long side of the particle to a short side of the flat particle (long side / short side) of 2/1 or more.
- the value can be read from, for example, an enlarged photograph of particles taken with a scanning electron microscope (SEM).
- SEM scanning electron microscope
- the aspect ratio is preferably 2/1 or more and 400/1 or less from a practical viewpoint.
- the aspect ratio can typically be obtained as follows. A predetermined number of particles (primary particles) in the nonaqueous electrolyte 36 are randomly selected, and each selected particle is observed three-dimensionally with a scanning electron microscope. Thus, the aspect ratio of each particle (long side) from the short side of the flat shape (length of the shortest part in the thickness direction) and the length of the longest part (long side) of the part (surface) orthogonal to the thickness direction ( Long side / short side). And an aspect ratio can be calculated
- the temperature at which the dehydration endothermic reaction occurs is preferably 160 ° C. or higher, more preferably 160 ° C. or higher and 900 ° C. or lower, and still more preferably 400 ° C. or higher and 900 ° C. or lower.
- the temperature at which the dehydration endothermic reaction occurs is lower than 160 ° C.
- the generated water is unstable and may react with the electrolyte and affect the battery characteristics.
- the temperature at which the dehydration endothermic reaction occurs is higher than 900 ° C., the endothermic action due to the dehydration reaction does not tend to occur in the usage state of the battery, and the effect tends to decrease.
- the temperature at which dehydration endothermic reaction occurs can be measured, for example, as follows.
- the battery is disassembled and the electrode is washed with a solvent such as DMC (dimethyl carbonate).
- a solvent such as DMC (dimethyl carbonate).
- the electrolyte component applied to the electrode surface is separated, and the solution from which the electrolyte component has been separated is separated by a centrifuge to obtain a filler component (filler 38).
- this filler component is heated up to 1000 ° C. at a rate of temperature increase of 10 ° C./min using a thermogravimetric analyzer (manufactured by SII, TG / DTA 6300), and dehydration endothermic reaction is performed from the temperature at which weight loss occurs. Can be measured.
- inorganic particles made of a substance that generates water by dehydration endothermic reaction include hydrate particles, metal hydroxide particles, mineral particles, and the like. These can be used individually by 1 type or in mixture of 2 or more types arbitrarily.
- sulfate hydrates such as magnesium sulfate (MgSO 4 ), calcium sulfate (CaSO 4 ), barium sulfate (BaSO 4 ), and strontium sulfate (SrSO 4 ) can be suitably used.
- MgSO 4 magnesium sulfate
- CaSO 4 calcium sulfate
- BaSO 4 barium sulfate
- SrSO 4 strontium sulfate
- AlOOH boehmite, Al 2 O 3 H 2 O
- magnesium hydroxide Mg (OH) 2 , brucite
- aluminum hydroxide Al (OH) 3 (Buyerlite, gibbsite)
- Hydrated hydroxides such as zinc hydroxide (Zn (OH) 2 ), oxidized hydroxides, hydrated oxides, and the like can be preferably used.
- mineral particles include clay mineral particles (clay mineral particles) and the like.
- clay mineral examples include a crystalline clay mineral, an amorphous or quasicrystalline clay mineral, and the like.
- crystalline clay minerals include layered silicate (phyllosilicate) minerals, those close to layered silicates, silicate minerals such as other silicate minerals, and layered carbonate minerals. .
- the layered silicate mineral includes a Si—O tetrahedral sheet and an octahedral sheet such as Al—O and Mg—O combined with the tetrahedral sheet.
- Layered silicates are typically classified by the number of tetrahedral and octahedral sheets, the number of cations in the octahedron, and the layer charge.
- the layered silicate mineral may be one obtained by substituting all or part of metal ions between layers with organic ammonium ions or the like.
- the layered silicate minerals include a kaolinite-serpentine group with a 1: 1 type structure, a pyrophyllite-talc group, a smectite group, a vermiculite group, a mica group with a 2: 1 type structure. And those corresponding to the brittle mica (brittle mica) family, chlorite (chlorite group), and the like.
- Examples of the kaolinite-serpentine group include chrysotile, antigolite, lizardite, kaolinite, and dickite.
- Examples of the pyrophyllite-talc family include talc (Mg 3 Si 4 O 10 (OH) 2 ), willemsite, and granite (pyrophyllite, Al 2 Si 4 O 10 (OH) 2. ) And the like.
- smectite group examples include saponite [(Ca / 2, Na) 0.33 (Mg, Fe 2+ ) 3 (Si, Al) 4 O 10 (OH) 2 .4H 2 O], hectorite, Sauconite, montmorillonite ⁇ (Na, Ca) 0.33 (Al, Mg) 2Si 4 O 10 (OH) 2 .nH 2 O, where clay containing montmorillonite as a main component is called bentonite ⁇ , beidellite, nontrite, etc. .
- examples of the mica (mica) group include sericite (sericite), phlogopite (phlogopite), biotite, and lipidoid (lithia mica).
- brittle mica brittle mica
- chlorite chlorite family
- examples of those belonging to the brittle mica (brittle mica) family include margarite, clintonite, and anandite.
- Examples of the chlorite (chlorite) family include kukkeite, sudokuite, clinochlore, chamosite, and nimite.
- a hydrous magnesium silicate having a 2: 1 ribbon structure in which a tetrahedron sheet arranged in a ribbon shape is connected to a tetrahedron sheet arranged in an adjacent ribbon shape while reversing the apex.
- the hydrous magnesium silicate include sepiolite (foamstone: Mg 9 Si 12 O 30 (OH) 6 (OH 2 ) 4 .6H 2 O), palygorskite and the like.
- silicate mineral porous aluminosilicate such as zeolite (M 2 / n O ⁇ Al 2 O 3 ⁇ xSiO 2 ⁇ yH 2 O, M represents a metal element, x ⁇ 2, y ⁇ 0 ), Attapulgite [(Mg, Al) 2 Si 4 O 10 (OH) ⁇ 6H 2 O] and the like.
- zeolite M 2 / n O ⁇ Al 2 O 3 ⁇ xSiO 2 ⁇ yH 2 O
- M represents a metal element, x ⁇ 2, y ⁇ 0
- Attapulgite [(Mg, Al) 2 Si 4 O 10 (OH) ⁇ 6H 2 O] and the like.
- the layered carbonate minerals hydrotalcite (Mg 6 Al 2 (CO 3 ) (OH) 16 ⁇ 4 (H 2 O)) and the like.
- amorphous or quasicrystalline clay minerals examples include bingellite, imogolite, and allophane.
- the mineral particles may be natural minerals or artificial minerals.
- the filler 38 is preferably in a state of being oriented parallel to the electrode surface.
- the state in which the fillers 38 (flat particles) are oriented parallel to the electrode surface means that the thickness direction of the plurality of flat particles (fillers 38) in the nonaqueous electrolyte 36 is the normal to the electrode surface. It refers to the state of being generally aligned in a direction parallel to the direction. Note that “parallel” includes substantially parallel.
- the orientation state of the flat particles (filler 38) in the nonaqueous electrolyte 36 can typically be confirmed by observing the cross section of the battery with a scanning electron microscope.
- the normal to the electrode surface is used as a reference line, and the angle with respect to the reference line in the thickness direction of the flat particles is set to 3 ⁇ m from at least one surface of the separator.
- Each of the predetermined number of particles (primary particles) existing in the region is obtained.
- the region may be a region from the surface where the particle-containing portion such as the electrode surface is formed to 3 ⁇ m.
- the filler 38 Since the filler 38 is oriented parallel to the electrode surface, the particles are easily connected in the direction parallel to the electrode surface (plane direction), but in the vertical direction (direction perpendicular to the plane direction) It becomes difficult to be connected. Therefore, for example, the heat generated from the electrode is easily dispersed uniformly in the plane in the plane direction, but is hardly dispersed in the direction perpendicular to the plane direction. That is, the non-aqueous electrolyte 36 containing the filler 38 has thermal conductivity anisotropy, and the thermal conductivity in the direction perpendicular to the electrode surface becomes smaller than the thermal conductivity in the direction parallel to the electrode surface. In addition, the heat insulation between different electrodes can be further improved.
- the orientation state can be identified from the X-ray diffraction pattern of the non-aqueous electrolyte 36 disposed on the electrode.
- the filler 38 is talc
- the (006) plane is oriented in a direction parallel to the electrode surface.
- the diffraction peak intensity of the surface for example, the (132) surface is relatively small. Therefore, if the peak intensity ratio ⁇ diffraction peak intensity of (006) plane / diffraction peak intensity of (132) plane ⁇ is 10 or more and 1000 or less, it can be confirmed that the filler 38 is oriented parallel to the electrode surface.
- the content ratio of the filler 38 (particles) to the matrix resin is typically, for example, from 1/1 to 25/1, and from 1/1 to 5 / 1 or less is preferable.
- the content ratio is less than 1/1, the effect of containing the inorganic particles tends to be small, and when the content ratio exceeds 5/1, battery characteristics such as cycle characteristics tend to deteriorate.
- the non-aqueous electrolyte of the present technology described above can suppress deterioration of battery characteristics of a battery including the same, and can improve heat dissipation against internal heat generation.
- Patent Document 1 Japanese Patent Laid-Open No. 10-214640
- the strength (load) until a short circuit occurs can be increased,
- the impregnation property of the electrolytic solution into the electrode is likely to decrease, and as a result, the battery characteristics may be deteriorated.
- Patent Document 2 Japanese Patent Laid-Open No. 2010-198757
- the strength against short circuit is improved, and the impregnation property of the electrolyte into the electrode is also improved.
- the heat dissipation when the temperature rises may not be sufficient.
- the nonaqueous electrolyte of the present technology can be formed thin by improving the coverage on the electrode by orienting the flat particles. Since the filler particles are flat, the insulation between the electrodes is superior to that of the fine particles, and even when foreign matter is mixed, occurrence of a short circuit between the positive electrode and the negative electrode can be suppressed. Thereby, safety can be improved.
- the non-aqueous electrolyte of the present technology suppresses the heat generated by the local short circuit of the negative electrode from being transmitted to the positive electrode even when a short circuit occurs, and by heat conduction in a direction parallel to the electrode. By dissipating heat, it is possible to prevent thermal runaway from local temperature rise. Thereby, safety can be improved.
- the filler performs a dehydration endothermic reaction, thereby suppressing a temperature rise due to heat generation. Thereby, safety can be improved.
- the nonaqueous electrolyte battery according to the second embodiment of the present technology is a laminated film type nonaqueous electrolyte battery including the nonaqueous electrolyte according to the first embodiment described above.
- This nonaqueous electrolyte battery is, for example, a nonaqueous electrolyte secondary battery that can be charged and discharged, and is, for example, a lithium ion secondary battery.
- two structural examples (a 1st example and a 2nd example) of a laminate film type nonaqueous electrolyte secondary battery are explained.
- FIG. 2 is an exploded perspective view showing a first example of the nonaqueous electrolyte secondary battery of the present technology.
- the secondary battery includes a wound electrode body 30 to which a positive electrode lead (positive electrode terminal) 31 and a negative electrode lead (negative electrode terminal) 32 are attached enclosed in a film-shaped exterior member 40. It is configured.
- the positive electrode lead 31 and the negative electrode lead 32 are led out, for example, in the same direction from the inside of the exterior member 40 to the outside.
- the positive electrode lead 31 and the negative electrode lead 32 are each made of a metal material such as aluminum (Al), copper (Cu), nickel (Ni), or stainless steel.
- the exterior member 40 is made of, for example, a rectangular laminate film in which a nylon film, an aluminum foil, and a polyethylene film are laminated in this order.
- the exterior member 40 is arrange
- An adhesion film 41 is inserted between the exterior member 40 and the positive electrode lead 31 and the negative electrode lead 32 to prevent intrusion of outside air.
- the adhesion film 41 is made of a material having adhesion to the positive electrode lead 31 and the negative electrode lead 32.
- polyethylene, polypropylene, modified It is preferably composed of a polyolefin resin such as polyethylene or modified polypropylene.
- the exterior member 40 may be composed of another structure, for example, a laminate film having no metal material, a polymer film such as polypropylene, or a metal film, instead of the above-described laminate film.
- the general structure of a laminate film can be represented by the laminated structure of exterior layer / metal foil / sealant layer (however, the exterior layer and sealant layer may be composed of a plurality of layers), and the above.
- the nylon film corresponds to the exterior layer
- the aluminum foil corresponds to the metal foil
- the polyethylene film corresponds to the sealant layer.
- metal foil it is sufficient if it functions as a moisture-permeable barrier film, and not only aluminum foil but also stainless steel foil, nickel foil, plated iron foil, etc. can be used. Thus, an aluminum foil excellent in workability can be suitably used.
- (exterior layer / metal foil / sealant layer) Ny (nylon) / Al (aluminum) / CPP (unstretched polypropylene), PET (polyethylene terephthalate) / Al / CPP, PET / Al / PET / CPP, PET / Ny / Al / CPP, PET / Ny / Al / Ny / CPP, PET / Ny / Al / Ny / PE (polyethylene), Ny / PE / Al / LLDPE (direct) Chain low density polyethylene), PET / PE / Al / PET / LDPE (low density polyethylene), and PET / Ny / Al / LDPE / CPP.
- FIG. 3 is a schematic cross-sectional view taken along line II of the spirally wound electrode body 30 shown in FIG.
- the wound electrode body 30 is formed by winding a positive electrode 33 and a negative electrode 34 facing each other with a nonaqueous electrolyte 36 and a separator 35 therebetween, and the outermost peripheral portion is a protective tape. 37 is protected.
- the nonaqueous electrolyte 36 is the same as that in the first embodiment described above. That is, the nonaqueous electrolyte 36 includes the same nonaqueous solvent as in the first embodiment, an electrolyte salt, a matrix resin, and a filler 38 (not shown).
- a positive electrode active material layer 33B is formed on both surfaces or one surface of a positive electrode current collector 33A having a pair of opposed surfaces, and both surfaces or one surface of the positive electrode current collector 33A is covered with the positive electrode active material layer 33B.
- the positive electrode current collector 33A has a portion that is exposed without being covered with the positive electrode active material layer 33B at one end portion in the longitudinal direction, and the positive electrode lead 31 is attached to the exposed portion.
- the positive electrode current collector 33A is made of a metal foil such as an aluminum foil, a nickel foil, or a stainless steel foil.
- the positive electrode active material layer 33B includes one or more positive electrode materials capable of inserting and extracting lithium ions as a positive electrode active material, and a conductive agent and a binder as necessary. May be included.
- positive electrode materials capable of inserting and extracting lithium ions include oxides such as vanadium oxide (V 2 O 5 ), titanium dioxide (TiO 2 ), manganese dioxide (MnO 2 ), sulfur (S), Disulfides such as iron disulfide (FeS 2 ), titanium disulfide (TiS 2 ), molybdenum disulfide (MoS 2 ), and chalcogenides that do not contain lithium such as niobium diselenide (NbSe 2 ) (particularly layered compounds and Spinel type compounds), lithium-containing compounds containing lithium, and conductive polymer compounds such as polyaniline, polythiophene, polyacetylene, and polypyrrole.
- oxides such as vanadium oxide (V 2 O 5 ), titanium dioxide (TiO 2 ), manganese dioxide (MnO 2 ), sulfur (S), Disulfides such as iron disulfide (FeS 2 ), titanium disulfide (TiS 2 ), molybden
- lithium-containing compounds are preferable because some compounds can obtain a high voltage and a high energy density.
- a lithium-containing compound include a composite oxide containing lithium and a transition metal element, and a phosphate compound containing lithium and a transition metal element.
- cobalt (Co), nickel (Ni), manganese (Mn), iron (Fe), copper (Cu), zinc (Zn), chromium (Cr), vanadium Those containing (V), titanium (Ti) or any mixture thereof are preferred.
- Such lithium-containing compounds typically include compounds represented by the following general formula (1) or (2).
- the compound of the general formula (1) generally has a layered structure
- the compound of the general formula (2) generally has an olivine structure.
- Li r MIO 2 (1) Li s MIIPO 4 (2) (In general formula (1) and general formula (2), M I and M II represent one or more transition metal elements. The values of r and s vary depending on the charge / discharge state of the battery, but usually 0.05 ⁇ r ⁇ 1.10, 0.05 ⁇ s ⁇ 1.10.
- the phosphate compound containing lithium and a transition metal element include, for example, a lithium iron phosphate compound having an olivine structure (LiFePO 4 ) and a lithium iron manganese phosphate compound (LiFe 1-z Mn z PO 4 (0 ⁇ z ⁇ 1)) and the like.
- the conductive agent is not particularly limited as long as an appropriate amount can be mixed with the positive electrode active material to impart conductivity, and examples thereof include carbon materials such as graphite, carbon black, and ketjen black. These are used alone or in combination of two or more.
- carbon material such as graphite, carbon black, and ketjen black. These are used alone or in combination of two or more.
- a metal material, a conductive polymer material, or the like may be used as long as it is a conductive material.
- a known binder that is usually used in a positive electrode mixture of this type of battery can be used, and preferably a fluorine such as polyvinyl fluoride, polyvinylidene fluoride, and polytetrafluoroethylene.
- synthetic rubbers such as styrene-based polymers, styrene butadiene rubbers, fluorine rubbers, and ethylene propylene diene rubbers. These may be used alone or in combination of two or more.
- the negative electrode 34 is provided with, for example, a negative electrode active material layer 34 ⁇ / b> B on both surfaces or one surface of a negative electrode current collector 34 ⁇ / b> A having a pair of opposing surfaces, and both surfaces or one surface of the negative electrode current collector 34 ⁇ / b> A is a negative electrode active material. It has a structure covered with the layer 34B.
- the negative electrode current collector 34A has an exposed portion where the negative electrode active material layer 34B is not provided at one end in the longitudinal direction, and the negative electrode lead 32 is attached to the exposed portion.
- the negative electrode current collector 34A is made of a metal foil such as a copper foil, a nickel foil, or a stainless steel foil.
- the negative electrode active material layer 34B contains one or more of a negative electrode material capable of occluding and releasing lithium ions and metallic lithium as a negative electrode active material, and a conductive agent and a binder as necessary.
- An adhesive may be included.
- Examples of the negative electrode material capable of inserting and extracting lithium ions include carbon materials, metal oxides, and polymer compounds.
- Examples of the carbon material include non-graphitizable carbon materials, artificial graphite materials, and graphite-based materials. More specifically, pyrolytic carbons, cokes, graphites, glassy carbons, and organic polymer compounds. There are fired bodies, carbon fibers, activated carbon, carbon black and the like. Among these, coke includes pitch coke, needle coke, petroleum coke, etc., and the organic polymer compound fired body is carbonized by firing a polymer material such as phenol resin or furan resin at an appropriate temperature. Say things.
- examples of the metal oxide include iron oxide, ruthenium oxide, molybdenum oxide, and the like
- examples of the polymer compound include polyacetylene and polypyrrole.
- examples of the negative electrode material capable of inserting and extracting lithium ions include a material containing at least one of a metal element and a metalloid element capable of forming an alloy with lithium as a constituent element.
- the negative electrode material may be a single element, alloy, or compound of a metal element or a metalloid element, or may have at least a part of one or more of these phases.
- the alloy includes an alloy containing one or more metal elements and one or more metalloid elements in addition to an alloy composed of two or more metal elements.
- the nonmetallic element may be included.
- Some of the structures include a solid solution, a eutectic (eutectic mixture), an intermetallic compound, or a mixture of two or more of these.
- metal elements or metalloid elements examples include tin (Sn), lead (Pb), magnesium (Mg), aluminum, indium (In), silicon (Si), zinc (Zn), antimony (Sb), Bismuth (Bi), gallium (Ga), germanium (Ge), arsenic (As), silver (Ag), hafnium (Hf), zirconium (Zr) and yttrium (Y) can be mentioned.
- the group 14 metal element or metalloid element in the long-period periodic table is preferable, and silicon or tin is particularly preferable. This is because silicon and tin have a large ability to occlude and release lithium, and a high energy density can be obtained.
- alloy of tin for example, silicon, magnesium, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony and chromium (Cr) are used.
- the thing containing at least 1 sort (s) of the group which consists of is mentioned.
- alloy of silicon for example, as a second constituent element other than silicon, tin, magnesium, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony and chromium are used. The thing containing at least 1 sort (s) of them is mentioned.
- the tin compound or the silicon compound examples include those containing oxygen (O) or carbon (C), and may contain the second constituent element described above in addition to tin or silicon.
- the negative electrode material as described above may be an element that forms a composite oxide with lithium, such as titanium.
- metallic lithium may be precipitated and dissolved, and magnesium and aluminum other than lithium may be precipitated and dissolved.
- the conductive agent and the binder the same materials as those used for the positive electrode can be used.
- the separator 35 is an insulating material having a high ion permeability and a predetermined mechanical strength, such as a porous film made of a polyolefin-based synthetic resin such as polypropylene or polyethylene, or a porous film made of an inorganic material such as a ceramic nonwoven fabric. It consists of a thin film. In addition, it is good also as a structure which laminated
- the positive electrode 33 is produced.
- a positive electrode mixture is prepared by mixing the positive electrode active material with a conductive agent and a binder as necessary, and a dispersion medium such as N-methyl-2-pyrrolidone is prepared.
- a positive electrode mixture slurry is applied to the positive electrode current collector 33A, dried, and compression molded to form the positive electrode active material layer 33B.
- the negative electrode 34 is produced.
- a negative electrode mixture is prepared by mixing a negative electrode active material and, if necessary, a conductive agent and a binder, and a dispersion medium such as N-methyl-2-pyrrolidone. To prepare a negative electrode mixture slurry. Thereafter, the negative electrode mixture slurry is applied to the negative electrode current collector 34A, dried, and compression molded to form the negative electrode active material layer 34B.
- non-aqueous electrolyte material for forming the above-described non-aqueous electrolyte 36 is prepared.
- the non-aqueous electrolyte material is prepared by mixing a non-aqueous solvent, an electrolyte salt, a matrix resin, and inorganic filler particles (filler 38), and adjusting the viscosity to 150 mPa ⁇ s or more, preferably 40 mPa ⁇ s to 70 mPa ⁇ s. By doing so, it can be obtained.
- the orientation state of the inorganic filler particles in the nonaqueous electrolyte 36 can be made predetermined.
- the viscosity is higher than 150 mPa ⁇ s, the movement of the inorganic filler particles is hindered in the applied nonaqueous electrolyte material layer, and it tends to be difficult to obtain a desired orientation state.
- the viscosity is lower than 40 mPa ⁇ s, when the electrolyte material is laminated on the positive electrode 33 or the negative electrode 34, the end shape of the electrolyte material is likely to be disturbed, and the coating speed needs to be reduced. This is because if the shape of the electrolyte material is disturbed, the safety and battery characteristics may be deteriorated due to variations in the distance between the electrodes. On the other hand, even when the viscosity is higher than 70 mPa ⁇ s, there is a possibility that the conductivity is affected and the battery capacity is lowered. Further, as the nonaqueous electrolyte material, a material further containing a viscosity adjusting solvent can be used.
- a viscosity adjusting solvent for example, it is preferable to use a solvent that volatilizes when the nonaqueous electrolyte 36 is disposed in contact with the positive electrode 33, the negative electrode 34, and the like. Thereby, it can suppress that the nonaqueous electrolyte 36 obtained reduces a battery characteristic.
- a solvent for adjusting viscosity those applicable as a non-aqueous solvent can be used, and examples thereof include dimethyl carbonate and ethyl methyl carbonate.
- the above-described nonaqueous electrolyte material is applied to at least one of the positive electrode 33 and the negative electrode 34. Thereby, the layer of the nonaqueous electrolyte 36 is formed.
- the negative electrode 34, the separator 35, the positive electrode 33, and the separator 35 are sequentially laminated and wound, and the protective tape 37 is adhered to the outermost peripheral portion to form the wound electrode body 30, and the wound electrode body 30 is attached to the exterior member.
- 40 is sandwiched between laminate films as an example, and the outer peripheral edge except one side is heat-sealed to form a bag.
- the opening of the laminate film is heat-sealed and sealed. Thereby, the layer of the nonaqueous electrolyte 36 is formed, and the nonaqueous electrolyte secondary battery shown in FIGS. 2 to 3 is completed.
- FIG. 4A is an external view of the nonaqueous electrolyte secondary battery 62 in which the laminated electrode body 70 is accommodated.
- FIG. 4B is an exploded perspective view showing a state in which the laminated electrode body 70 is accommodated in the exterior member 60.
- FIG. 4C is an external view showing an external appearance from the bottom surface side of the nonaqueous electrolyte secondary battery 62 shown in FIG. 4A.
- the laminated electrode body 70 uses a laminated electrode body 70 in which a rectangular positive electrode 73 and a negative electrode 74 are laminated via a separator 75 and fixed by a fixing member 76.
- the nonaqueous electrolyte is provided in contact with the positive electrode 73 and the negative electrode 74.
- a nonaqueous electrolyte (not shown) is provided between the positive electrode 73 and the separator 75 and between the negative electrode 74 and the separator 75. This nonaqueous electrolyte is the same as the nonaqueous electrolyte according to the first embodiment.
- a positive electrode lead 71 connected to the positive electrode 73 and a negative electrode lead 72 connected to the negative electrode 74 are led out from the laminated electrode body 70, and the positive electrode lead 71, the negative electrode lead 72, and the exterior member 60 are in close contact with each other.
- a film 61 is provided.
- the formation method of the nonaqueous electrolyte and the heat fusion method of the exterior member 60 are the same as those in the first example described above.
- a battery pack according to a third embodiment of the present technology will be described.
- the battery pack according to the third embodiment of the present technology is a battery pack of a laminate film type battery including the same nonaqueous electrolyte as that of the first embodiment.
- two configuration examples first example and second example
- a first example of the battery pack of the laminate film type battery according to the third embodiment will be described with reference to the drawings.
- a wound electrode body covered with a hard laminate film and a soft laminate film is referred to as a battery cell
- a circuit board is connected to the battery cell
- a top cover and a rear cover A battery pack is referred to as a battery pack.
- the lead-out side of the positive electrode terminal and the negative electrode terminal is referred to as a top portion
- the side facing the top portion is referred to as a bottom portion
- two sides excluding the top portion and the bottom portion are referred to as side portions.
- the length in the side portion-side portion direction is referred to as the width direction
- the length in the top portion-bottom portion direction is referred to as the height.
- FIG. 5 is a perspective view showing a configuration example of the first example of the battery pack according to the third embodiment.
- FIG. 6 is an exploded perspective view showing the structure of the battery cell.
- FIG. 7 is a top view and a side view showing a state in the middle of manufacturing the battery cell according to the third embodiment.
- FIG. 8 is a cross-sectional view showing a cross-sectional structure of the battery cell.
- the battery pack 90 is, for example, a battery pack of a nonaqueous electrolyte battery having a square shape or a flat shape. As shown in FIGS. 5 and 6, the battery pack 90 has both ends opened to form an opening, and the battery cell 80 in which the wound electrode body 50 is housed in the exterior material, and the battery cell 80 A top cover 82a and a bottom cover 82b fitted to the openings at both ends are provided.
- the wound electrode body 50 accommodated in the battery pack 90 is the same as the wound electrode body 30 of the second embodiment.
- the positive electrode lead 51 and the negative electrode lead 52 connected to the wound electrode body 50 are led out from the fused portion of the exterior material via the adhesion film 61, and the positive electrode lead 51 and the negative electrode lead 52 are connected. Are connected to the circuit board 81.
- the exterior material has a plate shape as a whole, and has a rectangular shape when viewed from the surface direction, and a length in the side portion direction than the hard laminate film 83. Consists of a soft laminate film 85 having a short rectangular shape.
- the opening at both ends of the battery cell 80 has a rectangular shape as a whole, and both short sides swell outwardly to form an elliptical arc.
- the battery cell 80 includes a soft laminate film 85 provided with a recess 86, a wound electrode body 50 accommodated in the recess 86, and a hard provided so as to cover the opening of the recess 86 that accommodates the wound electrode body 50. It consists of a laminate film 83.
- the hard laminate film 83 is set so that the short sides of both sides abut or face each other with a slight gap in a state in which the recess 86 in which the wound electrode body 50 is housed is wrapped.
- a cutout portion 84 may be provided on the long side of the top side of the hard laminate film 83.
- the notches 84 are provided so as to be located on both short sides when viewed from the front of the battery cell 80. By providing the notch portion 84, the top cover 82a can be easily fitted.
- the positive electrode lead 51 and the negative electrode lead 52 electrically connected to the positive electrode 53 and the negative electrode 54 of the wound electrode body 50 respectively. Has been derived.
- the top cover 82a and the bottom cover 82b have shapes that can be fitted into openings at both ends of the battery cell 80. Specifically, when viewed from the front, the top cover 82a and the bottom cover 82b have a rectangular shape as a whole, and both short sides thereof are It swells to form an elliptical arc toward the outside. Note that the front indicates a direction in which the battery cell 80 is viewed from the top side.
- this exterior material covers a soft laminate film 85 provided with a recess 86 for housing the wound electrode body 50, and covers the recess 86 on the soft laminate film 85. And a hard laminate film 83 stacked on top of each other.
- the soft laminate film 85 has the same configuration as that of the exterior member 60 in the second embodiment.
- the soft laminate film 85 is characterized in that a soft metal material such as annealed aluminum (JIS A8021P-O) or (JIS A8079P-O) is used as the metal layer.
- a soft metal material such as annealed aluminum (JIS A8021P-O) or (JIS A8079P-O) is used as the metal layer.
- the soft laminate film 85 has a function of maintaining the shape after bending and withstanding deformation from the outside. For this reason, a hard metal material such as aluminum (Al), stainless steel (SUS), iron (Fe), copper (Cu), or nickel (Ni) is used as the metal layer, and in particular, a hard material without annealing treatment. It is characterized in that aluminum (JIS A3003P-H18) or (JIS A3004P-H18) or austenitic stainless steel (SUS304) is used.
- a hard metal material such as aluminum (Al), stainless steel (SUS), iron (Fe), copper (Cu), or nickel (Ni) is used as the metal layer, and in particular, a hard material without annealing treatment. It is characterized in that aluminum (JIS A3003P-H18) or (JIS A3004P-H18) or austenitic stainless steel (SUS304) is used.
- the wound electrode body 50 has the same configuration as that of the wound electrode body 30 according to the second embodiment.
- the laminated electrode body 70 described in the second example of the second embodiment may be used.
- Nonaqueous electrolyte The nonaqueous electrolyte formed between the positive electrode 53 and the separator 55 and between the negative electrode 54 and the separator 55 is the same as the nonaqueous electrolyte of the first embodiment.
- the separator 55 is the same as the separator 35 of the second embodiment.
- the circuit board 81 is one in which the positive electrode lead 51 and the negative electrode lead 52 of the wound electrode body 50 are electrically connected.
- the circuit board 81 is mounted with a protection circuit including a temperature protection element such as a fuse, a thermal resistance element (Positive Temperature Coefficient; PTC element), a thermistor, etc., and an ID resistor for identifying the battery pack. (For example, three) contact portions are formed.
- the protection circuit is provided with a charge / discharge control FET (Field Effect Transistor), an IC (Integrated Circuit) for monitoring the battery cell 80 and controlling the charge / discharge control FET, and the like.
- the thermal resistance element is connected in series with the wound electrode body, and when the temperature of the battery becomes higher than the set temperature, the electrical resistance increases rapidly and substantially blocks the current flowing through the battery.
- the fuse is also connected in series with the wound electrode body, and when an overcurrent flows through the battery, it is blown by its own current to cut off the current.
- a heater resistor is provided in the vicinity of the fuse. When an overvoltage is applied, the temperature of the heater resistor rises, so that the current is cut off.
- the battery cell 80 when the terminal voltage of the battery cell 80 becomes higher than the charge prohibition voltage higher than the full charge voltage, the battery cell 80 may be in a dangerous state such as heat generation and ignition. For this reason, the protection circuit monitors the voltage of the battery cell 80, and when the battery cell 80 reaches the charge prohibition voltage, the charge control FET is turned off to prohibit charging. Furthermore, when the terminal voltage of the battery cell 80 is over-discharged to a voltage lower than the discharge inhibition voltage and the battery cell 80 voltage becomes 0 V, the battery cell 80 may be in an internal short circuit state and may not be recharged. For this reason, when the battery cell 80 voltage is monitored and the discharge inhibition voltage is reached, the discharge control FET is turned off to inhibit discharge.
- the top cover 82a is fitted into the top side opening of the battery cell 80, and a side wall for fitting into the top side opening is provided along part or all of the outer periphery of the top cover 82a. .
- the battery cell 80 and the top cover 82a are bonded by heat-sealing the side wall of the top cover 82a and the inner surface of the end of the hard laminate film 83.
- the circuit board 81 is accommodated in the top cover 82a.
- the top cover 82a is provided with a plurality of openings at positions corresponding to the contact portions so that the plurality of contact portions of the circuit board 81 are exposed to the outside.
- the contact portion of the circuit board 81 contacts the electronic device through the opening of the top cover 82a. Thereby, the battery pack 90 and the electronic device are electrically connected.
- Such a top cover 82a is produced in advance by injection molding.
- the bottom cover 82b is fitted into the bottom opening of the battery cell 80, and a side wall for fitting into the bottom opening is provided along a part or all of the outer periphery of the bottom cover 82b. .
- the battery cell 80 and the bottom cover 82b are bonded by heat-sealing the side wall of the bottom cover 82b and the inner surface of the end of the hard laminate film 83.
- Such a bottom cover 82b is produced in advance by injection molding. It is also possible to use a method in which the battery cell 80 is installed in a mold and a hot melt resin is poured into the bottom portion so as to be molded integrally with the battery cell 80.
- the wound electrode body 50 is accommodated in the recess 86 of the soft laminate film 85, and the hard laminate film 83 is disposed so as to cover the recess 86.
- the hard laminate film 83 and the soft laminate film 85 are disposed so that the inner resin layer of the hard laminate film 83 and the inner resin layer of the soft laminate film 85 face each other.
- the hard laminate film 83 and the soft laminate film 85 are sealed along the periphery of the recess 86.
- the sealing is performed by using a metal heater head (not shown) and thermally fusing the inner resin layer of the hard laminate film 83 and the inner resin layer of the soft laminate film 85 while reducing the pressure.
- the wound electrode body 50 may be formed by previously forming a gel electrolyte on both surfaces of the positive electrode and the negative electrode.
- the hard laminate film 83 is deformed so that the short sides of the hard laminate film 83 are in contact with each other.
- an adhesive film 87 made of a resin material having high adhesion to both the inner resin layer of the hard laminate film 83 and the outer resin layer of the soft laminate film 85 is provided. insert.
- the inner resin layer of the hard laminate film 83 and the outer resin layer of the soft laminate film 85 are heat-sealed by heating the one surface of the hard laminate film 83 where the short side seam is located with a heater head.
- the battery cell 80 is obtained.
- an adhesive layer made of a resin having high adhesiveness with the outer resin layer of the soft laminate film 85 may be provided on the surface of the inner resin layer of the hard laminate film 83 and heat-sealed. Good.
- the fitting portions of the top cover 82a and the bottom cover 82b are respectively heated by the heater head, and the top cover 82a and the bottom cover 82b and the inner resin layer of the hard laminate film 83 are heat-sealed. Thereby, the battery pack 90 is produced.
- (3-2) Second Example A second example of the battery pack of the laminate film type battery according to the third embodiment will be described.
- This battery pack is a so-called simplified battery pack (also referred to as a soft pack).
- a simple battery pack is built in an electronic device.
- a battery cell, a protection circuit, etc. are fixed with an insulating tape or the like, a part of the battery cell is exposed, and a connector is connected to the main body of the electronic device. are provided.
- FIG. 9 is an exploded perspective view showing a configuration example of a simplified battery pack.
- FIG. 10A is a schematic perspective view showing an external appearance of a simple battery pack
- FIG. 10B is a schematic perspective view showing an external appearance of the simple battery pack.
- the simplified battery pack includes a battery cell 101, leads 102a and 102b derived from the battery cell 101, insulating tapes 103a to 103c, an insulating plate 104, A circuit board 105 on which a protection circuit (PCM (Protection Circuit Module)) is formed and a connector 106 are provided.
- the battery cell 101 is the same as the nonaqueous electrolyte secondary battery according to the second embodiment, for example.
- the insulating plate 104 and the circuit board 105 are disposed on the terrace portion 101 a at the front end of the battery cell 101, and the leads 102 a and the leads 102 b led out from the battery cell 101 are connected to the circuit board 105.
- a connector 106 for output is connected to the circuit board 105.
- Members such as the battery cell 101, the insulating plate 104, and the circuit board 105 are fixed by applying insulating tapes 103a to 103c to predetermined positions.
- FIG. 11 is a block diagram illustrating a circuit configuration example in a case where a battery according to the second embodiment of the present technology (hereinafter appropriately referred to as a secondary battery) is applied to a battery pack.
- the battery pack includes a switch unit 304 including an assembled battery 301, an exterior, a charge control switch 302a, and a discharge control switch 303a, a current detection resistor 307, a temperature detection element 308, and a control unit 310.
- the battery pack includes a positive electrode terminal 321 and a negative electrode lead 322, and at the time of charging, the positive electrode terminal 321 and the negative electrode lead 322 are connected to the positive electrode terminal and the negative electrode terminal of the charger, respectively, and charging is performed. Further, when the electronic device is used, the positive electrode terminal 321 and the negative electrode lead 322 are connected to the positive electrode terminal and the negative electrode terminal of the electronic device, respectively, and discharge is performed.
- the assembled battery 301 is formed by connecting a plurality of secondary batteries 301a in series and / or in parallel.
- the secondary battery 301a is a secondary battery of the present technology.
- FIG. 11 although the case where the six secondary batteries 301a are connected to 2 parallel 3 series (2P3S) is shown as an example, other n parallel m series (n and m are integers) Any connection method may be used.
- the switch unit 304 includes a charge control switch 302a and a diode 302b, and a discharge control switch 303a and a diode 303b, and is controlled by the control unit 310.
- the diode 302b has a reverse polarity with respect to the charging current flowing from the positive electrode terminal 321 in the direction of the assembled battery 301 and the forward polarity with respect to the discharging current flowing from the negative electrode lead 322 in the direction of the assembled battery 301.
- the diode 303b has a forward polarity with respect to the charging current and a reverse polarity with respect to the discharging current.
- the switch unit 304 is provided on the + side, but may be provided on the-side.
- the charge control switch 302a is turned off when the battery voltage becomes the overcharge detection voltage, and is controlled by the charge / discharge control unit so that the charge current does not flow in the current path of the assembled battery 301. After the charging control switch 302a is turned off, only discharging is possible via the diode 302b. Further, it is turned off when a large current flows during charging, and is controlled by the control unit 310 so that the charging current flowing in the current path of the assembled battery 301 is cut off.
- the discharge control switch 303 a is turned off when the battery voltage becomes the overdischarge detection voltage, and is controlled by the control unit 310 so that the discharge current does not flow in the current path of the assembled battery 301. After the discharge control switch 303a is turned off, only charging is possible via the diode 303b. Further, it is turned off when a large current flows during discharging, and is controlled by the control unit 310 so as to cut off the discharging current flowing in the current path of the assembled battery 301.
- the temperature detection element 308 is, for example, a thermistor, is provided in the vicinity of the assembled battery 301, measures the temperature of the assembled battery 301, and supplies the measured temperature to the control unit 310.
- the voltage detection unit 311 measures the voltage of the assembled battery 301 and each secondary battery 301a constituting the assembled battery 301, performs A / D conversion on the measured voltage, and supplies it to the control unit 310.
- the current measurement unit 313 measures the current using the current detection resistor 307 and supplies this measurement current to the control unit 310.
- the switch control unit 314 controls the charge control switch 302a and the discharge control switch 303a of the switch unit 304 based on the voltage and current input from the voltage detection unit 311 and the current measurement unit 313.
- the switch control unit 314 sends a control signal to the switch unit 304 when any voltage of the secondary battery 301a falls below the overcharge detection voltage or overdischarge detection voltage, or when a large current flows suddenly. By sending, overcharge, overdischarge, and overcurrent charge / discharge are prevented.
- the overcharge detection voltage is determined to be 4.20 V ⁇ 0.05 V, for example, and the overdischarge detection voltage is determined to be 2.4 V ⁇ 0.1 V, for example. .
- the charge / discharge switch for example, a semiconductor switch such as a MOSFET can be used.
- the parasitic diode of the MOSFET functions as the diodes 302b and 303b.
- the switch control unit 314 supplies control signals DO and CO to the gates of the charge control switch 302a and the discharge control switch 303a, respectively.
- the charge control switch 302a and the discharge control switch 303a are P-channel type, they are turned on by a gate potential that is lower than the source potential by a predetermined value or more. That is, in normal charging and discharging operations, the control signals CO and DO are set to the low level, and the charging control switch 302a and the discharging control switch 303a are turned on.
- control signals CO and DO are set to the high level, and the charge control switch 302a and the discharge control switch 303a are turned off.
- the memory 317 includes a RAM and a ROM, and includes, for example, an EPROM (Erasable Programmable Read Only Memory) that is a nonvolatile memory.
- EPROM Erasable Programmable Read Only Memory
- the numerical value calculated by the control unit 310, the internal resistance value of the battery in the initial state of each secondary battery 301a measured in the manufacturing process, and the like are stored in advance, and can be appropriately rewritten. . (Also, by storing the full charge capacity of the secondary battery 301a, for example, the remaining capacity can be calculated together with the control unit 310.
- the temperature detection unit 318 measures the temperature using the temperature detection element 308, performs charge / discharge control at the time of abnormal heat generation, and performs correction in the calculation of the remaining capacity.
- the battery according to the second embodiment of the present technology described above and the battery pack according to the third embodiment and the fourth embodiment using the battery are mounted on devices such as an electronic device, an electric vehicle, and a power storage device, for example. Or it can be used to supply power.
- Examples of electronic devices include notebook computers, PDAs (personal digital assistants), mobile phones, cordless phones, video movies, digital still cameras, electronic books, electronic dictionaries, music players, radios, headphones, game consoles, navigation systems, Memory card, pacemaker, hearing aid, electric tool, electric shaver, refrigerator, air conditioner, TV, stereo, water heater, microwave oven, dishwasher, washing machine, dryer, lighting equipment, toys, medical equipment, robots, road conditioners, traffic lights Etc.
- examples of the electric vehicle include a railway vehicle, a golf cart, an electric cart, an electric vehicle (including a hybrid vehicle), and the like, and these are used as a driving power source or an auxiliary power source.
- Examples of power storage devices include power storage power supplies for buildings such as houses or power generation facilities.
- the first power storage system is a power storage system in which a power storage device is charged by a power generation device that generates power from renewable energy.
- the second power storage system is a power storage system that includes a power storage device and supplies power to an electronic device connected to the power storage device.
- the third power storage system is an electronic device that receives power supply from the power storage device.
- the fourth power storage system includes an electric vehicle having a conversion device that receives power supplied from the power storage device and converts the power into a driving force of the vehicle, and a control device that performs information processing related to vehicle control based on information related to the power storage device. It is.
- the fifth power storage system is a power system that includes a power information transmission / reception unit that transmits / receives signals to / from other devices via a network, and performs charge / discharge control of the power storage device described above based on information received by the transmission / reception unit.
- the sixth power storage system is a power system that receives power from the power storage device described above or supplies power from the power generation device or the power network to the power storage device.
- the power storage system will be described.
- a power storage device using a battery of the present technology is applied to a residential power storage system
- a power storage system 400 for a house 401 power is stored from a centralized power system 402 such as a thermal power generation 402a, a nuclear power generation 402b, and a hydroelectric power generation 402c through a power network 409, an information network 412, a smart meter 407, a power hub 408, and the like.
- a power storage device 403 Supplied to the device 403.
- power is supplied to the power storage device 403 from an independent power source such as the power generation device 404 in the home.
- the electric power supplied to the power storage device 403 is stored. Electric power used in the house 401 is supplied using the power storage device 403.
- the same power storage system can be used not only for the house 401 but also for buildings.
- the house 401 is provided with a power generation device 404, a power consumption device 405, a power storage device 403, a control device 410 that controls each device, a smart meter 407, and a sensor 411 that acquires various types of information.
- Each device is connected by a power network 409 and an information network 412.
- a solar cell, a fuel cell, or the like is used as the power generation device 404, and the generated power is supplied to the power consumption device 405 and / or the power storage device 403.
- the power consuming device 405 is a refrigerator 405a, an air conditioner 405b, a television receiver 405c, a bath 405d, and the like.
- the electric power consumption device 405 includes an electric vehicle 406.
- the electric vehicle 406 is an electric vehicle 406a, a hybrid car 406b, and an electric motorcycle 406c.
- the battery of the present technology is applied to the power storage device 403.
- the battery of the present technology may be configured by, for example, the above-described lithium ion secondary battery.
- the smart meter 407 has a function of measuring the usage amount of commercial power and transmitting the measured usage amount to an electric power company.
- the power network 409 may be any one or a combination of DC power supply, AC power supply, and non-contact power supply.
- the various sensors 411 are, for example, human sensors, illuminance sensors, object detection sensors, power consumption sensors, vibration sensors, contact sensors, temperature sensors, infrared sensors, and the like. Information acquired by various sensors 411 is transmitted to the control device 410. Based on the information from the sensor 411, the weather condition, the condition of the person, and the like can be grasped, and the power consumption device 405 can be automatically controlled to minimize the energy consumption. Furthermore, the control apparatus 410 can transmit the information regarding the house 401 to an external electric power company etc. via the internet.
- the power hub 408 performs processing such as branching of power lines and DC / AC conversion.
- Communication methods of the information network 412 connected to the control device 410 include a method using a communication interface such as UART (Universal Asynchronous Receiver-Transceiver), wireless communication such as Bluetooth, ZigBee, Wi-Fi, etc.
- a communication interface such as UART (Universal Asynchronous Receiver-Transceiver), wireless communication such as Bluetooth, ZigBee, Wi-Fi, etc.
- Bluetooth method is applied to multimedia communication and can perform one-to-many connection communication.
- ZigBee uses the physical layer of IEEE (Institute of Electrical and Electronics Electronics) (802.15.4).
- IEEE802.15.4 is a name of a short-range wireless network standard called PAN (Personal Area Network) or W (Wireless) PAN.
- the control device 410 is connected to an external server 413.
- the server 413 may be managed by any one of the house 401, the power company, and the service provider.
- the information transmitted and received by the server 413 is, for example, information related to power consumption information, life pattern information, power charges, weather information, natural disaster information, and power transactions. These pieces of information may be transmitted / received from a power consuming device (for example, a television receiver) in the home, or may be transmitted / received from a device outside the home (for example, a mobile phone). Such information may be displayed on a device having a display function, for example, a television receiver, a mobile phone, a PDA (Personal Digital Assistant) or the like.
- the control device 410 that controls each unit includes a CPU (Central Processing Unit), a RAM (Random Access Memory), a ROM (Read Only Memory), and the like, and is stored in the power storage device 403 in this example.
- the control device 410 is connected to the power storage device 403, the domestic power generation device 404, the power consumption device 405, various sensors 411, the server 413 and the information network 412, and adjusts, for example, the amount of commercial power used and the amount of power generation It has a function to do. In addition, you may provide the function etc. which carry out an electric power transaction in an electric power market.
- the power generation device 404 (solar power generation, wind power generation) in the home is used as the power storage device 403. Can be stored. Therefore, even if the generated power of the power generation device 404 in the home fluctuates, it is possible to perform control such that the amount of power transmitted to the outside is constant or discharge is performed as necessary. For example, the power obtained by solar power generation is stored in the power storage device 403, and the nighttime power at a low charge is stored in the power storage device 403 at night, and the power stored by the power storage device 403 is discharged during a high daytime charge. You can also use it.
- control device 410 is stored in the power storage device 403 .
- control device 410 may be stored in the smart meter 407 or may be configured independently.
- the power storage system 400 may be used for a plurality of homes in an apartment house, or may be used for a plurality of detached houses.
- FIG. 13 schematically shows an example of the configuration of a hybrid vehicle that employs a series hybrid system to which the present technology is applied.
- a series hybrid system is a car that runs on an electric power driving force conversion device using electric power generated by a generator driven by an engine or electric power once stored in a battery.
- the hybrid vehicle 500 includes an engine 501, a generator 502, a power driving force conversion device 503, driving wheels 504 a, driving wheels 504 b, wheels 505 a, wheels 505 b, a battery 508, a vehicle control device 509, various sensors 510, and a charging port 511. Is installed.
- the battery of the present technology described above is applied to the battery 508.
- Hybrid vehicle 500 travels using power driving force conversion device 503 as a power source.
- An example of the power / driving force conversion device 503 is a motor.
- the electric power / driving force converter 503 is operated by the electric power of the battery 508, and the rotational force of the electric power / driving force converter 503 is transmitted to the driving wheels 504a and 504b.
- DC-AC DC-AC
- AC-DC conversion AC-DC conversion
- the power driving force converter 503 can be applied to either an AC motor or a DC motor.
- the various sensors 510 control the engine speed through the vehicle control device 509 and control the opening (throttle opening) of a throttle valve (not shown).
- Various sensors 510 include a speed sensor, an acceleration sensor, an engine speed sensor, and the like.
- the rotational force of the engine 501 is transmitted to the generator 502, and the electric power generated by the generator 502 by the rotational force can be stored in the battery 508.
- the resistance force at the time of deceleration is applied as a rotational force to the electric power driving force conversion device 503, and the regenerative electric power generated by the electric power driving force conversion device 503 by this rotational force becomes the battery 508. Accumulated in.
- the battery 508 is connected to an external power source of the hybrid vehicle 500, so that it can receive power from the external power source using the charging port 511 as an input port and store the received power.
- an information processing device that performs information processing related to vehicle control based on information related to the secondary battery may be provided.
- an information processing apparatus for example, there is an information processing apparatus that displays a battery remaining amount based on information on the remaining amount of the battery.
- the present technology is also effective for a parallel hybrid vehicle in which the engine and motor outputs are both driving sources, and the system is switched between the three modes of driving with only the engine, driving with the motor, and engine and motor. Applicable. Furthermore, the present technology can be effectively applied to a so-called electric vehicle that travels only by a drive motor without using an engine.
- Example 1 (Preparation of positive electrode) First, 91 parts by mass of lithium cobalt composite oxide (LiCoO 2 ) as a positive electrode active material, 6 parts by mass of graphite as a conductive agent, and 10 parts by mass of polyvinylidene fluoride (PVdF) as a binder are homogeneously mixed. Then, it was dispersed in N-methyl-2-pyrrolidone (NMP) to obtain a positive electrode mixture slurry.
- NMP N-methyl-2-pyrrolidone
- the obtained positive electrode mixture slurry was uniformly applied to both surfaces of a 20 ⁇ m-thick strip-shaped aluminum foil serving as a positive electrode current collector, and dried to form a positive electrode active material layer. This was cut into a shape having a width of 38 mm and a length of 700 mm to produce a positive electrode, and a positive electrode terminal was further attached.
- LiPF lithium hexafluorophosphate
- nonaqueous electrolyte secondary battery Preparation of non-aqueous electrolyte secondary battery
- the obtained nonaqueous electrolyte material is applied to both surfaces of the obtained positive electrode and negative electrode to form a nonaqueous electrolyte layer (gel electrolyte layer), and the positive electrode and negative electrode on which the nonaqueous electrolyte layer is formed have a thickness.
- a non-aqueous electrolyte secondary battery of Example 1 was obtained by laminating and winding through a separator made of a 12 ⁇ m microporous polyethylene film and sealing it in an exterior member made of an aluminum laminate film.
- Example 2 to Example 9 non-aqueous electrolyte secondary batteries were obtained in the same manner as in Example 1 except that at least one of the aspect ratio of the inorganic particles used for the filler and the orientation degree of the inorganic particles was changed. It was.
- the degree of orientation was adjusted by changing at least one of the viscosity of the nonaqueous electrolyte material and the aspect ratio of the inorganic particles. For example, by reducing the aspect ratio of the inorganic particles, it can be adjusted in a direction in which the degree of orientation is lowered, and by increasing the aspect ratio of the inorganic particles, it can be adjusted in a direction in which the degree of orientation is increased. Moreover, the orientation degree of a filler can be adjusted to a low direction or a high direction by changing the viscosity of a nonaqueous electrolyte material. (The same applies to the following examples and comparative examples)
- Example 10 to Example 18 non-aqueous electrolyte secondary batteries were obtained in the same manner as in Example 6 except that the mass ratio of inorganic particles to matrix resin (inorganic particles / matrix resin) was changed.
- Example 20 to Example 27 a nonaqueous electrolyte secondary battery was obtained in the same manner as in Example 19 except that at least one of the aspect ratio of the inorganic particles used for the filler and the orientation degree of the inorganic particles was changed. It was.
- Example 28 to Example 36 nonaqueous electrolyte secondary batteries were fabricated in the same manner as in Example 24 except that the mass ratio of inorganic particles to matrix resin (inorganic particles / matrix resin) was changed.
- Example 37 to Example 73 In Examples 37 to 73, the type of inorganic particles as the filler was changed as shown in Table 1 below. Moreover, the degree of orientation was adjusted by changing the viscosity of the non-aqueous electrolyte material as necessary. A nonaqueous electrolyte secondary battery was produced in the same manner as Example 1 except for the above.
- Comparative Example 1 a nonaqueous electrolyte containing no inorganic particles was prepared.
- a nonaqueous electrolyte secondary battery was produced in the same manner as Example 1 except for the above.
- Comparative Example 2 to Comparative Example 6 the type of inorganic particles as the filler was changed as shown in Table 1 below. Moreover, the degree of orientation was adjusted by changing the viscosity of the non-aqueous electrolyte material as necessary. A nonaqueous electrolyte secondary battery was produced in the same manner as Example 1 except for the above.
- each of the 50 particles existing in the region from each surface of at least one of the separators to 3 ⁇ m with respect to the reference line in the thickness direction of the particle with the normal of the electrode surface as the reference line Asked about.
- the angle of 70% or more (number basis) of the particles existing in the region is 0 ° to 30 °, the particles are aligned in parallel with the electrode surface (high degree of orientation, medium).
- the degree of orientation is high when the angle of 70% or more (number basis) of the particles existing in the region is 0 ° to 10 °.
- FIG. 14A shows a scanning electron microscope (SEM) photograph of the cross section of the nonaqueous electrolyte of the nonaqueous electrolyte secondary battery of Example 1.
- FIG. 14B shows a scanning electron micrograph of the nonaqueous electrolyte cross section of the nonaqueous electrolyte secondary battery of Comparative Example 2.
- FIG. 15A shows an enlarged SEM photograph of a part of FIG. 14A.
- FIG. 15B shows an enlarged SEM photograph of a part of FIG. 14B.
- the degree of orientation was also evaluated by X-ray diffraction measurement of the nonaqueous electrolyte.
- the peak intensity ratio diffraction peak intensity on the (006) plane / diffraction peak intensity on the (132) plane
- the degree of orientation is evaluated as low, and the peak intensity ratio is 10 or more.
- Those having a peak intensity ratio of 50 or more and 1,000 or less were evaluated as having a high degree of orientation.
- Examples 1 to 6 and Examples 10 to 16 have a high degree of orientation
- Examples 7 to 9 and Example 17 have a high degree of orientation
- Examples 18 and Comparative Example 4 have a low degree of orientation. This result was consistent with the evaluation of the degree of orientation by observation with a scanning microscope.
- FIG. 16 shows the X-ray diffraction pattern and peak intensity ratio (diffraction peak intensity on the (006) plane / diffraction peak intensity on the (132) plane) for Samples 1 to 3 below.
- line S ⁇ b> 1 indicates an X-ray diffraction pattern for sample 1
- line S ⁇ b> 2 indicates an X-ray diffraction pattern for sample 2
- line S ⁇ b> 3 indicates an X-ray diffraction pattern for sample 3.
- Example 3 An X-ray diffraction measurement was performed on the electrode on which the same nonaqueous electrolyte as in Example 1 was formed, and a peak for talc was extracted.
- the temperature at which the dehydration endothermic reaction of the filler material occurs was measured according to the following procedure.
- the produced battery was disassembled, and the electrode was washed with dimethyl carbonate (DMC).
- DMC dimethyl carbonate
- the nonaqueous electrolyte component (gel electrolyte component) applied to the electrode surface was separated.
- the solution from which this nonaqueous electrolyte component (gel electrolyte component) was separated was separated by a centrifuge to obtain a filler component.
- the obtained filler component was heated to 1000 ° C. at a rate of temperature increase of 10 ° C./min using a thermogravimetric analyzer (manufactured by SII, TG / DTA6300). (Decomposition temperature in Comparative Example 6) was obtained.
- the aspect ratio was measured as follows. Fifty particles (primary particles) in the nonaqueous electrolyte were randomly selected, and each selected particle was observed three-dimensionally with a scanning electron microscope. Thus, the aspect ratio of each inorganic particle from the short side of the flat shape (length of the shortest part in the thickness direction) and the length of the longest part (long side) of the part (surface) orthogonal to the thickness direction (Long side / short side) was obtained. And the aspect-ratio was calculated
- Capacity maintenance rate [%] (discharge capacity at 500th cycle / initial capacity) ⁇ 100 [%]
- Table 1 shows the measurement results.
- Comparative Example 1 and Comparative Example 6 it was found that the battery was in a dangerous state in the short circuit test. Further, Comparative Examples 2 to 5 were not in a dangerous state, but the temperature increase was larger than that of Examples 1 to 73, and the effect of improving the heat dissipation by the filler was small. Further, according to the comparison between Examples 1 to 18 and Examples 19 to 36, it was confirmed that the heat dissipation can be further improved by the filler being oriented parallel to the electrode surface.
- the battery structure is.
- the laminate film type the case where the electrode body has a wound structure or a laminated structure has been described as an example, but the present invention is not limited thereto.
- the electrolyte of the present technology can be similarly applied to a case of having another battery structure such as a cylindrical shape, a coin shape, a square shape, or a button shape.
- the separator 35 is a particle-containing insulating portion (provided on at least one main surface of both the main surfaces of the separator base material 35 a and the separator base material 35 a ( Particle-containing insulating layer) 35b.
- the example shown in FIG. 17 is a configuration in which the particle-containing insulating portions 35b are provided on both main surfaces of the separator base material 35a, and although not shown, the particle-containing insulating portions are provided on one main surface of the separator base material 35a. It is good also as a structure which provided 35b.
- the particle-containing insulating portion 35b is disposed between the positive electrode 33 and the negative electrode 34 together with the separator base material 35a, includes a filler 38 and a resin, and insulates the positive electrode 33 and the negative electrode 34 together with the separator base material 35a and the nonaqueous electrolyte 36.
- the separator base material 35a has the same configuration as that of the separator 35 of the first embodiment.
- the filler 38 and the resin are the same as those in the first embodiment.
- the non-aqueous electrolyte 36 may not contain the filler 38, and the non-aqueous electrolyte 36 may be a liquid electrolyte solution that does not contain a resin that holds the electrolyte solution.
- this technique can also take the following structures.
- the battery is a battery that is a substance that causes a dehydration endothermic reaction and has a flat shape with an aspect ratio of 2/1 or more.
- a temperature at which the dehydration endothermic reaction occurs is 160 ° C. or higher.
- the particle-containing insulating portion has thermal conductivity anisotropy, and the thermal conductivity in the direction perpendicular to the electrode surface is smaller than the thermal conductivity in the direction parallel to the electrode surface.
- a battery according to any one of the above. [5] The battery according to any one of [1] to [4], wherein the particles include inorganic particles. [6] The battery according to [5], wherein the inorganic particles are at least one of hydrate particles, metal hydroxide particles, and mineral particles.
- the hydrate salt is at least one selected from the group consisting of magnesium sulfate hydrate and calcium sulfate hydrate
- the metal hydroxide is at least one selected from the group consisting of boehmite, aluminum hydroxide, and magnesium hydroxide
- the minerals include talc, chrysotile, antigolite, lizardite, kaolinite, dickite, willemsite, granite, saponite, hectorite, sauconite, montmorillonite, hydridelite, nontrite, sericite, phlogopite, biocite, lepidite , At least one selected from the group consisting of margarite, clintnite, anandite, kukeite, sudite, clinochlore, chamosite, nimite, sepiolite, palygorskite, zeolite, attapulgite, hydrotalcite, bingelite, imogolite and allophane [ 6].
- the particles are talc particles;
- the peak intensity ratio ⁇ diffraction peak intensity of (006) plane / diffraction peak intensity of (132) plane ⁇ of the X-ray diffraction pattern of the particle-containing insulating portion is any of [1] to [7] of 10 or more and 1000 or less
- the particle-containing insulating portion further includes an electrolytic solution held in the resin.
- a separator The battery according to [10], wherein the particle-containing insulating portion is provided between the separator and at least one of the negative electrode and the positive electrode.
- the electrolytic solution includes an electrolyte salt and a nonaqueous solvent in which the electrolyte salt is dissolved.
- the separator substrate provided with the particle-containing insulating portion on at least one surface;
- the particle-containing insulating portion is disposed between the separator substrate and at least one of the negative electrode and the positive electrode.
- the particle is a substance that causes a dehydration endothermic reaction and has a flat shape with an aspect ratio of 2/1 or more.
- An electronic apparatus comprising the battery according to [1] and receiving power supply from the battery.
- An electric vehicle comprising: a control device that performs information processing related to vehicle control based on information related to the battery.
- a power storage device that has the battery according to [1] and supplies power to an electronic device connected to the battery.
- a power information control device that transmits and receives signals to and from other devices via a network, The power storage device according to [18], wherein charge / discharge control of the battery is performed based on information received by the power information control device.
- the electric power system which receives supply of electric power from the battery as described in [1], or supplies electric power to the said battery from a generator or an electric power network.
- Negative electrode current collector, 54B ... Negative electrode active material layer, 55 ... Separator, 56 ... Gel electrolyte layer, 57 ... Protective tape, 60 ... Exterior Member, 61 ... Adhesion film, 70 ... Laminated electrode body, 71 ... Positive Lead, 72 ... Negative electrode lead, 73 ... Positive electrode, 74 ... Negative electrode, 75 ... Separator, 76 ... Fixing member, 80 ... Cell, 81 ... Circuit board, 82a ... Top cover, 82b ... Bottom cover, 83 ... Hard laminate film, 84 ... notches, 85 ... soft laminate film, 86 ... recess, 87 ... adhesive film, 90 ... battery pack, 301 ... assembled battery, 301a ...
- Power consumption device 405a ... Refrigerator, 405b ... Air conditioning device, 405c ... Television receiver, 405d ... Bath, 406 ... Electric vehicle, 406a ... Electric car, 406b ... Hybrid car, 406c ... Electric bike, 407 ... Smart meter, 408 ... Power hub, 409 ... Power network, 410 ... control device, 411 ... sensor, 412 ... information network, 413 ... server, 500 ... hybrid vehicle, 501 ... engine, 502 ... Generator, 503 ... Electric power / driving force conversion device, 504a ... Driving wheel, 504b ... Driving wheel, 505a ... Wheel, 505b ... Wheel, 508 ... Battery, 509 ... Vehicle control device, 510 ... sensor, 511 ... charge port
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Abstract
Description
1.第1の実施の形態(非水電解質の例)
2.第2の実施の形態(電池の第1の例、第2の例)
3.第3の実施の形態(電池パックの第1の例、第2の例)
4.第4の実施の形態(電池パックの例)
5.第5の実施の形態(蓄電システム等の例)
6.他の実施の形態 (変形例)
なお、以下に説明する実施の形態等は本技術の好適な具体例であり、本技術の内容がこれらの実施の形態等に限定されるものではない。また、本明細書に記載された効果はあくまで例示であって限定されるものではなく、また例示した効果と異なる効果が存在することを否定するものではない。
[非水電解質の構成例]
本技術の第1の実施の形態による非水電解質(電解質)の構成例について説明する。図1は、本技術の非水電解質の一例の構成を示す模式的な断面図である。なお、図1は、非水電解質を電池に用いた場合の概略的な構成例を示す。
非水電解質36は、非水溶媒と、電解質塩と、樹脂(マトリックス樹脂)と、フィラー38とを含む。非水電解質36では、例えば、マトリックス樹脂に電解液(非水溶媒および電解質塩)が含浸および保持されている。非水電解質36は、例えば、フィラー38を含有し、電解液によりマトリックス樹脂が膨潤されることにより、ゲル状になっているゲル状のイオン伝導体である。また、非水電解質36は、フィラー38と樹脂とを含有し、且つ、正極33および負極34の間に配置され、正極33および負極34の間をセパレータ35と共に絶縁する粒子含有絶縁部(粒子含有絶縁層)である。なお、セパレータ35を省略した構成としてもよく、この場合、非水電解質36は、正極33および負極34間に配置され、正極33および負極34の間を単独で絶縁する粒子含有絶縁部となる。
非水溶媒としては、各種の高誘電率溶媒や低粘度溶媒を用いることができる。高誘電率溶媒としては、エチレンカーボネートとプロピレンカーボネートとを含むものを好適例として挙げることができるが、これに限定されるものではない。高誘電率溶媒としては、例えば、ブチレンカーボネート、ビニレンカーボネート、4-フルオロ-1,3-ジオキソラン-2-オン(フルオロエチレンカーボネート)、4-クロロ-1,3-ジオキソラン-2-オン(クロロエチレンカーボネート)、トリフルオロメチルエチレンカーボネート等の環状炭酸エステルを挙げることもできる。また、高誘電率溶媒として、環状炭酸エステルの代わりにまたはこれと併用して、γ-ブチロラクトンやγ-バレロラクトン等のラクトン、N-メチルピロリドン等のラクタム、N-メチルオキサゾリジノン等の環状カルバミン酸エステル、テトラメチレンスルホン等のスルホン化合物等も使用可能である。
電解質塩としては、非水溶媒に溶解ないしは分散してイオンを生ずるものであればよく、六フッ化リン酸リチウム(LiPF6)を好適に使用することができるが、これに限定されるものではないことは言うまでもない。例えば、四フッ化ホウ酸リチウム(LiBF4)、六フッ化ヒ酸リチウム(LiAsF6)、六フッ化アンチモン酸リチウム(LiSbF6)、過塩素酸リチウム(LiClO4)、四塩化アルミニウム酸リチウム(LiAlCl4)等の無機リチウム塩や、トリフルオロメタンスルホン酸リチウム(LiCF3SO3)、リチウムビス(トリフルオロメタンスルホン)イミド(LiN(CF3SO2)2)、リチウムビス(ペンタフルオロエタンスルホン)メチド(LiC(C2F5SO2)2)、リチウムトリス(トリフルオロメタンスルホン)メチド(LiC(CF3SO2)3)等のパーフルオロアルカンスルホン酸誘導体のリチウム塩等も使用可能であり、1種を単独でまたは2種以上を任意に混合して用いることも可能である。なお、このような電解質塩の含有量は、電解液の質量に対して、10質量%以上30質量%以下とすることが好ましい。10質量%未満では、十分な伝導度が得られないことがあり、30質量%を超えると、粘度が上昇し過ぎることがある。
マトリックス樹脂としては、電解液(非水溶媒および電解質塩)およびフィラー38を含浸ないしは保持し得るものであれば、特に限定されるものではない。例えば、マトリックス樹脂の構成成分としては、フッ化ビニリデンやヘキサフルオロプロピレン、ポリテトラフルオロエチレン等を含む重合体、即ち単独重合体、共重合体および多元共重合体が好ましい。具体的には、ポリフッ化ビニリデン(PVdF)、ポリフッ化ビニリデン-ヘキサフルオロプロピレン共重合体(PVdF-HFP)、ポリフッ化ビニリデン-ヘキサフルオロプロピレン-クロロトリフルオロエチレン共重合体(PVdF-HEP-CTFE)等を挙げることができる。なお、マトリックス樹脂には、非水溶媒や電解質塩を含浸ないしは保持して膨潤し、ゲル化ないしは非流動化するものがある。これにより電池において、非水電解質36の漏液を抑制することができる。
フィラー38としては、脱水吸熱反応が生じて水を生成する物質(脱水反応が生じる物質)であり、且つ、アスペクト比が2/1以上の扁平形状の無機粒子等の粒子を用いることができる。脱水吸熱反応が生じて水を生成する物質は、温度が上昇した場合に脱水吸熱反応によって吸熱し、温度の上昇を抑制する作用がある。粒子がアスペクト比2/1以上の扁平形状であることによって、電池内で安定して存在でき、且つ、電池反応に悪影響を与えることがなく、且つ、電気絶縁性および熱伝導性が良好である。
フィラー38は、電極面に平行に配向している状態となっていることが好ましい。フィラー38(扁平形状の粒子)が電極面に平行に配向している状態とは、非水電解質36中の複数個の扁平形状の粒子(フィラー38)の厚さ方向が、電極面の法線方向に平行になるような向きに、概ね揃っている状態を指す。なお、平行はほぼ平行を含む。
フィラー38(粒子)とマトリックス樹脂との含有比率(質量比:「粒子」/「マトリックス樹脂」)は、典型的には、例えば、1/1以上25/1以下であり、1/1以上5/1以下であることが好ましい。含有比率が1/1未満の場合、無機粒子を含有させた効果が少ない傾向にあり、含有比率が5/1を超えると、サイクル特性等の電池特性が低下する傾向にある。
以上説明した本技術の非水電解質は、これを備えた電池の電池特性の低下を抑制でき、且つ、内部発熱に対する放熱性を向上できる。なお、例えば、[背景技術]の欄で述べた特許文献1(特開平10-214640号公報)に記載の電池においては、ショートが発生するまでの強度(荷重)を高くすることができるものの、電極への電解液の含浸性が低下し易く、その結果、電池特性の低下を招くことがある。
本技術の第2の実施の形態による非水電解質電池(電池)について説明する。本技術の第2の実施の形態による非水電解質電池は、上述した第1の実施の形態による非水電解質を備えたラミネートフィルム型の非水電解質電池である。この非水電解質電池は、例えば充電および放電が可能な非水電解質二次電池であり、また、例えばリチウムイオン二次電池である。以下では、ラミネートフィルム型の非水電解質二次電池の2つの構成例(第1の例および第2の例)について説明する。
[非水電解質二次電池の構成]
非水電解質二次電池の第1の例について説明する。図2は、本技術の非水電解質二次電池の第1の例を示す分解斜視図である。図2に示すように、この二次電池は、正極リード(正極端子)31と負極リード(負極端子)32が取り付けられた巻回電極体30をフィルム状の外装部材40の内部に封入して構成されている。正極リード31および負極リード32は、外装部材40の内部から外部に向かって、例えば同一方向にそれぞれ導出されている。正極リード31および負極リード32は、例えばアルミニウム(Al)、銅(Cu)、ニッケル(Ni)またはステンレス等の金属材料によりそれぞれ構成される。
図3は、図2に示した巻回電極体30のI-I線に沿った模式的な断面図である。図3において、この巻回電極体30は、正極33と負極34とが非水電解質36およびセパレータ35を介して対向して位置し、巻回されているものであり、最外周部は保護テープ37により保護されている。なお、非水電解質36は上述した第1の実施の形態と同様である。すなわち、非水電解質36は、第1の実施の形態と同様の非水溶媒と、電解質塩と、マトリックス樹脂と、フィラー38(図示省略)を含む。
正極33は、例えば対向する一対の面を有する正極集電体33Aの両面または片面に、正極活物質層33Bが形成され、正極集電体33Aの両面または片面が正極活物質層33Bに被覆された構造を有している。正極集電体33Aには、長手方向における一方の端部に正極活物質層33Bが被覆されずに露出している部分があり、この露出部分に正極リード31が取り付けられている。
LirMIO2 ・・・(1)
LisMIIPO4・・・(2)
(一般式(1)および一般式(2)中、MIおよびMIIは1種類以上の遷移金属元素を示す。rおよびsの値は電池の充放電状態によって異なるが、通常0.05≦r≦1.10、0.05≦s≦1.10である。)
負極34は、正極33と同様に、例えば対向する一対の面を有する負極集電体34Aの両面または片面に負極活物質層34Bが設けられ、負極集電体34Aの両面または片面が負極活物質層34Bに被覆された構造を有している。負極集電体34Aには、長手方向における一方の端部に負極活物質層34Bが設けられず露出している部分があり、この露出部分に負極リード32が取り付けられている。
セパレータ35は、ポリプロピレン若しくはポリエチレン等のポリオレフィン系の合成樹脂から成る多孔質膜、またはセラミック製の不織布等の無機材料から成る多孔質膜等、イオン透過度が大きく、所定の機械的強度を有する絶縁性の薄膜から構成されている。なお、これらの多孔質膜を2種以上積層した構造としてもよい。特に、ポリオレフィン系の多孔質膜を含むものは、正極33と負極34との分離性に優れ、内部短絡や開回路電圧の低下をいっそう低減できるので好適である。
上述した非水電解質二次電池の製造方法の一例につき説明する。まず、正極33を作製する。例えば粒子状の正極活物質を用いる場合には、正極活物質と必要に応じて導電剤および結着剤とを混合して正極合剤を調製し、N‐メチル‐2‐ピロリドン等の分散媒に分散させて正極合剤スラリーを作製する。次いで、この正極合剤スラリーを正極集電体33Aに塗布し乾燥させ、圧縮成型して正極活物質層33Bを形成する。
以上説明した非水電解質二次電池では、典型的には、例えば、充電を行うと、正極活物質層33Bからリチウムイオンが放出され、非水電解質36を介して負極活物質層34Bにリチウムイオンが吸蔵される。放電を行うと、負極活物質層34Bからリチウムイオンが放出され、非水電解質36を介して正極活物質層33Bにリチウムイオンが吸蔵される。
上述の第1の例では、巻回電極体50が外装部材60で外装された非水電解質二次電池62について説明したが、図4A~図4Cに示すように、巻回電極体30の代わりに積層電極体70を用いてもよい。以下では、巻回電極体30の代わりに積層電極体70を用いた、本技術の第3の実施の形態による非水電解質二次電池(電池)の第2の例(非水電解質二次電池62)について説明する。
[電池パックの例]
本技術の第3の実施の形態による電池パックについて説明する。本技術の第3の実施の形態による電池パックは、第1の実施の形態と同様の非水電解質を備えたラミネートフィルム型電池の電池パックである。以下では、2つの構成例(第1の例および第2の例)について説明する。
第3の実施の形態のラミネートフィルム型電池の電池パックの第1の例について、図面を参照しながら説明する。なお、以下の電池パックの第1の例の説明では、巻回電極体を硬質ラミネートフィルムおよび軟質ラミネートフィルムで外装したものを電池セルと称し、電池セルに回路基板を接続し、トップカバーおよびリアカバーを嵌合したものを電池パックと称する。電池パックおよび電池セルにおいて、正極端子および負極端子の導出側をトップ部、トップ部と対向する側をボトム部、トップ部とボトム部とを除く二辺をサイド部と称する。また、サイド部-サイド部方向の長さを幅方向、トップ部-ボトム部方向の長さを高さと称する。
図5は、第3の実施の形態による電池パックの第1の例の一構成例を示す斜視図である。図6は、電池セルの構造を示す分解斜視図である。図7は、第3の実施の形態による電池セルの製造途中の状態を示す上面図および側面図である。図8は、電池セルにおける断面構造を示す断面図である。
図6および図7に示すように、この外装材は、巻回電極体50を収納するための凹部86が設けられた軟質ラミネートフィルム85と、この軟質ラミネートフィルム85上に凹部86を覆うようにして重ねられる硬質ラミネートフィルム83とからなる。
軟質ラミネートフィルム85は、第2の実施の形態における外装部材60と同様の構成を有している。特に、軟質ラミネートフィルム85は、金属層として軟質の金属材料、例えば焼きなまし処理済みのアルミニウム(JIS A8021P-O)または(JIS A8079P-O)等が用いられる点に特徴を有している。
軟質ラミネートフィルム85は、曲げた後の形状を維持し、外部からの変形に耐える機能を有する。このため、金属層として硬質の金属材料、例えばアルミニウム(Al)、ステンレス(SUS)、鉄(Fe)、銅(Cu)あるいはニッケル(Ni)等の金属材料が用いられ、特に焼きなまし処理なしの硬質アルミニウム(JIS A3003P-H18)または(JIS A3004P-H18)、もしくはオーステナイト系ステンレス(SUS304)等が用いられる点に特徴を有している。
巻回電極体50は、第2の実施の形態の巻回電極体30と同様の構成である。なお、巻回電極体50の代わりに、第2の実施の形態の第2の例で説明した積層電極体70を用いてもよい。
正極53およびセパレータ55の間、並びに、負極54およびセパレータ55の間に形成される非水電解質は、第1の実施の形態の非水電解質と同様である。
セパレータ55は、第2の実施の形態のセパレータ35と同様である。
回路基板81は、巻回電極体50の正極リード51および負極リード52が電気的に接続されるものである。回路基板81には、ヒューズ、熱感抵抗素子(Positive Temperature Coefficient;PTC素子)、サーミスタ等の温度保護素子を含む保護回路の他、電池パックを識別するためのID抵抗等がマウントされ、更に複数個(例えば3個)の接点部が形成されている。保護回路には、充放電制御FET(Field Effect Transistor;電界効果トランジスタ)、電池セル80の監視と充放電制御FETの制御を行うIC(Integrated Circuit)等が設けられている。
トップカバー82aは、電池セル80のトップ側開口に嵌合されるものであり、トップカバー82aの外周の一部または全部に沿って、トップ側開口に嵌合するための側壁が設けられている。電池セル80とトップカバー82aとは、トップカバー82aの側壁と、硬質ラミネートフィルム83の端部内面とが熱融着されて接着される。
ボトムカバー82bは、電池セル80のボトム側開口に嵌合されるものであり、ボトムカバー82bの外周の一部または全部に沿って、ボトム側開口に嵌合するための側壁が設けられている。電池セル80とボトムカバー82bとは、ボトムカバー82bの側壁と、硬質ラミネートフィルム83の端部内面とが熱融着されて接着される。
(電池セルの作製)
軟質ラミネートフィルム85の凹部86に巻回電極体50を収容し、凹部86を覆うように硬質ラミネートフィルム83が配置される。このとき、硬質ラミネートフィルム83の内側樹脂層と、軟質ラミネートフィルム85の内側樹脂層とが対向するように硬質ラミネートフィルム83と軟質ラミネートフィルム85とを配設する。この後、硬質ラミネートフィルム83および軟質ラミネートフィルム85を、凹部86の周縁に沿って封止する。封止は、図示しない金属製のヒータヘッドを用い、硬質ラミネートフィルム83の内側樹脂層と、軟質ラミネートフィルム85の内側樹脂層とを減圧しながら熱融着することにより行う。
続いて、電池セル80から導出された正極リード51と負極リード52とを回路基板81に接続した後、回路基板81を、トップカバー82aに収納し、トップカバー82aを電池セル80のトップ側開口に嵌合する。また、ボトムカバー82bを、電池セル80のボトム側開口に嵌合する。
第3の実施の形態によるラミネートフィルム型電池の電池パックの第2の例について説明する。この電池パックは、いわゆる簡易型の電池パック(ソフトパックとも称する)である。簡易型の電池パックは、電子機器に内蔵されるものであり、電池セルや保護回路等が絶縁テープ等で固定され、電池セルの一部が露出され、電子機機本体に接続されるコネクタ等の出力が設けられたものである。
図11は、本技術の第2の実施の形態による電池(以下、二次電池と適宜称する)を電池パックに適用した場合の回路構成例を示すブロック図である。電池パックは、組電池301、外装、充電制御スイッチ302aと、放電制御スイッチ303a、を備えるスイッチ部304、電流検出抵抗307、温度検出素子308、制御部310を備えている。
上述した本技術の第2の実施の形態による電池およびこれを用いた第3の実施の形態および第4の実施の形態による電池パックは、例えば電子機器や電動車両、蓄電装置等の機器に搭載または電力を供給するために使用することができる。
本技術の電池を用いた蓄電装置を住宅用の蓄電システムに適用した例について、図12を参照して説明する。例えば住宅401用の蓄電システム400においては、火力発電402a、原子力発電402b、水力発電402c等の集中型電力系統402から電力網409、情報網412、スマートメータ407、パワーハブ408等を介し、電力が蓄電装置403に供給される。これと共に、家庭内の発電装置404等の独立電源から電力が蓄電装置403に供給される。蓄電装置403に供給された電力が蓄電される。蓄電装置403を使用して、住宅401で使用する電力が給電される。住宅401に限らずビルに関しても同様の蓄電システムを使用できる。
本技術を車両用の蓄電システムに適用した例について、図13を参照して説明する。図13に、本技術が適用されるシリーズハイブリッドシステムを採用するハイブリッド車両の構成の一例を概略的に示す。シリーズハイブリッドシステムはエンジンで動かす発電機で発電された電力、あるいはそれをバッテリーに一旦貯めておいた電力を用いて、電力駆動力変換装置で走行する車である。
(正極の作製)
まず、正極活物質としてのリチウムコバルト複合酸化物(LiCoO2)91質量部と、導電剤としての黒鉛6質量部と、結着剤としてのポリフッ化ビニリデン(PVdF)10質量部とを均質に混合し、N-メチル-2-ピロリドン(NMP)に分散させて、正極合剤スラリーを得た。
次に、負極活物質としての人造黒鉛90質量部と、結着剤としてのPVdF10質量部とを均質に混合し、NMPに分散させて、負極合剤スラリーを得た。次いで、得られた負極合剤スラリーを、負極集電体となる厚み10μmの帯状銅箔の両面に均一に塗布し、乾燥して、負極活物質層を形成した。これを幅40mm、長さ650mmの形状に切断して、負極を作製し、更に負極端子を取り付けた。
また、非水電解質材料としては、非水電解液90質量部と、マトリックス樹脂としてのポリフッ化ビニリデン-ヘキサフルオロプロピレン共重合体(PVdF:HFP=93.1:6.9(質量比))10質量部と、フィラー(無機粒子)としての、タルク(Mg3Si4O10(OH)2)の粒子(アスペクト比(長辺/短辺)=400/1)10質量部とを混合し、更に粘度調整用溶媒としてジメチルカーボネートを添加して、粘度を50mPa・sに調整したものを用いた。
得られた正極および負極のそれぞれの両面に、得られた非水電解質材料を塗布して非水電解質層(ゲル状電解質層)を形成し、非水電解質層が形成された正極および負極を厚み12μmの微多孔性ポリエチレンフィルムからなるセパレータを介して積層して巻き取り、アルミニウムラミネートフィルムから成る外装部材内に封止して、実施例1の非水電解質二次電池を得た。
実施例2~実施例9では、フィラーに用いる無機粒子のアスペクト比および無機粒子の配向度の少なくともいずれかを変えたこと以外は、実施例1と同様にして、非水電解質二次電池を得た。
実施例10~実施例18では、無機粒子とマトリックス樹脂との質量比(無機粒子/マトリックス樹脂)を変えたこと以外は、実施例6と同様にして、非水電解質二次電池を得た。
フィラーとして、タルク粒子の代わりに、ベーマイト粒子(アスペクト比(長辺/短辺)=400/1)を用いたこと以外は、実施例1と同様にして、非水電解質二次電池を得た。
実施例20~実施例27では、フィラーに用いる無機粒子のアスペクト比および無機粒子の配向度の少なくともいずれかを変えたこと以外は、実施例19と同様にして、非水電解質二次電池を得た。
実施例28~実施例36では、無機粒子とマトリックス樹脂との質量比(無機粒子/マトリックス樹脂)を変えたこと以外は、実施例24と同様にして、非水電解質二次電池を作製した。
実施例37~実施例73では、フィラーとしての無機粒子の種類を下掲の表1に示すように変えた。また、必要に応じて、非水電解質材料の粘度を変えることにより配向度を調整した。以上のこと以外は、実施例1と同様にして、非水電解質二次電池を作製した。
比較例1では無機粒子を含まない非水電解質を調製した。以上のこと以外は、実施例1と同様にして、非水電解質二次電池を作製した。
比較例2~比較例6では、フィラーとしての無機粒子の種類を下掲の表1に示すように変えた。また、必要に応じて、非水電解質材料の粘度を変えることにより配向度を調整した。以上のこと以外は、実施例1と同様にして、非水電解質二次電池を作製した。
上述の実施例および比較例において、配向度は非水電解質電池の断面の一部を走査型顕微鏡にて観察することで評価した。
タルク(アスペクト比(長辺/短辺)=50/1)粉末を、サンプルホルダに載せただけの状態のものについて、X線回折測定を行った。
タルク(アスペクト比(長辺/短辺)=50/1)粉末を、サンプルホルダに載せた後、圧縮して配向があるように調整したものについて、X線回折測定を行った。
実施例1と同様の非水電解質が形成された電極について、X線回折測定を行い、タルクについてのピークを抽出した。
上述の実施例および比較例において、フィラー材料の脱水吸熱反応が生じる温度(脱水吸熱反応発生温度)の測定は以下の手順に従って行った。作製した電池を解体し、電極をジメチルカーボネート(DMC)で洗浄した。これによって電極表面に塗布された非水電解質成分(ゲル状電解質成分)を分離した。この非水電解質成分(ゲル状電解質成分)を分離した溶液を遠心分離機によって分離して、フィラー成分を得た。得られたフィラー成分を熱重量分析装置(SII社製、TG/DTA6300)を使用して、10℃/分の昇温速度で1000℃まで昇温し、減量の起こる温度より脱水吸熱反応発生温度(比較例6では分解温度)を得た。
上述の実施例および比較例において、アスペクト比を以下のように測定した。非水電解質中の50個の粒子(一次粒子)をランダムに選択して、選択した各粒子を走査型電子顕微鏡で、3次元的に観察した。これにより、扁平形状の短辺(厚さ方向の最短部分の長さ)と、厚さ方向と直交する部分(面)の最長部分の長さ(長辺)とから、各無機粒子のアスペクト比(長辺/短辺)を得た。そして、これらの平均値を算出することより、アスペクト比を求めた。
以上のようにして得られた各例の電池について下記の性能評価を行った。実施例1~実施例73および比較例1~比較例6の性能評価結果を表1に示す。
作製した各実施例および各比較例のラミネートフィルム型電池について、23℃の雰囲気下において1Cの充電電流で電池電圧4.2Vまで定電流充電を行った後、4.2Vにて定電圧充電を行い、充電電流が0.5mAとなった時点で充電を終了した。その後、1Cの放電電流で電池電圧3.0Vまで定電流放電を行い、このときの放電容量を測定して初回容量とした。なお、「1C」とは、理論容量を1時間で放電しきる電流値である。続いて、上述の充放電条件と同様の条件で500サイクルまで充放電を行い、500サイクル目の放電容量を測定した。下記の式から、容量維持率を算出した。
容量維持率[%]=(500サイクル目の放電容量/初回容量)×100[%]
作製した各実施例および各比較例のラミネートフィルム型電池について、電池外部にて正極および負極を電気的に短絡させ、ラミネートフィルム型電池の発熱温度の測定およびガス噴出の有無の確認を行った。
短絡時において、ラミネートフィルム型電池の発熱温度が100℃以下である場合は安全状態であると判断した。この場合、セパレータのシャットダウンやラミネートフィルム型電池内部での断線等により、電池は100℃以下の発熱を伴うものの、その後は電池が使用できない状態となって電池の温度が低下し、それ以上の危険性は生じない。なお、電池の最高温度が80℃以下であれば、セパレータのシャットダウンや電池内部での断線が生じないため、電池温度が低下した際には、電池が引き続き使用可能であるためより好ましい。
電池からガスが噴出した場合には、危険状態であると判断した。セパレータのシャットダウン、電池内部での断線等が生じても、正極が著しい過熱状態になった場合には正極が熱分解反応をおこし、電池内部からガスが噴出してしまう。
本技術は、上述した本技術の実施の形態に限定されるものでは無く、本技術の要旨を逸脱しない範囲内で様々な変形や応用が可能である。
正極および負極からなる電極と、
前記正極および前記負極間に設けられ、且つ、粒子および樹脂を含む粒子含有絶縁部と
を備え、
前記粒子は、脱水吸熱反応を生じる物質であり、且つ、アスペクト比が2/1以上の扁平形状を有する電池。
[2]
前記脱水吸熱反応が生じる温度は、160℃以上である[1]に記載の電池。
[3]
前記粒子は、前記電極面に平行に配向された[1]~[2]の何れかに記載の電池。
[4]
前記粒子含有絶縁部は、熱伝導異方性を有し、前記電極面に垂直な方向の熱伝導率が前記電極面に平行な方向の熱伝導率より小さい[1]~[3]の何れかに記載の電池。
[5]
前記粒子は、無機粒子を含む[1]~[4]の何れかに記載の電池。
[6]
前記無機粒子は、水和物の粒子、金属水酸化物の粒子および鉱物の粒子の少なくとも何れかである[5]に記載の電池。
[7]
前記水和物塩は、硫酸マグネシウム水和物および硫酸カルシウム水和物からなる群より選ばれた少なくとも1種であり、
前記金属水酸化物は、ベーマイト、水酸化アルミニウムおよび水酸化マグネシウムからなる群より選ばれた少なくとも1種であり、
前記鉱物は、タルク、クリソタイル、アンチゴライト、リザーダイト、カオリナイト、ディッカイト、ウィレムサイト、葉ろう石、サポナイト、ヘクトライト、ソーコナイト、モンモリロナイト、ハイデライト、ノントライト、セリサイト、フロゴパイト、バイオクタイト、レピドライト、マーガライト、クリントナイト、アナンダイト、クッケアイト、スドーアイト、クリノクロア、シャモサイト、ニマイト、セピオライト、パリゴルスカイト、ゼオライト、アタパルジャイト、ハイドロタルサイト、ビンゲライト、イモゴライトおよびアロフェンからなる群より選ばれた少なくとも1種である[6]に記載の電池。
[8]
前記粒子は、タルクの粒子であり、
前記粒子含有絶縁部のX線回折パターンのピーク強度比{(006)面の回折ピーク強度/(132)面の回折ピーク強度}は、10以上1000以下である[1]~[7]の何れかに記載の電池。
[9]
前記粒子と前記樹脂との質量比(粒子の質量/樹脂の質量)は、1/1以上5/1以下である[1]~[8]の何れかに記載の電池。
[10]
前記粒子含有絶縁部は、前記樹脂に保持された電解液をさらに含むものである[1]~[9]の何れかに記載の電池。
[11]
セパレータをさらに備え、
前記粒子含有絶縁部は、前記セパレータと、前記負極および前記正極の少なくとも何れか一の電極との間に設けられた[10]に記載の電池。
[12]
前記電解液は、電解質塩および該電解質塩が溶解された非水溶媒を含む[10]~[11]の何れかに記載の電池。
[13]
前記粒子含有絶縁部が少なくとも一方の面に設けられたセパレータ基材をさらに備え、
前記粒子含有絶縁部は、前記セパレータ基材と、前記負極および前記正極の少なくとも何れか一の電極との間に配置された[1]~[9]の何れかに記載の電池。
[14]
粒子と電解液と樹脂とを含み、
前記粒子は、脱水吸熱反応を生じる物質であり、且つ、アスペクト比が2/1以上の扁平形状を有する電解質。
[15]
[1]に記載の電池と、
前記電池を制御する制御部と、
前記電池を内包する外装と
を有する電池パック。
[16]
[1]に記載の電池を有し、前記電池から電力の供給を受ける電子機器。
[17]
[1]に記載の電池と、
前記電池から電力の供給を受けて車両の駆動力に変換する変換装置と、
前記電池に関する情報に基づいて車両制御に関する情報処理を行う制御装置と
を有する電動車両。
[18]
[1]に記載の電池を有し、前記電池に接続される電子機器に電力を供給する蓄電装置。
[19]
他の機器とネットワークを介して信号を送受信する電力情報制御装置を備え、
前記電力情報制御装置が受信した情報に基づき、前記電池の充放電制御を行う[18]に記載の蓄電装置。
[20]
[1]に記載の電池から電力の供給を受け、または、発電装置もしくは電力網から前記電池に電力が供給される電力システム。
Claims (20)
- 正極および負極からなる電極と、
前記正極および前記負極間に設けられ、且つ、粒子および樹脂を含む粒子含有絶縁部と
を備え、
前記粒子は、脱水吸熱反応を生じる物質であり、且つ、アスペクト比が2/1以上の扁平形状を有する電池。 - 前記脱水吸熱反応が生じる温度は、160℃以上である請求項1に記載の電池。
- 前記粒子は、前記電極面に平行に配向された請求項1に記載の電池。
- 前記粒子含有絶縁部は、熱伝導異方性を有し、前記電極面に垂直な方向の熱伝導率が前記電極面に平行な方向の熱伝導率より小さい請求項1に記載の電池。
- 前記粒子は、無機粒子を含む請求項1に記載の電池。
- 前記無機粒子は、水和物の粒子、金属水酸化物の粒子および鉱物の粒子の少なくとも何れかである請求項5に記載の電池。
- 前記水和物は、硫酸マグネシウム水和物および硫酸カルシウム水和物からなる群より選ばれた少なくとも1種であり、
前記金属水酸化物は、ベーマイト、水酸化アルミニウムおよび水酸化マグネシウムからなる群より選ばれた少なくとも1種であり、
前記鉱物は、タルク、クリソタイル、アンチゴライト、リザーダイト、カオリナイト、ディッカイト、ウィレムサイト、葉ろう石、サポナイト、ヘクトライト、ソーコナイト、モンモリロナイト、ハイデライト、ノントライト、セリサイト、フロゴパイト、バイオクタイト、レピドライト、マーガライト、クリントナイト、アナンダイト、クッケアイト、スドーアイト、クリノクロア、シャモサイト、ニマイト、セピオライト、パリゴルスカイト、ゼオライト、アタパルジャイト、ハイドロタルサイト、ビンゲライト、イモゴライトおよびアロフェンからなる群より選ばれた少なくとも1種である請求項6に記載の電池。 - 前記粒子は、タルクの粒子であり、
前記粒子含有絶縁部のX線回折パターンのピーク強度比{(006)面の回折ピーク強度/(132)面の回折ピーク強度}は、10以上1000以下である請求項1に記載の電池。 - 前記粒子と前記樹脂との質量比(粒子の質量/樹脂の質量)は、1/1以上5/1以下である請求項1に記載の電池。
- 前記粒子含有絶縁部は、前記樹脂に保持された電解液をさらに含むものである請求項1に記載の電池。
- セパレータをさらに備え、
前記粒子含有絶縁部は、前記セパレータと、前記負極および前記正極の少なくとも何れか一の電極との間に設けられた請求項10に記載の電池。 - 前記電解液は、電解質塩および該電解質塩が溶解された非水溶媒を含む請求項10に記載の電池。
- 前記粒子含有絶縁部が少なくとも一方の面に設けられたセパレータ基材をさらに備え、
前記粒子含有絶縁部は、前記セパレータ基材と、前記負極および前記正極の少なくとも何れか一の電極との間に配置された請求項1に記載の電池。 - 粒子と電解液と樹脂とを含み、
前記粒子は、脱水吸熱反応を生じる物質であり、且つ、アスペクト比が2/1以上の扁平形状を有する電解質。 - 請求項1に記載の電池と、
前記電池を制御する制御部と、
前記電池を内包する外装と
を有する電池パック。 - 請求項1に記載の電池を有し、前記電池から電力の供給を受ける電子機器。
- 請求項1に記載の電池と、
前記電池から電力の供給を受けて車両の駆動力に変換する変換装置と、
前記電池に関する情報に基づいて車両制御に関する情報処理を行う制御装置と
を有する電動車両。 - 請求項1に記載の電池を有し、前記電池に接続される電子機器に電力を供給する蓄電装置。
- 他の機器とネットワークを介して信号を送受信する電力情報制御装置を備え、
前記電力情報制御装置が受信した情報に基づき、前記電池の充放電制御を行う請求項18に記載の蓄電装置。 - 請求項1に記載の電池から電力の供給を受け、または、発電装置もしくは電力網から前記電池に電力が供給される電力システム。
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JP2018190722A (ja) * | 2017-04-28 | 2018-11-29 | 住友化学株式会社 | 非水電解液二次電池用絶縁性多孔質層 |
CN109686907A (zh) * | 2017-10-18 | 2019-04-26 | 丰田自动车株式会社 | 隔板、非水电解质二次电池、以及隔板的制造方法 |
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KR102107877B1 (ko) | 2020-05-07 |
CN105594054A (zh) | 2016-05-18 |
US9954212B2 (en) | 2018-04-24 |
US20160233474A1 (en) | 2016-08-11 |
KR20160065094A (ko) | 2016-06-08 |
JP6699171B2 (ja) | 2020-05-27 |
CN105594054B (zh) | 2019-05-14 |
JPWO2015049824A1 (ja) | 2017-03-09 |
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