WO2014148036A1 - セパレータ、電池、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
セパレータ、電池、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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- WO2014148036A1 WO2014148036A1 PCT/JP2014/001523 JP2014001523W WO2014148036A1 WO 2014148036 A1 WO2014148036 A1 WO 2014148036A1 JP 2014001523 W JP2014001523 W JP 2014001523W WO 2014148036 A1 WO2014148036 A1 WO 2014148036A1
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- battery
- separator
- negative electrode
- particles
- positive electrode
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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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- 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
- B60L58/00—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles
- B60L58/10—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling batteries
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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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
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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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/454—Separators, membranes or diaphragms characterised by the material having a layered structure comprising a non-fibrous layer and a fibrous layer superimposed on one another
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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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
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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 separators.
- the present technology also relates to a battery having a separator between electrodes, and a battery pack, an electronic device, an electric vehicle, a power storage device, and a power system using the battery.
- the separator shown in Patent Document 2 can be suitably used when a conventional carbon-based negative electrode active material is used.
- the calorific value at the time of short circuit is remarkably large, and the electrode and the separator are in direct contact with each other.
- the resin material constituting the separator is melted.
- a further short circuit may occur, or a large amount of heat may have already propagated to the positive electrode before thermal shutdown occurs before the shutdown becomes effective.
- a layer containing a large amount of inorganic particles such as alumina may be provided between the electrode and the separator.
- inorganic particles such as alumina have high thermal conductivity, and from the viewpoint of preventing the heat generated in the negative electrode from being transmitted to the positive electrode side, the presence of a high-density inorganic particle layer has an adverse effect.
- Patent Document 3 avoids the thermal decomposition reaction of the positive electrode by adding inorganic particles having high thermal conductivity to the electrolyte and promoting heat dissipation. However, the negative effect on the heat generated by the negative electrode is similarly reversed as the concentration increases.
- the present technology has been made in view of such problems of the prior art, and the object of the present technology is to provide a layer that absorbs heat generated in the electrode and does not transmit heat to the other electrode. It is in providing the separator which has.
- an object of the present technology is to provide a battery having a layer between a positive electrode and a negative electrode that absorbs heat generated by an electrode and prevents heat from being transmitted to another electrode.
- an object of the present technology is to provide a battery pack using a battery, an electronic device, an electric vehicle, a power storage device, and a power system.
- the separator of the present technology is formed on at least one surface of the base material and the base material, the heat capacity per unit area is 0.0001 J / Kcm 2 or more, and per unit volume.
- the separator of the present technology is formed on the base material and at least one surface side of the base material, at least a part thereof is included in the void in the base material, and the heat capacity per unit area is 0.0001 J / Kcm 2 or more. And a layer having a heat capacity per unit volume of 3.0 J / Kcm 3 or less, the layer containing particles and a resin material, the particles being boehmite, yttrium oxide, titanium oxide, magnesium oxide, oxide Zirconium, silicon oxide, zinc oxide, aluminum nitride, boron nitride, silicon nitride, titanium nitride, silicon carbide, boron carbide, barium titanate, strontium titanate, barium sulfate, porous aluminosilicate, layered silicate, Li 2 At least selected from O 4 , Li 3 PO 4 , LiF, aluminum hydroxide, graphite, carbon nanotube and diamond Both are characterized by containing one.
- the battery of the present technology includes an electrode body in which a positive electrode and a negative electrode face each other with a separator interposed therebetween, and an electrolyte.
- the separator is formed on at least one surface of a base material composed of a porous film and has a unit area.
- the layer contains particles and a resin material.
- Boehmite yttrium oxide, titanium oxide, magnesium oxide, zirconium oxide, silicon oxide, zinc oxide, aluminum nitride, boron nitride, silicon nitride, titanium nitride, silicon carbide, boron carbide, barium titanate, strontium titanate, barium sulfate, Porous aluminosilicate, layered silicate, Li 2 O 4 , Li 3 PO 4 , LiF, aluminum hydroxide, graphite, carbon It contains at least one selected from nanotubes and diamonds.
- the battery of the present technology includes an electrode body in which a positive electrode and a negative electrode face each other with a separator interposed therebetween, and an electrolyte.
- the separator is formed on at least one surface side of the base material and the base material, and at least a part of the base material A layer having a heat capacity per unit area of 0.0001 J / Kcm 2 or more and a heat capacity per unit volume of 3.0 J / Kcm 3 or less.
- the battery of the present technology includes a heat capacity per unit area provided between an electrode body in which a positive electrode and a negative electrode face each other via a separator, an electrolyte, and at least one of a positive electrode and a negative electrode that face each other through the separator and the separator.
- the layer contains particles and a resin material, and the particles are boehmite, Yttrium oxide, titanium oxide, magnesium oxide, zirconium oxide, silicon oxide, zinc oxide, aluminum nitride, boron nitride, silicon nitride, titanium nitride, silicon carbide, boron carbide, barium titanate, strontium titanate, barium sulfate, porous aluminosilicate Acid salt, layered silicate, Li 2 O 4 , Li 3 PO 4 , LiF, aluminum hydroxide, graphite, It contains at least one selected from carbon nanotubes and diamond.
- the battery pack, electronic device, electric vehicle, power storage device, and power system of the present technology include the above-described battery.
- the layer (with a heat capacity per unit area of 0.0001 J / Kcm 2 or more and a heat capacity per unit volume) between at least one of the positive electrode and the negative electrode and the separator or the base material or in the base material. Is a layer of 3.0 J / Kcm 3 or less. For this reason, for example, large heat generated in the negative electrode during short-circuit discharge can be absorbed by the above layer and not transmitted to the positive electrode. Even when the above layer is provided as a part of the separator, when the above layer is provided between at least one of the separator and the positive electrode and between the separator and the negative electrode or in the base material, the same effect is obtained. Have.
- FIG. 8 is a cross-sectional view illustrating a cross-sectional configuration along the line II of the spirally wound electrode body illustrated in FIG.
- FIG. 8 is a disassembled perspective view which shows the structure of the laminate film type nonaqueous electrolyte battery using a laminated electrode body.
- FIG. 8 is a disassembled perspective view which shows the structure of the battery pack of the laminate film type nonaqueous electrolyte battery which concerns on the 5th Embodiment of this technique.
- FIG. It is a disassembled perspective view which shows the structure of the battery cell of the battery pack shown in FIG. It is an expanded view which shows the structure of the battery cell of the battery pack shown in FIG. It is sectional drawing which shows the structure of the battery cell of the battery pack shown in FIG. It is a block diagram which shows the circuit structural example of the battery pack by embodiment of this technique. It is the schematic which shows the example applied to the electrical storage system for houses using the nonaqueous electrolyte battery of this technique. It is a schematic diagram showing roughly an example of composition of a hybrid vehicle which adopts a series hybrid system to which this art is applied.
- the separator which concerns on 1st Embodiment forms the heat absorption layer in the at least one surface of a base material.
- the separator of the present technology will be described in detail.
- the separator 1 according to the first embodiment includes a base material 2 made of a porous film and heat formed on at least one surface of the base material 2.
- An absorption layer 3. The separator 1 separates the positive electrode and the negative electrode in the battery, prevents a short circuit of current due to contact between the two electrodes, and is impregnated with a nonaqueous electrolyte.
- the heat absorption layer 3 of the separator 1 has an endothermic effect that absorbs heat generated in one electrode, and has a heat insulating effect that prevents the heat from being transmitted to the other electrode.
- the separator 1 of the present technology exhibits a particularly remarkable effect when applied to a battery in which a metal material or a metal alloy material is used as a negative electrode active material.
- a negative electrode in which a metal material or a metal alloy material is used as the negative electrode active material intense heat generation is likely to occur during short circuit discharge. Therefore, the separator 1 of the present technology exerts a remarkable effect of suppressing the thermal decomposition reaction of the positive electrode particularly in a battery using a metal-based material or a metal alloy-based material that easily generates intense heat as a negative electrode active material.
- FIG. 1 is an example of the separator 1 in which the heat absorption layer 3 is formed on both surfaces of the base material 2.
- the separator 1 may be one in which the heat absorption layer 3 is formed on either the positive electrode-facing side surface or the negative electrode-facing side surface of the substrate 2.
- the substrate 2 is a porous film composed of an insulating film having a high ion permeability and a predetermined mechanical strength.
- the separator 1 When the separator 1 is applied to a nonaqueous electrolyte battery, the nonaqueous electrolyte is held in the pores of the substrate 2.
- the base material 2 While the base material 2 has a predetermined mechanical strength as a main part of the separator 1, the base material 2 has a high resistance to a non-aqueous electrolyte, a low reactivity, and a property of being difficult to expand. Further, when used for an electrode body having a wound structure, flexibility is also required.
- a polyolefin resin such as polypropylene or polyethylene, an acrylic resin, a styrene resin, a polyester resin, or a nylon resin is preferably used as the resin material constituting the base material 2.
- polyethylene such as low density polyethylene, high density polyethylene and linear polyethylene, or their low molecular weight wax content, or polyolefin resin such as polypropylene is suitable because it has an appropriate melting temperature and is easily available.
- Those containing a porous membrane made of a polyolefin resin are excellent in separability between the positive electrode and the negative electrode, and can further reduce the decrease in internal short circuit.
- the thickness of the base material 2 can be arbitrarily set as long as it is equal to or greater than a thickness capable of maintaining a necessary strength.
- the base material 2 provides insulation between the positive electrode and the negative electrode, prevents a short circuit and the like, and has ion permeability for suitably performing a battery reaction via the separator 1, and in the battery reaction in the battery. It is preferable to set the thickness so that the volume efficiency of the contributing active material layer can be as high as possible.
- the thickness of the substrate 2 is preferably 7 ⁇ m or more and 20 ⁇ m or less.
- the porosity of the substrate 2 is preferably 25% or more and 80% or less, and more preferably 25% or more and 40% or less in order to obtain the above-described ion permeability.
- the thickness of the base material 2 is designed to be thin by the thickness of the heat absorption layer 3, and the separator 1 as a whole has a thickness equivalent to that of a single layer separator. It is common to do. For this reason, the strength of the separator 1 is highly dependent on the strength of the base material 2, and the base material 2 requires a certain strength or more.
- the base material 2 that can be used in the present technology can be roughly classified into, for example, a microporous film, a nonwoven fabric, and paper as follows.
- the microporous film is a material in which a material such as a resin is thinly stretched and has a porous structure.
- the microporous membrane is obtained by molding a material such as a resin by a stretch opening method or a phase separation method.
- a stretch opening method first, a molten polymer is extruded from a T die or a circular die, and further subjected to heat treatment to form a crystal structure with high regularity. Thereafter, stretching at a low temperature and then at a high temperature are performed to separate the crystal interface to form a gap between lamellas, thereby forming a porous structure.
- phase separation method a uniform solution prepared by mixing a polymer and a solvent at a high temperature is formed into a film by a T-die method, an inflation method, or the like, and then the solvent is extracted with another volatile solvent, whereby a microporous membrane is obtained. Can be obtained.
- the manufacturing method of a microporous film is not limited to these, The method proposed conventionally can be used widely.
- Nonwoven fabric is a structure made by bonding or entanglement between fibers, or by bonding and entanglement, without mechanically or chemically, or using a solvent, or a combination thereof, without weaving or knitting the fibers, This refers to the paper excluding paper described below. Most materials that can be processed into fibers can be used as the raw material of the nonwoven fabric, and by adjusting the shape such as fiber length and thickness, it is possible to provide functions according to the purpose and application.
- the method for producing a nonwoven fabric typically has two stages: a process of forming a fiber accumulation layer called a fleece, and a bonding process of bonding fleece fibers.
- a dry method a wet method, a spun bond method, a melt blow method, or the like can be used as a process for forming the fleece.
- a bonding step for bonding the fibers of the fleece a thermal bond method, a chemical bond method, a needle punch method, a spunlace method (a hydroentanglement method), a stitch bond method, a steam jet method, or the like can be used as a bonding step for bonding the fibers of the fleece.
- a thermal bond method a chemical bond method, a needle punch method, a spunlace method (a hydroentanglement method), a stitch bond method, a steam jet method, or the like can be used as a thermal bond method, a chemical bond method, a needle punch method, a spunlace method (a hydroentanglement method), a stitch bond method, a steam jet method, or the like can be used as a thermal bond method, a chemical bond method, a needle punch method, a spunlace method (a hydroentanglement method), a stitch
- nonwoven fabric examples include a polyethylene terephthalate permeable membrane (polyethylene terephthalate nonwoven fabric) using polyethylene terephthalate (PET) fibers.
- PET polyethylene terephthalate
- the air permeable film refers to a film having air permeability.
- examples of the nonwoven fabric include aramid fibers, glass fibers, cellulose fibers, polyolefin fibers, nylon fibers, and the like.
- the nonwoven fabric may use two or more kinds of fibers.
- Paper refers to paper in a narrow sense, for example, paper made using pulp. Pulp refers to a collection of plant fibers extracted from wood or other plants by mechanical or chemical treatment. Mixed paper made by mixing materials other than pulp (for example, minerals such as talc) is also included in the paper. As the paper, a cellulose permeable membrane made from cellulose pulp can be used. In addition, when distinguishing the wet nonwoven fabric and paper using a wet method, it distinguishes according to the definition of ISO 9092. That is, when the ratio of length to diameter (aspect ratio) is 300 or more and the mass ratio is 50% or more, or the density is 0.4 g / cc or less, the ratio of length to diameter is 300 or more. The fiber having a mass ratio of 30% or more is defined as a wet nonwoven fabric, and the other fibers are distinguished from paper.
- the porosity of the base material 2 may be more than 40%.
- the effect of the heat absorption layer 3 can be improved as compared with the case where the heat absorption layer 3 is formed only on the surface of the base material 2. Since it can exhibit more effectively, it is preferable.
- the heat absorption layer 3 is a layer formed on at least one surface of the substrate 2 and has a function of mainly absorbing heat generated in the negative electrode and preventing the heat generated in the negative electrode from being transmitted to the positive electrode. It is a quality layer.
- the heat absorption layer 3 contains a resin material having heat resistance and particles such as solid particles such as inorganic particles and organic particles that function as heat absorption particles having excellent heat resistance and oxidation resistance.
- the heat absorbing layer 3 is preferably made to have particles dispersed therein for the purpose of making it difficult to transmit heat.
- dispersion refers to a state where particles or secondary particle groups are scattered without being connected, but a part of the particles or secondary particle groups are connected. There may be. That is, it is preferable that the heat absorbing layer 3 as a whole is in a state where particles are dispersed.
- the heat absorption layer 3 may be formed not only on at least one surface of the base material 2 but also on a gap in the base material 2 in addition to at least one surface of the base material 2. Further, the heat absorption layer 3 may be formed only in the voids in the base material 2. That is, the heat absorption layer 3 at least partially contained in the voids in the base material 2 may be formed on one surface side or the other surface side of the base material 2, and one surface of the base material 2. It may be formed on the side and the other surface side.
- the heat absorption layer 3 is formed on one surface of the substrate 2.
- the heat absorption layer 3 is formed from the inner region to the outer region of one surface of the substrate 2, or the heat absorption layer 3 is formed from one surface of the substrate 2 to the inner region of one surface of the substrate.
- the heat absorption layer 3 is formed in a gap in the substrate 2 in a region inside one surface of the substrate 2.
- the heat absorption layer 3 is formed from the region inside the one surface of the base material 2 to the region outside the one surface of the base material 2,
- the heat absorption layer 3 formed in the region and the heat absorption layer 3 formed outside the one surface of the base material 2 are continuously connected, one surface of the base material 2
- the heat absorption layer 3 formed in the inner region of the substrate and the heat absorption layer 3 formed on the outer side of one surface of the substrate 2 are not connected to each other.
- the heat absorption layer 3 is formed on the other surface of the base material 2.
- the heat absorbing layer 3 is formed from the inner region to the outer region of the other surface of the substrate 2, or the heat absorbing layer 3 is formed from the other surface of the substrate 2 to the inner region of the other surface of the substrate.
- the heat absorption layer 3 is formed in the space
- the heat absorption layer 3 is formed from a region inside the other surface of the base material 2 to a region outside the other surface of the base material 2,
- the heat absorption layer 3 formed in the region and the heat absorption layer 3 formed outside the other surface of the substrate 2 are continuously connected to each other, the other surface of the substrate 2 is formed.
- the case where the heat absorption layer 3 formed in the inner region of the substrate and the heat absorption layer 3 formed on the outer side of the other surface of the substrate 2 are not connected to each other can be mentioned.
- FIG. 2 is a secondary electron image obtained by a scanning electron microscope (SEM) showing the structure of the heat absorption layer 3.
- the heat absorption layer 3 preferably has a three-dimensional network structure in which the resin material constituting the heat absorption layer 3 is fibrillated and the fibrils are continuously connected to each other. The particles can be maintained in a dispersed state without being connected to each other by being supported on the resin material having the three-dimensional network structure.
- the heat-absorbing layer 3 in order to sufficiently absorb the heat generated at the negative electrode, the heat capacity per unit area is the 0.0001J / Kcm 2 or more, that are 0.0003J / Kcm 2 or more More preferred.
- the heat capacity per area is represented by the product of the mass of particles per unit area and the specific heat of the particles.
- the heat capacity per area is calculated based on the mass of particles and specific heat existing on both surfaces of the base material 2 in a unit area.
- the non-aqueous electrolyte retained in the heat absorption layer 3 also has a heat capacity, but may be dissipated from the heat absorption layer 3 due to gas generation due to abnormal heat generation. For this reason, in the present technology, the heat capacity of the endothermic particles alone is defined as the heat capacity per area of the heat absorption layer 3.
- the heat-absorbing layer 3 in order to suppress convey the heat generated at the negative electrode to the positive electrode, the heat capacity per volume is the 3.0 J / Kcm 3 or less, more it is a 2.5 J / Kcm 3 or less preferable.
- the heat capacity per volume is represented by the product of the filling rate of particles in a unit volume, the true density, and the specific heat, and is proportional to the packing density of particles on the substrate 2.
- a heat capacity of 3.0 J / Kcm 3 or less per volume of the heat absorption layer 3 is a physical property when the separator 1 is formed. That is, when charging and discharging are performed after application to a nonaqueous electrolyte battery, the heat absorption layer 3 is crushed according to the expansion of the electrode and the like, and the heat capacity per volume increases.
- the separator 1 having the heat absorption layer 3 with a heat capacity of 3.0 J / Kcm 3 per volume and a thickness of 15 ⁇ m is used, it is generally after the first charge of the nonaqueous electrolyte battery, although it depends on the configuration of the heat absorption layer 3.
- the heat capacity per volume of the heat absorption layer 3 is about 3.2 J / Kcm 3 . Further, as the charge / discharge of the nonaqueous electrolyte battery progresses, the heat absorption layer 3 is crushed, and after 500 cycles of charge / discharge, the heat capacity per volume of the heat absorption layer 3 is about 3.8 J / Kcm 3 . In general, non-aqueous electrolyte batteries are shipped after being charged for the first time. Propagation of heat between electrodes can be suppressed by setting the heat capacity per volume of the heat absorption layer 3 of the separator 1 to 3.2 J / Kcm 3 or less at the time of shipment.
- the heat absorption layer 3 having a heat capacity per volume of 3.0 J / Kcm 3 or less is formed when the separator 1 is formed.
- the heat capacity per volume at the first charge shipment time
- the heat capacity per volume at the first charge shipment time
- the separator 1 is compressed as the cycle progresses, if the heat capacity per volume of the heat absorption layer 3 is in the range of 3.8 J / Kcm 3 or less, the “increase in heat conduction amount per area accompanying the cycle progress” "And” decrease in the amount of heat generated per area at the time of short circuit "are offset.
- the heat absorption layer is compressed and the heat capacity per volume increases, and the heat conduction per area also increases. This is because the output (current) decreases due to the increase, and the heat generation amount per area decreases. For this reason, the safety of the entire battery is maintained.
- a substance having a large heat capacity often has a high thermal conductivity, and if it is closely packed, heat from the negative electrode may be efficiently transmitted to the positive electrode.
- the endothermic particles need to be dispersed sparsely in the heat absorption layer 3 to reduce the heat capacity per volume, and the endothermic particles need to be dispersed without being connected to each other.
- the heat absorption layer 3 When the heat absorption layer 3 is provided on the side surface of the substrate 2 facing the negative electrode, the temperature rise in the vicinity of the separator 1 becomes moderate, and the time until the substrate 2 is melted after being shut down can be lengthened. For this reason, discharge reaction can be suppressed and heat generation can be suppressed.
- a layer having a flat surface and excellent heat resistance and oxidation resistance may be provided on the positive electrode facing side surface.
- the full charge voltage of the battery is set to 4.25 V or higher, which is higher than before, the vicinity of the positive electrode may be in an oxidizing atmosphere during full charge. For this reason, the positive electrode facing side surface may be oxidized and deteriorated.
- a layer containing a resin material having particularly excellent properties with respect to heat resistance and oxidation resistance may be formed.
- the heat absorption layer 3 is provided on the side of the base 2 facing the positive electrode, even if the base 2 is melted, the particles maintain insulation between the positive and negative electrodes, and The heat generated in the negative electrode can be absorbed and the heat transfer to the positive electrode can be suppressed. For this reason, the time margin until the nonaqueous electrolyte solution at the interface between the negative electrode and the separator 1 evaporates and the discharge reaction stops can be created.
- the separator 1 in which the heat absorption layer 3 was provided on both surfaces of the base material 2 can obtain both functions when the heat absorption layer 3 is provided on the negative electrode facing side surface and the positive electrode facing side surface of the base material 2. Therefore, it is particularly preferable.
- the surface of the heat absorption layer 3 may be smooth or may have an uneven shape.
- the heat absorption layer 3 can have a configuration in which particles are sparsely dispersed as a whole of the heat absorption layer 3 by adjusting the thickness.
- the heat absorption layer 3 can also have a sparse configuration by making the surface of the heat absorption layer 3 uneven.
- the convex portions of the heat absorption layer 3 come into contact with the positive electrode and the negative electrode, respectively, and the distance between the positive electrode and the negative electrode can be maintained.
- the convex portions of the heat absorption layer 3 have a heat absorption function and a heat insulation function between the positive electrode and the negative electrode without being connected to each other.
- Examples of the concavo-convex shape on the surface of the heat absorbing layer 3 include shapes such as a mottled shape shown in FIG. 3A, a lattice shape shown in FIG. 3B, a dot shape shown in FIG. 3C, and a pinhole shape shown in FIG.
- Examples of the resin material constituting the heat absorption layer 3 include fluorine-containing resins such as polyvinylidene fluoride and polytetrafluoroethylene, fluorine-containing rubbers such as vinylidene fluoride-tetrafluoroethylene copolymer and ethylene-tetrafluoroethylene copolymer.
- fluorine-containing resins such as polyvinylidene fluoride and polytetrafluoroethylene
- fluorine-containing rubbers such as vinylidene fluoride-tetrafluoroethylene copolymer and ethylene-tetrafluoroethylene copolymer.
- a material having a specific heat of 0.5 J / gK or more as particles such as solid particles such as inorganic particles and organic particles constituting the heat absorption layer 3. This is because the endothermic effect is increased.
- the amount (mass) of particles necessary for obtaining a heat capacity per predetermined area can be reduced, the amount (mass) of the resin material supporting the particles can also be reduced.
- a material having a melting point of 1000 ° C. or higher This is because the heat resistance can be increased.
- metal oxides examples include metal oxides, metal oxide hydrates, metal hydroxides, metal nitrides, metal carbides, and metal sulfides that are electrically insulating inorganic particles.
- the metal oxide or metal oxide hydrate include aluminum oxide (alumina, Al 2 O 3 ), boehmite (Al 2 O 3 H 2 O or AlOOH), magnesium oxide (magnesia, MgO), titanium oxide (titania, TiO 2 ), zirconium oxide (zirconia, ZrO 2 ), silicon oxide (silica, SiO 2 ), yttrium oxide (yttria, Y 2 O 3 ), zinc oxide (ZnO), or the like can be suitably used.
- silicon nitride (Si 3 N 4 ), aluminum nitride (AlN), boron nitride (BN), titanium nitride (TiN), or the like can be preferably used.
- metal carbide silicon carbide (SiC) or boron carbide (B 4 C) can be suitably used.
- metal sulfide barium sulfate (BaSO 4 ) or the like can be suitably used.
- metal hydroxide aluminum hydroxide (Al (OH) 3 ) or the like can be used.
- zeolite M 2 / n O ⁇ Al 2 O 3 ⁇ xSiO 2 ⁇ yH 2 O, M represents a metal element, x ⁇ 2, y ⁇ 0 ) porous aluminosilicates such as, talc (Mg 3 Si 4 O Layered silicates such as 10 (OH) 2 ), minerals such as barium titanate (BaTiO 3 ) or strontium titanate (SrTiO 3 ) may be used. It may also be used Li 2 O 4, Li 3 PO 4, lithium compound such as LiF. Carbon materials such as graphite, carbon nanotubes, and diamond may be used. Among these, alumina, boehmite, talc, titania (particularly those having a rutile structure), silica or magnesia are preferably used, and alumina or boehmite is more preferably used.
- the inorganic particles may be used alone or in combination of two or more.
- the inorganic particles also have oxidation resistance.
- the inorganic particles have strong resistance to an oxidizing environment in the vicinity of the positive electrode during charging.
- the shape of the inorganic particles is not particularly limited, and any of a spherical shape, a fiber shape, a needle shape, a scale shape, a plate shape, a random shape, and the like can be used.
- Materials constituting the organic particles include fluorine-containing resins such as polyvinylidene fluoride and polytetrafluoroethylene, fluorine-containing rubbers such as vinylidene fluoride-tetrafluoroethylene copolymer and ethylene-tetrafluoroethylene copolymer, styrene Butadiene copolymer or its hydride, acrylonitrile-butadiene copolymer or its hydride, acrylonitrile-butadiene-styrene copolymer or its hydride, methacrylic acid ester-acrylic acid ester copolymer, styrene-acrylic acid ester copolymer Polymer, acrylonitrile-acrylic acid ester copolymer, rubber such as ethylene propylene rubber, polyvinyl alcohol, polyvinyl acetate, ethyl cellulose, methyl cellulose, hydroxyethyl cellulose, carboxymethyl Cellulose derivatives such as
- the shape of the organic particles is not particularly limited, and any of a spherical shape, a fiber shape, a needle shape, a scale shape, a plate shape, a random shape, and the like can be used.
- particles having anisotropy such as needle shape, plate shape, and scale shape. Since the heat absorption layer 3 is formed by coating on the surface of the separator or electrode, the particles having anisotropy are in a direction parallel to the surface of the separator or the electrode that is the coating direction (the plane direction). The longest part of the particles (referred to as the major axis) tends to be oriented. For example, a needle-like long axis or a plate-like plane is oriented in the plane direction. For this reason, although it is easy to connect particles in a plane direction, it becomes difficult to connect particles in the perpendicular direction (direction perpendicular to the plane direction).
- the heat generated from the negative electrode is easily dispersed uniformly in the plane in the plane direction, but is less likely to be dispersed in the direction perpendicular to the plane direction.
- the heat insulation of the transmitted heat can be further improved.
- the particles having anisotropy for example, since the heat insulation can be further improved, for example, the length of the longest part of the particle (referred to as the major axis) and the shortest part of the particle in the direction perpendicular to the major axis (the minor axis) 3) or more (the length of the long axis (the length of the longest part of the particle) / the length of the short axis (the length of the shortest part of the particle))))
- a particle having a shape of is preferred.
- the particles preferably have an average primary particle size of several ⁇ m or less.
- the average particle size of the primary particles is preferably 1.0 ⁇ m or less, and more preferably 0.3 ⁇ m or more and 0.8 ⁇ m or less.
- Primary particles such as .01 ⁇ m or more and 0.10 ⁇ m or less may be combined.
- the average particle size of such primary particles can be measured by a method of analyzing a photograph obtained with an electron microscope with a particle size measuring instrument.
- the separator When the average particle size of the primary particles of the particles exceeds 1.0 ⁇ m, the separator becomes brittle and the coated surface may become rough.
- the heat-absorbing layer 3 containing particles is formed on the base material 2 by coating, if the primary particles of the particles are too large, a coating surface such as a portion where the coating liquid containing the particles is not applied is generated. May be rough.
- the particles having a large average particle diameter are mixed with the primary particles having an average particle diameter of 0.3 ⁇ m or more and 0.8 ⁇ m and used, the drop of the concavo-convex shape can be increased. The problem that the work surface becomes rough can be taken in reverse.
- the content of the particles is small outside the above range, the thickness of the heat absorption layer 3 necessary for obtaining a predetermined heat capacity is increased, which is not preferable from the viewpoint of volume efficiency.
- grains outside the said range the amount of resin materials which carry
- the gel electrolyte when a gel electrolyte (gel electrolyte) is used as the non-aqueous electrolyte, the gel electrolyte has a certain strength, and therefore has a role of reinforcing the heat absorption layer 3. For this reason, when the gel electrolyte is provided, the content of the particles is not limited to the above range. If the resin material of the heat absorption layer 3 and the resin material of the gel electrolyte are of the same type, Including the electrolyte resin material, the particles may be 50% by mass or more, and preferably 60% by mass or less and 95% by mass or less.
- the heat absorbing layer 3 preferably has a thickness of 1.0 ⁇ m or more. When the thickness is less than 1.0 ⁇ m, sufficient tear strength cannot be obtained, and the effect of forming the heat absorption layer 3 is reduced. Moreover, the heat absorption layer 3 has a higher tear strength as the thickness increases, but the volumetric efficiency of the battery decreases. For this reason, it is preferable to select the thickness as required.
- the heat absorption layer 3 preferably has a porosity equal to or higher than the porosity of the base material 2 so as not to hinder the ion permeation function, the nonaqueous electrolyte retention function, and the like of the base material 2.
- the porosity is 95% or less.
- the porosity of the heat absorption layer 3 is preferably 45% or more and 95% or less, more preferably 59% or more and 93% or less, and further preferably 65% or more and 90% or less. preferable.
- the porosity of the heat absorption layer 3 When the porosity of the heat absorption layer 3 is small outside the above range, the ion permeability of the heat absorption layer 3 is lowered and the heat insulation effect between the electrodes of the present technology is reduced. Moreover, when the porosity of the heat absorption layer 3 is large outside the above range, the strength of the heat absorption layer 3 is lowered.
- Examples of the method for transferring the resin solution include a method of applying the resin solution to the surface of a roller or the like having an uneven shape on the surface and transferring the resin solution to the surface of the substrate 2.
- the surface shape of a roller or the like for transferring a resin solution having an uneven shape on the surface can be various shapes as shown in FIG.
- the base material 2 coated with the resin solution is immersed in a water bath to phase separate the resin solution, and the heat absorption layer 3 is formed.
- the resin solution applied to the surface of the substrate 2 is brought into contact with water, which is a poor solvent for the resin material dissolved in the resin solution, and a good solvent for the dispersion solvent for dissolving the resin material, and finally Dry with hot air.
- the separator 1 in which the heat absorption layer 3 made of a resin material having a three-dimensional network structure in which particles are supported on the surface of the substrate 2 can be obtained.
- the heat absorption layer 3 is formed by a rapid poor solvent-induced phase separation phenomenon, and the heat absorption layer 3 has a structure in which a skeleton made of a resin material is connected in a fine three-dimensional network. That is, by dissolving the resin material and bringing the resin solution containing the particles into contact with a solvent such as water that is a poor solvent for the resin material and a good solvent for the dispersion solvent that dissolves the resin material. Solvent exchange occurs. As a result, rapid (high speed) phase separation accompanied by spinodal decomposition occurs, and the resin material has a unique three-dimensional network structure.
- the heat absorption layer 3 produced in this way forms a unique porous structure by utilizing a rapid poor solvent-induced phase separation phenomenon accompanied by spinodal decomposition by a poor solvent. Furthermore, this structure makes it possible to achieve excellent nonaqueous electrolyte impregnation and ionic conductivity.
- the heat absorption layer 3 of the present technology in order to make the heat absorption layer 3 sparse and to have a heat capacity per volume of 3.0 J / Kcm 3 or less, in the first manufacturing method, the following Various adjustments can be made.
- the heat absorption layer 3 which has an uneven
- the speed of phase separation can be adjusted, for example, by adding a small amount of a dispersion solvent such as N-methyl-2-pyrrolidone to a solvent such as water that is a good solvent for the dispersion solvent used during phase separation.
- a dispersion solvent such as N-methyl-2-pyrrolidone
- water such as water that is a good solvent for the dispersion solvent used during phase separation.
- the greater the amount of N-methyl-2-pyrrolidone mixed in water the slower the phase separation, and the most rapid phase separation occurs when phase separation is performed using only water.
- the heat absorption layer 3 after completion can be made into a sparser state, so that the speed
- the dispersion solvent used for the resin solution any solvent that can dissolve the resin material of the present technology can be used.
- the dispersion solvent include N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, toluene, acetonitrile, and the like. From the viewpoint of solubility and high dispersibility, N-methyl is used. It is preferable to use -2-pyrrolidone.
- the base material 2 coated with the resin solution is dried by a method such as passing through a drying furnace to volatilize the dispersion solvent to form the heat absorption layer 3.
- a method such as passing through a drying furnace to volatilize the dispersion solvent to form the heat absorption layer 3.
- the third production method by generating bubbles in the resin solution in the drying step, bubbles are rapidly generated in the resin solution, and the formed heat absorption layer 3 has a porous structure, so that the particles are resin. It becomes the structure which was carry
- the surface of the heat absorption layer 3 can be made into the structure which has a mottled uneven
- porous aluminosilicate such as zeolite as particles. This is because in the drying process, gas is generated from the pores of the particles, and a porous structure can be formed more effectively.
- the boiling point of 2-butanone which is an example of a dispersion solvent, is 80 ° C. Therefore, when 2-butanone is used as the dispersion solvent, by setting the drying temperature to about 100 ° C., 2-butanone is vaporized and bubbles are generated in the resin solution.
- a drying temperature of about 100 ° C. is preferable because the substrate 2 is not damaged when the heat absorption layer 3 is formed on the surface of the substrate 2.
- the generated bubbles gather to form large bubbles, forming irregularities, and the resin solution thinly covers the surface of the substrate 2 again and heat absorption layer 3 is formed.
- small bubbles generated in the resin solution realize a three-dimensional network structure of the resin material.
- the second manufacturing method includes the following various methods. Adjustments can be made.
- the heat capacity per unit volume of the heat absorption layer 3 can be adjusted by changing drying conditions such as drying temperature and drying time in the drying step. That is, by raising the drying temperature in the drying step, more bubbles can be generated, and the heat absorption layer 3 after completion can be made sparser. Similarly, by increasing the drying time in the drying step, more bubbles can be generated, and the completed heat absorption layer 3 can be made sparser.
- the porosity of the low porosity layer 3a becomes too high and the strength of the heat absorption layer 3 may be insufficient. Further, when the drying temperature is too low or the drying time is too short, the generation of bubbles is small, and the porosity of the heat absorption layer 3 cannot be made higher than the porosity of the substrate 2.
- the boiling point of N-methyl-2-pyrrolidone which is an example of a dispersion solvent, is about 200 ° C. Therefore, when N-methyl-2-pyrrolidone is used as the dispersion solvent, the drying temperature needs to be higher than 200 ° C. Therefore, when the heat absorption layer 3 is formed using N-methyl-2-pyrrolidone as a dispersion solvent, the base material 2 is composed of a resin material having a melting point or a thermal decomposition temperature higher than the boiling point of the dispersion solvent.
- the heat absorption layer 3 of the present technology is formed on at least one surface of the positive electrode and the negative electrode, the heat resistance of the positive electrode and the negative electrode is high, so that N-methyl-2-pyrrolidone is used as a dispersion solvent. May be used.
- the heat absorption layer 3 of the present technology may be a layer that exists at the boundary between the substrate 2 and at least one of the positive electrode and the negative electrode, and is not necessarily a part of the separator 1 (surface Layer). That is, as another example of the present technology, it is also conceivable to use a separator having a conventional configuration (configuration including only the base material 2) and form a heat absorption layer on at least one of the positive electrode surface and the negative electrode surface. When the heat absorption layer is formed on at least one of the positive electrode surface and the negative electrode surface, the heat absorption layer 3 is always formed on at least one of the positive electrode and the negative electrode facing each other through one separator. In such a configuration, the second manufacturing method can be applied as a method for forming the heat absorption layer on the electrode surface.
- Each material constituting the positive electrode current collector and the positive electrode active material layer, and the negative electrode current collector and the negative electrode current collector is made of a material having heat resistance with respect to a temperature of about the boiling point of the dispersion solvent.
- the manufacturing method is suitable.
- a predetermined amount of particles may be included in the gel electrolyte layer so as to serve also as a heat absorption layer.
- the gel electrolyte layer includes a non-aqueous electrolyte and a polymer compound that holds the non-aqueous electrolyte.
- a gel electrolyte layer is formed by applying a precursor solution containing particles together with a non-aqueous electrolyte and a polymer compound to the positive electrode and the negative electrode, or the separator surface, so that heat is absorbed between the positive electrode and the negative electrode together.
- a layer can be formed.
- FIG. 4 is a cross-sectional view illustrating an example of the nonaqueous electrolyte battery 10 according to the second embodiment.
- the nonaqueous electrolyte battery 10 is a nonaqueous electrolyte secondary battery that can be charged and discharged, for example.
- This non-aqueous electrolyte battery 10 is a so-called cylindrical type, and has a belt-like shape together with a liquid non-aqueous electrolyte (not shown) (hereinafter appropriately referred to as a non-aqueous electrolyte) inside a substantially hollow cylindrical battery can 11.
- the positive electrode 21 and the negative electrode 22 have a wound electrode body 20 wound with a separator 23 interposed therebetween.
- the wound electrode body 20 is easily subjected to tensile stress in the winding direction of the separator due to expansion and contraction of the active material layer. For this reason, it is preferable to apply the separator of the present technology to the nonaqueous electrolyte battery 10 having the wound electrode body 20.
- the battery can 11 is made of, for example, iron plated with nickel, and has one end closed and the other end open. Inside the battery can 11, a pair of insulating plates 12 a and 12 b are respectively arranged perpendicular to the winding peripheral surface so as to sandwich the winding electrode body 20.
- Examples of the material of the battery can 11 include iron (Fe), nickel (Ni), stainless steel (SUS), aluminum (Al), titanium (Ti), and the like.
- the battery can 11 may be plated with nickel or the like, for example, in order to prevent corrosion due to the electrochemical non-aqueous electrolyte accompanying charging / discharging of the non-aqueous electrolyte battery 10.
- a battery lid 13 that is a positive electrode lead plate, and a safety valve mechanism and a heat sensitive resistance element (PTC element: PositivePoTemperature Coefficient) 17 provided inside the battery lid 13 are insulated and sealed. It is attached by caulking through a gasket 18 for
- the battery lid 13 is made of, for example, the same material as the battery can 11 and is provided with an opening for discharging gas generated inside the battery.
- a safety valve 14, a disk holder 15, and a shut-off disk 16 are sequentially stacked.
- the protrusion 14 a of the safety valve 14 is connected to a positive electrode lead 25 led out from the wound electrode body 20 through a sub disk 19 disposed so as to cover a hole 16 a provided in the center of the shutoff disk 16. .
- the safety valve mechanism is electrically connected to the battery lid 13 via the heat sensitive resistance element 17.
- the safety valve mechanism when the internal pressure of the nonaqueous electrolyte battery 10 exceeds a certain level due to internal short circuit or heating from the outside of the battery, the safety valve 14 is reversed, and the protrusion 14a, the battery lid 13 and the wound electrode body 20 are reversed. The electrical connection with is disconnected. That is, when the safety valve 14 is reversed, the positive electrode lead 25 is pressed by the shut-off disk 16 and the connection between the safety valve 14 and the positive electrode lead 25 is released.
- the disc holder 15 is made of an insulating material, and when the safety valve 14 is reversed, the safety valve 14 and the shut-off disc 16 are insulated.
- a plurality of vent holes are provided around the hole 16a of the shut-off disk 16, and when gas is generated from the wound electrode body 20, the gas is effectively removed from the battery lid. It is set as the structure which can discharge
- the resistance element 17 increases in resistance when the temperature rises, cuts off the current by disconnecting the electrical connection between the battery lid 13 and the wound electrode body 20, and generates abnormal heat due to an excessive current.
- the gasket 18 is made of, for example, an insulating material, and the surface is coated with asphalt.
- the wound electrode body 20 accommodated in the nonaqueous electrolyte battery 10 is wound around the center pin 24.
- the wound electrode body 20 is formed by sequentially laminating a positive electrode 21 and a negative electrode 22 with a separator 23 interposed therebetween, and is wound in the longitudinal direction.
- a positive electrode lead 25 is connected to the positive electrode 21, and a negative electrode lead 26 is connected to the negative electrode 22.
- the positive electrode lead 25 is welded to the safety valve 14 and is electrically connected to the battery lid 13, and the negative electrode lead 26 is welded to and electrically connected to the battery can 11.
- FIG. 5 shows an enlarged part of the spirally wound electrode body 20 shown in FIG.
- the positive electrode 21, the negative electrode 22, and the separator 23 will be described in detail.
- the positive electrode 21 is obtained by forming a positive electrode active material layer 21B containing a positive electrode active material on both surfaces of the positive electrode current collector 21A.
- a metal foil such as an aluminum (Al) foil, a nickel (Ni) foil, or a stainless steel (SUS) foil can be used.
- the positive electrode active material layer 21B includes, for example, a positive electrode active material, a conductive agent, and a binder.
- a positive electrode active material any one or more of positive electrode materials capable of inserting and extracting lithium can be used, and other materials such as a binder and a conductive agent can be used as necessary. May be included.
- a lithium-containing compound As the positive electrode material capable of inserting and extracting lithium, for example, a lithium-containing compound is preferable. This is because a high energy density can be obtained.
- the 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.
- the group which consists of cobalt (Co), nickel (Ni), manganese (Mn), and iron (Fe) as a transition metal element is preferable. This is because a higher voltage can be obtained.
- a lithium-containing compound represented by Li x M1O 2 or Li y M2PO 4 can be used as the positive electrode material.
- M1 and M2 represent one or more transition metal elements.
- the values of x and y vary depending on the charge / discharge state of the battery, and are generally 0.05 ⁇ x ⁇ 1.10 and 0.05 ⁇ y ⁇ 1.10.
- Examples of the composite oxide containing lithium and a transition metal element include lithium cobalt composite oxide (Li x CoO 2 ), lithium nickel composite oxide (Li x NiO 2 ), and lithium nickel cobalt composite oxide (Li x Ni).
- lithium nickel cobalt manganese composite oxide Li x Ni (1-vw) Co v Mn w O 2 (0 ⁇ v + w ⁇ 1, v> 0, w > 0)
- lithium manganese composite oxide LiMn 2 O 4
- lithium manganese nickel composite oxide LiMn 2 ⁇ t N t O 4 (0 ⁇ t ⁇ 2) having a spinel structure.
- a complex oxide containing cobalt is preferable. This is because a high capacity can be obtained and excellent cycle characteristics can be obtained.
- Examples of the phosphate compound containing lithium and a transition metal element include a lithium iron phosphate compound (LiFePO 4 ) or a lithium iron manganese phosphate compound (LiFe 1-u Mn u PO 4 (0 ⁇ u ⁇ 1). ) And the like.
- lithium composite oxide examples include lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), and lithium manganate (LiMn 2 O 4 ).
- LiCoO 2 lithium cobaltate
- LiNiO 2 lithium nickelate
- LiMn 2 O 4 lithium manganate
- a solid solution in which a part of the transition metal element is substituted with another element can also be used.
- nickel cobalt composite lithium oxide LiNi 0.5 Co 0.5 O 2 , LiNi 0.8 Co 0.2 O 2, etc.
- composite particles in which the surfaces of particles made of any of the above lithium-containing compounds are coated with fine particles made of any of the other lithium-containing compounds can be used. Good.
- positive electrode materials capable of inserting and extracting lithium include oxides such as vanadium oxide (V 2 O 5 ), titanium dioxide (TiO 2 ), manganese dioxide (MnO 2 ), and iron disulfide. (FeS 2 ), disulfides such as titanium disulfide (TiS 2 ) and molybdenum disulfide (MoS 2 ), and chalcogenides containing no lithium such as niobium diselenide (NbSe 2 ) (particularly layered compounds and spinel compounds) ), Lithium-containing compounds containing lithium, and conductive polymers such as sulfur, polyaniline, polythiophene, polyacetylene, or polypyrrole.
- the positive electrode material capable of inserting and extracting lithium may be other than the above. Further, two or more kinds of the series of positive electrode materials described above may be mixed in any combination.
- a carbon material such as carbon black or graphite
- the binder include resin materials such as polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN), styrene butadiene rubber (SBR), and carboxymethyl cellulose (CMC), and these resin materials. At least one selected from a copolymer or the like mainly composed of is used.
- the positive electrode 21 has a positive electrode lead 25 connected to one end of the positive electrode current collector 21A by spot welding or ultrasonic welding.
- the positive electrode lead 25 is preferably a metal foil or a mesh-like one, but there is no problem even if it is not a metal as long as it is electrochemically and chemically stable and can conduct electricity. Examples of the material of the positive electrode lead 25 include aluminum (Al) and nickel (Ni).
- the negative electrode 22 has, for example, a structure in which a negative electrode active material layer 22B is provided on both surfaces of a negative electrode current collector 22A having a pair of opposed surfaces. Although not shown, the negative electrode active material layer 22B may be provided only on one surface of the negative electrode current collector 22A.
- the anode current collector 22A is made of, for example, a metal foil such as a copper foil.
- the negative electrode active material layer 22B includes one or more negative electrode materials capable of inserting and extracting lithium as the negative electrode active material, and the positive electrode active material layer 21B as necessary. Other materials such as a binder and a conductive agent similar to those described above may be included.
- the electrochemical equivalent of the negative electrode material capable of occluding and releasing lithium is larger than the electrochemical equivalent of the positive electrode 21, and theoretically, the negative electrode 22 is in the middle of charging. Lithium metal is prevented from precipitating.
- the nonaqueous electrolyte battery 10 is designed such that an open circuit voltage (that is, a battery voltage) in a fully charged state is in a range of, for example, 2.80 V or more and 6.00 V or less.
- an open circuit voltage that is, a battery voltage
- the open circuit voltage in the fully charged state is, for example, in the range of 4.20 V to 6.00 V.
- the open circuit voltage in the fully charged state is preferably 4.25V or more and 6.00V or less.
- the open circuit voltage in the fully charged state is 4.25 V or higher
- the amount of lithium released per unit mass is increased even with the same positive electrode active material as compared to the 4.20 V battery. Accordingly, the amounts of the positive electrode active material and the negative electrode active material are adjusted. Thereby, a high energy density can be obtained.
- Examples of the negative electrode material capable of inserting and extracting lithium include non-graphitizable carbon, graphitizable carbon, graphite, pyrolytic carbons, cokes, glassy carbons, and fired organic polymer compounds And carbon materials such as carbon fiber and activated carbon.
- examples of coke include pitch coke, needle coke, and petroleum coke.
- An organic polymer compound fired body is a carbonized material obtained by firing a polymer material such as a phenol resin or a furan resin at an appropriate temperature, and part of it is non-graphitizable carbon or graphitizable carbon.
- These carbon materials are preferable because the change in crystal structure that occurs during charge and discharge is very small, a high charge and discharge capacity can be obtained, and good cycle characteristics can be obtained.
- graphite is preferable because it has a high electrochemical equivalent and can provide a high energy density.
- non-graphitizable carbon is preferable because excellent cycle characteristics can be obtained.
- those having a low charge / discharge potential, specifically, those having a charge / discharge potential close to that of lithium metal are preferable because a high energy density of the battery can be easily realized.
- lithium can be inserted and extracted, and at least one of a metal element and a metalloid element can be used.
- a material containing as a constituent element is included. This is because a high energy density can be obtained by using such a material. In particular, the use with a carbon material is more preferable because a high energy density can be obtained and excellent cycle characteristics can be obtained.
- the negative electrode material may be a single element, alloy or compound of a metal element or metalloid element, or may have at least a part of one or more of these phases.
- the alloy includes an alloy including 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.
- Examples of the metal element or metalloid element constituting the negative electrode material include a metal element or metalloid element capable of forming an alloy with lithium.
- a metal element or metalloid element capable of forming an alloy with lithium.
- the negative electrode material examples include lithium titanate (Li 4 Ti 5 O 12 ). Further, the negative electrode material preferably includes a group 4B metal element or metalloid element in the short-period periodic table as a constituent element, more preferably at least one of silicon (Si) and tin (Sn). And particularly preferably those containing at least silicon. This is because silicon (Si) and tin (Sn) have a large ability to occlude and release lithium, and a high energy density can be obtained. Examples of the negative electrode material having at least one of silicon and tin include at least a part of a simple substance, an alloy or a compound of silicon, a simple substance, an alloy or a compound of tin, or one or more phases thereof. The material which has in is mentioned.
- tin alloys include silicon (Si), nickel (Ni), copper (Cu), iron (Fe), cobalt (Co), and manganese (Mn) as second constituent elements other than tin (Sn).
- tin (Sn) compound or silicon (Si) compound examples include those containing oxygen (O) or carbon (C).
- O oxygen
- C carbon
- the above-described compounds are used. Two constituent elements may be included.
- cobalt (Co), tin (Sn), and carbon (C) are included as constituent elements, and the carbon content is 9.9 mass% or more and 29.7 mass% or less.
- SnCoC containing material whose ratio of cobalt (Co) with respect to the sum total of tin (Sn) and cobalt (Co) is 30 mass% or more and 70 mass% or less is preferable. This is because a high energy density can be obtained in such a composition range, and excellent cycle characteristics can be obtained.
- This SnCoC-containing material may further contain other constituent elements as necessary.
- other constituent elements include silicon (Si), iron (Fe), nickel (Ni), chromium (Cr), indium (In), niobium (Nb), germanium (Ge), titanium (Ti), and molybdenum.
- Mo silicon
- Al aluminum
- phosphorus (P) gallium
- Ga bismuth
- This SnCoC-containing material has a phase containing tin (Sn), cobalt (Co), and carbon (C), and this phase has a low crystallinity or an amorphous structure. It is preferable.
- this SnCoC-containing material it is preferable that at least a part of carbon (C) as a constituent element is bonded to a metal element or a metalloid element as another constituent element.
- the decrease in cycle characteristics is considered to be due to aggregation or crystallization of tin (Sn) or the like.
- the combination of carbon (C) with other elements suppresses such aggregation or crystallization. Because it can.
- XPS X-ray photoelectron spectroscopy
- the peak of the carbon 1s orbital (C1s) appears at 284.5 eV in an energy calibrated apparatus so that the peak of the gold atom 4f orbital (Au4f) is obtained at 84.0 eV if it is graphite. .
- Au4f gold atom 4f orbital
- it will appear at 284.8 eV.
- the charge density of the carbon element increases, for example, when carbon is bonded to a metal element or a metalloid element, the C1s peak appears in a region lower than 284.5 eV.
- the peak of the synthetic wave of C1s obtained for the SnCoC-containing material appears in a region lower than 284.5 eV
- at least a part of the carbon contained in the SnCoC-containing material is a metal element or a half of other constituent elements. Combined with metal elements.
- the C1s peak is used to correct the energy axis of the spectrum.
- the C1s peak of the surface-contaminated carbon is set to 284.8 eV, which is used as an energy standard.
- the waveform of the C1s peak is obtained as a shape including the surface contamination carbon peak and the carbon peak in the SnCoC-containing material. Therefore, by analyzing using, for example, commercially available software, the surface contamination The carbon peak and the carbon peak in the SnCoC-containing material are separated. In the waveform analysis, the position of the main peak existing on the lowest bound energy side is used as the energy reference (284.8 eV).
- the separator 23 is the same as the separator 1 according to the first embodiment.
- the nonaqueous electrolytic solution includes an electrolyte salt and a nonaqueous solvent that dissolves the electrolyte salt.
- the electrolyte salt contains, for example, one or more light metal compounds such as lithium salts.
- the lithium salt include lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium perchlorate (LiClO 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium tetraphenylborate (LiB (C 6 H 5) 4), methanesulfonic acid lithium (LiCH 3 SO 3), lithium trifluoromethanesulfonate (LiCF 3 SO 3), tetrachloroaluminate lithium (LiAlCl 4), six Examples thereof include dilithium fluorosilicate (Li 2 SiF 6 ), lithium chloride (LiCl), and lithium bromide (LiBr).
- At least one selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, and lithium hexafluoroarsenate is preferable, and lithium hexafluorophosphate is more preferable.
- non-aqueous solvent examples include lactone solvents such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, and ⁇ -caprolactone, ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, dimethyl carbonate, ethyl methyl carbonate, Carbonate ester solvents such as diethyl carbonate, ether solvents such as 1,2-dimethoxyethane, 1-ethoxy-2-methoxyethane, 1,2-diethoxyethane, tetrahydrofuran or 2-methyltetrahydrofuran, and nitriles such as acetonitrile
- Nonaqueous solvents such as solvents, sulfolane-based solvents, phosphoric acids, phosphate ester solvents, and pyrrolidones are exemplified. Any one type of solvent may be used alone, or two or more types may be mixed and used.
- a mixture of a cyclic carbonate and a chain carbonate as the non-aqueous solvent, and it may contain a compound in which a part or all of the hydrogen of the cyclic carbonate or the chain carbonate includes a fluorination.
- the fluorinated compounds include fluoroethylene carbonate (4-fluoro-1,3-dioxolan-2-one: FEC) and difluoroethylene carbonate (4,5-difluoro-1,3-dioxolan-2-one: DFEC) is preferably used.
- the negative electrode 22 containing a compound such as silicon (Si), tin (Sn), or germanium (Ge) is used as the negative electrode active material, charge / discharge cycle characteristics can be improved.
- difluoroethylene carbonate is preferably used as the non-aqueous solvent. This is because the cycle characteristic improvement effect is excellent.
- the nonaqueous electrolytic solution may be held in a polymer compound to be a gel electrolyte.
- the polymer compound that holds the non-aqueous electrolyte is not particularly limited as long as it absorbs the non-aqueous solvent and gels.
- PVdF polyvinylidene fluoride
- VdF vinylidene fluoride
- HFP hexafluoropropylene
- a fluorine-based polymer compound such as a copolymer containing a repeating unit, an ether-based polymer compound such as polyethylene oxide (PEO) or a crosslinked product containing polyethylene oxide (PEO), polyacrylonitrile (PAN), polypropylene oxide (PPO) ) Or polymethyl methacrylate (PMMA) as a repeating unit. Any one of these polymer compounds may be used alone, or two or more thereof may be mixed and used.
- a fluorine-based polymer compound is desirable, and among them, a copolymer containing vinylidene fluoride and hexafluoropropylene as components is preferable. Further, this copolymer is composed of unsaturated dibasic acid monoester such as maleic acid monomethyl ester (MMM), halogenated ethylene such as ethylene trifluorochloride (PCTFE), and unsaturated compound such as vinylene carbonate (VC).
- MMM maleic acid monomethyl ester
- PCTFE halogenated ethylene
- VC vinylene carbonate
- the cyclic carbonate ester or epoxy group-containing acrylic vinyl monomer may be included as a component. This is because higher characteristics can be obtained.
- Nonaqueous electrolyte battery manufacturing method A positive electrode active material, a conductive agent, and a binder are mixed to prepare a positive electrode mixture, and the positive electrode mixture is dispersed in a solvent such as N-methyl-2-pyrrolidone to form a paste-like positive electrode mixture slurry Is made. Next, the positive electrode mixture slurry is applied to the positive electrode current collector 21A, the solvent is dried, and the positive electrode active material layer 21B is formed by compression molding with a roll press machine or the like, and the positive electrode 21 is manufactured.
- a solvent such as N-methyl-2-pyrrolidone
- a negative electrode active material and a binder are mixed to prepare a negative electrode mixture, and the negative electrode mixture is dispersed in a solvent such as N-methyl-2-pyrrolidone to prepare a paste-like negative electrode mixture slurry.
- the negative electrode mixture slurry is applied to the negative electrode current collector 22A, the solvent is dried, and the negative electrode active material layer 22B is formed by compression molding with a roll press or the like, thereby producing the negative electrode 22.
- the nonaqueous electrolytic solution is prepared by dissolving an electrolyte salt in a nonaqueous solvent.
- the positive electrode lead 25 is attached to the positive electrode current collector 21A by welding or the like, and the negative electrode lead 26 is attached to the negative electrode current collector 22A by welding or the like. Then, the positive electrode 21 and the negative electrode 22 are wound through the separator 23 of the present technology to form a wound electrode body 20.
- the tip of the positive electrode lead 25 is welded to the safety valve mechanism, and the tip of the negative electrode lead 26 is welded to the battery can 11. Thereafter, the wound surface of the wound electrode body 20 is sandwiched between the pair of insulating plates 12 and 13 and stored in the battery can 11.
- a non-aqueous electrolyte is injected into the battery can 11 and impregnated in the separator 23.
- the safety valve mechanism including the battery lid 13 and the safety valve 14 and the heat sensitive resistance element 17 are fixed to the opening end of the battery can 11 by caulking through the gasket 18. Thereby, the nonaqueous electrolyte battery 10 of the present technology shown in FIG. 4 is formed.
- nonaqueous electrolyte battery 10 when charged, for example, lithium ions are released from the positive electrode active material layer 21 ⁇ / b> B and inserted into the negative electrode active material layer 22 ⁇ / b> B through the nonaqueous electrolyte solution impregnated in the separator 23.
- lithium ions when discharging is performed, for example, lithium ions are released from the negative electrode active material layer 22B and inserted into the positive electrode active material layer 21B through the nonaqueous electrolytic solution impregnated in the separator 23.
- heat generation at the negative electrode particularly heat generation at the negative electrode using a negative electrode active material containing at least one of a metal element and a metalloid element as a constituent element, is generated.
- it can be insulated by the heat absorption layer. For this reason, the heat generation at the negative electrode is hardly transmitted to the positive electrode, and the thermal decomposition reaction of the positive electrode can be suppressed. Further, the insulating property can be maintained by the heat absorption layer even when the separator is melted by heat generation at a high temperature.
- FIG. 6 shows the configuration of a nonaqueous electrolyte battery 30 according to the third embodiment.
- This non-aqueous electrolyte battery is a so-called square battery, in which the wound electrode body 40 is accommodated in a rectangular outer can 31.
- the nonaqueous electrolyte battery 30 includes a rectangular tube-shaped outer can 31, a wound electrode body 40 that is a power generation element housed in the outer can 31, a battery lid 32 that closes an opening of the outer can 31, a battery An electrode pin 33 and the like provided at substantially the center of the lid 32 are used.
- the outer can 31 is formed, for example, as a hollow, bottomed rectangular tube with a conductive metal such as iron (Fe).
- the inner surface of the outer can 31 is preferably configured to increase the conductivity of the outer can 31 by, for example, applying nickel plating or applying a conductive paint.
- the outer peripheral surface of the outer can 31 may be covered with an outer label formed of, for example, a plastic sheet or paper, or may be protected by applying an insulating paint.
- the battery lid 32 is formed of a conductive metal such as iron (Fe), for example, as with the outer can 31.
- the wound electrode body 40 is obtained by laminating a positive electrode and a negative electrode with a separator interposed between them and winding them in an oval shape. Since the positive electrode, the negative electrode, the separator, and the nonaqueous electrolytic solution are the same as those in the first embodiment or the second embodiment, detailed description thereof is omitted.
- a gel-like non-aqueous electrolyte layer (gel electrolyte layer) in which a non-aqueous electrolyte is held in a polymer compound may be formed between the positive electrode and the negative electrode and the separator.
- the wound electrode body 40 having such a configuration is provided with a number of positive terminals 41 connected to the positive current collector and a number of negative terminals connected to the negative current collector. All the positive terminals 41 and the negative terminals are led to one end of the spirally wound electrode body 40 in the axial direction.
- the positive terminal 41 is connected to the lower end of the electrode pin 33 by fixing means such as welding.
- the negative electrode terminal is connected to the inner surface of the outer can 31 by fixing means such as welding.
- the electrode pin 33 is made of a conductive shaft member, and is held by an insulator 34 with its head protruding to the upper end.
- the electrode pin 33 is fixed to a substantially central portion of the battery lid 32 through the insulator 34.
- the insulator 34 is made of a highly insulating material and is fitted into a through hole 35 provided on the surface side of the battery lid 32. Further, the electrode pin 33 is passed through the through hole 35, and the tip end portion of the positive electrode terminal 41 is fixed to the lower end surface thereof.
- the battery lid 32 provided with such electrode pins 33 and the like is fitted into the opening of the outer can 31, and the contact surface between the outer can 31 and the battery lid 32 is joined by fixing means such as welding. Yes. Thereby, the opening part of the armored can 31 is sealed by the battery cover 32, and is comprised airtight and liquid-tight.
- the battery lid 32 is provided with an internal pressure release mechanism 36 that breaks a part of the battery lid 32 to release (release) the internal pressure to the outside when the pressure in the outer can 31 rises above a predetermined value. ing.
- the internal pressure release mechanism 36 includes two first opening grooves 36a (one first opening groove 36a not shown) linearly extending in the longitudinal direction on the inner surface of the battery lid 32, and the battery.
- the inner surface of the lid 32 includes a second opening groove 36b extending in the width direction orthogonal to the longitudinal direction and having both ends communicating with the two first opening grooves 36a.
- the two first opening grooves 36 a are provided in parallel to each other along the outer edge of the long side of the battery lid 32 in the vicinity of the inner side of the two long sides positioned so as to face the width direction of the battery lid 32.
- the second opening groove 36 b is provided so as to be positioned at a substantially central portion between one short side outer edge and the electrode pin 33 on one side in the longitudinal direction of the electrode pin 33.
- Both the first opening groove 36a and the second opening groove 36b are, for example, V-shaped with a cross-sectional shape opened to the lower surface side.
- the shapes of the first opening groove 36a and the second opening groove 36b are not limited to the V shape shown in this embodiment.
- the shapes of the first opening groove 36a and the second opening groove 36b may be U-shaped or semicircular.
- the electrolyte injection port 37 is provided so as to penetrate the battery lid 32.
- the electrolyte inlet 37 is used to inject a non-aqueous electrolyte after the battery lid 32 and the outer can 31 are caulked, and is sealed by a sealing member 38 after the non-aqueous electrolyte is injected.
- the electrolyte solution inlet 37 and the sealing member 38 may not be provided.
- the separator can have the same configuration as that of the separator 1 in the first embodiment.
- Non-aqueous electrolyte As the non-aqueous electrolyte, the one described in the second embodiment can be used. Moreover, you may use the gel electrolyte which hold
- This nonaqueous electrolyte battery can be manufactured, for example, as follows.
- the positive electrode and the negative electrode can be produced by the same method as in the second embodiment.
- a positive electrode, a negative electrode, and a separator of the present technology are sequentially laminated and wound to produce a wound electrode body 40 that is wound in an oblong shape. Subsequently, the wound electrode body 40 is accommodated in the outer can 31.
- the electrode pin 33 provided on the battery lid 32 and the positive electrode terminal 41 led out from the wound electrode body 40 are connected.
- the negative electrode terminal led out from the wound electrode body 40 and the battery can are connected.
- the outer can 31 and the battery lid 32 are fitted together, and, for example, a non-aqueous electrolyte is injected from the electrolyte inlet 37 under reduced pressure and sealed with a sealing member 38. As described above, the nonaqueous electrolyte battery 30 can be obtained.
- the third embodiment can obtain the same effects as those of the second embodiment.
- FIG. 7 shows the configuration of a nonaqueous electrolyte battery 62 according to the fourth embodiment.
- This non-aqueous electrolyte battery 62 is a so-called laminate film type, in which a wound electrode body 50 to which a positive electrode lead 51 and a negative electrode lead 52 are attached is housed in a film-like exterior member 60.
- the positive electrode lead 51 and the negative electrode lead 52 are led out from the inside of the exterior member 60 toward the outside, for example, in the same direction.
- the positive electrode lead 51 and the negative electrode lead 52 are made of, for example, a metal material such as aluminum, copper, nickel, or stainless steel, and each have a thin plate shape or a mesh shape.
- the exterior member 60 is made of, for example, a laminate film in which resin layers are formed on both surfaces of a metal layer.
- an outer resin layer is formed on the surface of the metal layer that is exposed to the outside of the battery, and an inner resin layer is formed on the inner surface of the battery facing the power generation element such as the wound electrode body 50.
- the metal layer plays the most important role in preventing moisture, oxygen and light from entering and protecting the contents.
- Aluminum (Al) is most often used because of its lightness, extensibility, price and ease of processing.
- the outer resin layer has a beautiful appearance, toughness, flexibility, and the like, and a resin material such as nylon or polyethylene terephthalate (PET) is used. Since the inner resin layer is a portion that melts and fuses with heat or ultrasonic waves, a polyolefin resin is appropriate, and unstretched polypropylene (CPP) is often used.
- An adhesive layer may be provided between the metal layer, the outer resin layer, and the inner resin layer as necessary.
- the exterior member 60 is provided with a recess that accommodates the wound electrode body 50 formed by, for example, deep drawing from the inner resin layer side toward the outer resin layer, and the inner resin layer serves as the wound electrode body 50. It is arrange
- the inner resin layers facing each other of the exterior member 60 are in close contact with each other by fusion or the like at the outer edge of the recess.
- the adhesion film 61 is made of a resin material having high adhesion to a metal material, and is made of, for example, polyethylene, polypropylene, or a polyolefin resin such as modified polyethylene or modified polypropylene obtained by modifying these materials.
- the exterior member 60 may be made of a laminated film having another structure, a polymer film such as polypropylene, or a metal film, instead of the aluminum laminated film whose metal layer is made of aluminum (Al).
- FIG. 8 shows a cross-sectional structure taken along line II of the spirally wound electrode body 50 shown in FIG.
- the wound electrode body 50 is obtained by laminating a positive electrode 53 and a negative electrode 54 via a separator 55 and a gel electrolyte 56 and winding them, and the outermost peripheral portion is protected by a protective tape 57 as necessary.
- the positive electrode 53 has a structure in which a positive electrode active material layer 53B is provided on one or both surfaces of the positive electrode current collector 53A.
- the configurations of the positive electrode current collector 53A and the positive electrode active material layer 53B are the same as those of the positive electrode current collector 21A and the positive electrode active material layer 21B of the second embodiment described above.
- the negative electrode 54 has a structure in which a negative electrode active material layer 54B is provided on one surface or both surfaces of a negative electrode current collector 54A, and the negative electrode active material layer 54B and the positive electrode active material layer 53B are arranged to face each other. Yes.
- the configurations of the negative electrode current collector 54A and the negative electrode active material layer 54B are the same as those of the negative electrode current collector 22A and the negative electrode active material layer 22B of the second embodiment described above.
- the separator 55 is the same as the separator 1 according to the first embodiment.
- the gel electrolyte 56 is a non-aqueous electrolyte, and includes a non-aqueous electrolyte and a polymer compound that serves as a holding body that holds the non-aqueous electrolyte, and has a so-called gel shape.
- a gel electrolyte is preferable because high ion conductivity can be obtained and battery leakage can be prevented.
- the same non-aqueous electrolyte as in the second embodiment may be used instead of the gel electrolyte 56.
- This nonaqueous electrolyte battery 62 can be manufactured as follows, for example.
- the positive electrode 53 and the negative electrode 54 can be manufactured by the same method as in the second embodiment.
- a precursor solution containing a nonaqueous electrolytic solution, a polymer compound, and a mixed solvent is applied to both surfaces of the positive electrode 53 and the negative electrode 54, and the mixed solvent is volatilized to form a gel electrolyte 56. Thereafter, the positive electrode lead 51 is attached to the end of the positive electrode current collector 53A by welding, and the negative electrode lead 52 is attached to the end of the negative electrode current collector 54A by welding.
- the positive electrode 53 and the negative electrode 54 on which the gel electrolyte 56 is formed are laminated through a separator 55 to form a laminated body, and then the laminated body is wound in the longitudinal direction, and the protective tape 57 is attached to the outermost peripheral portion.
- the wound electrode body 50 is formed by bonding.
- the wound electrode body 50 is sandwiched between the exterior members 60, and the outer edges of the exterior members 60 are sealed and sealed by thermal fusion or the like.
- an adhesion film 61 is inserted between the positive electrode lead 51 and the negative electrode lead 52 and the exterior member 60.
- the nonaqueous electrolyte battery 62 shown in FIGS. 7 and 8 is completed.
- the nonaqueous electrolyte battery 62 may be manufactured as follows. First, the positive electrode 53 and the negative electrode 54 are prepared as described above, and after the positive electrode lead 51 and the negative electrode lead 52 are attached to the positive electrode 53 and the negative electrode 54, the positive electrode 53 and the negative electrode 54 are stacked and wound via the separator 55. Rotate and adhere the protective tape 57 to the outermost periphery to form the wound electrode body 50. Next, the wound electrode body 50 is sandwiched between the exterior members 60, and the outer peripheral edge except for one side is heat-sealed to form a bag shape and stored inside the exterior member 60.
- an electrolyte composition containing a monomer that is a raw material for the polymer compound, a polymerization initiator, and other materials such as a polymerization inhibitor as necessary is prepared together with the non-aqueous electrolyte, and the exterior member 60 is prepared. Inject inside.
- the opening of the exterior member 60 is heat-sealed in a vacuum atmosphere and sealed. Next, heat is applied to polymerize the monomer to form a polymer compound, thereby forming a gel-like gel electrolyte 56, and assembling the nonaqueous electrolyte battery 62 shown in FIGS.
- the positive electrode 53 and the negative electrode 54 are laminated and wound via the separator 55, and the protective tape 57 is attached to the outermost periphery.
- the wound electrode body 50 is formed by bonding.
- the wound electrode body 50 is sandwiched between the exterior members 60, and the outer peripheral edge except for one side is heat-sealed to form a bag shape and stored inside the exterior member 60.
- the non-aqueous electrolyte battery 62 is assembled by injecting a non-aqueous electrolyte into the exterior member 60 and thermally sealing the opening of the exterior member 60 in a vacuum atmosphere.
- FIG. 9A is an external view of the nonaqueous electrolyte battery 62 that houses the laminated electrode body 70.
- FIG. 9B is an exploded perspective view showing a state in which the laminated electrode body 70 is accommodated in the exterior member 60.
- FIG. 9C is an external view showing an external appearance from the bottom surface side of the nonaqueous electrolyte battery 62 shown in FIG. 9A.
- 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.
- 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 method for forming the gel electrolyte 56 or the method for injecting the non-aqueous electrolyte and the method for thermally fusing the exterior member 60 are the same as in the case of using the spirally wound electrode body 50 described in (4-2).
- a battery pack of a laminated film type nonaqueous electrolyte battery according to a fifth 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 battery pack is formed by connecting a circuit board to the battery cell and fitting a top cover and a rear cover. Called.
- 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. 10 is a perspective view showing a configuration example of the battery pack 90 according to the fifth embodiment.
- FIG. 11 is an exploded perspective view showing the structure of the battery cell 80.
- FIG. 12 is a top view and a side view showing a state in the middle of manufacturing the battery cell 80 according to the fifth embodiment.
- FIG. 13 is a cross-sectional view showing a cross-sectional structure in the battery cell 80.
- the battery pack 90 is, for example, a battery pack of a nonaqueous electrolyte battery having a square shape or a flat shape, and as shown in FIG. 10, both ends are opened to form an opening, and a wound electrode is formed in the exterior material.
- the battery cell 80 in which the body 50 is accommodated, and the top cover 82a and the bottom cover 82b respectively fitted to the openings at both ends of the battery cell 80 are provided.
- the wound electrode body 50 accommodated in the battery pack 90 can use the same wound electrode body 50 as in the fourth 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 the 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 come into contact with each other or face each other with a slight gap in a state where 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 fourth 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 can have the same configuration as that of the fourth embodiment. Moreover, you may use the laminated electrode body 70 demonstrated in the other example of 4th Embodiment.
- Nonaqueous electrolyte, gel electrolyte The non-aqueous electrolyte injected into the battery cell 80 or the gel electrolyte formed on the surfaces of the positive electrode 53 and the negative electrode 54 can have the same configuration as in the second embodiment.
- the separator 55 As the separator 55, the separator 1 of the present technology can be used. Further, the base material 2 in the first embodiment may be a separator, and the heat absorption layer 3 may be provided on the surfaces of the positive electrode 53 and the negative electrode 54.
- 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.
- FIG. 14 is a block diagram illustrating a circuit configuration example when the nonaqueous electrolyte battery of the present technology 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 also includes a positive electrode terminal 321 and a negative electrode terminal 322.
- the positive electrode terminal 321 and the negative electrode terminal 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 terminal 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 nonaqueous electrolyte batteries 301a in series and / or in parallel.
- This nonaqueous electrolyte battery 301a is a nonaqueous electrolyte battery of the present technology.
- FIG. 14 although the case where the six nonaqueous electrolyte batteries 301a are connected to 2 parallel 3 series (2P3S) is shown as an example, in addition, n parallel m series (n and m are integers). As such, 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 terminal 321 in the direction of the assembled battery 301 and the forward polarity with respect to the discharging current flowing from the negative terminal 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 portion 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 charge control switch is turned off, only discharging is possible through 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 non-aqueous electrolyte battery 301 a that constitutes the same, performs A / D conversion on the measured voltage, and supplies the voltage 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 nonaqueous electrolyte battery 301a becomes equal to or lower than the overcharge detection voltage or overdischarge detection voltage, or when a large current flows suddenly. To prevent overcharge, overdischarge and overcurrent charge / discharge.
- the overcharge detection voltage is, for example, 4.20V ⁇ 0.05V is determined, and the overdischarge detection voltage is determined to be, for example, 2.4V ⁇ 0.1V.
- 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 nonaqueous electrolyte battery 301a measured in the manufacturing process, and the like are stored in advance, and can be appropriately rewritten. is there. (In addition, by storing the full charge capacity of the nonaqueous electrolyte 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 non-aqueous electrolyte battery according to the second to fourth embodiments and the electronic device including the battery pack according to the fifth and sixth embodiments, electric Devices such as vehicles and power storage devices will be described.
- the nonaqueous electrolyte batteries and battery packs described in the second to fifth embodiments can be used to supply electric power to devices such as electronic devices, electric vehicles, and power storage devices.
- 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 machines, 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, toy, medical equipment, robot, road conditioner, traffic light 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.
- the house 101 is provided with a home power generation device 104, a power consumption device 105, a power storage device 103, a control device 110 that controls each device, a smart meter 107, and a sensor 111 that acquires various types of information.
- Each device is connected by a power network 109 and an information network 112.
- a solar cell, a fuel cell, or the like is used as the home power generation device 104, and the generated power is supplied to the power consumption device 105 and / or the power storage device 103.
- the power consuming device 105 is a refrigerator 105a, an air conditioner 105b, a television receiver 105c, a bath 105d, and the like.
- the electric power consumption device 105 includes an electric vehicle 106.
- the electric vehicle 106 is an electric vehicle 106a, a hybrid car 106b, and an electric motorcycle 106c.
- the nonaqueous electrolyte battery of the present technology is applied to the power storage device 103.
- the nonaqueous electrolyte battery of the present technology may be constituted by, for example, the above-described lithium ion secondary battery.
- the smart meter 107 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 109 may be one or a combination of DC power supply, AC power supply, and non-contact power supply.
- the various sensors 111 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 111 is transmitted to the control device 110. Based on the information from the sensor 111, the weather condition, the human condition, etc. can be grasped, and the power consumption device 105 can be automatically controlled to minimize the energy consumption. Furthermore, the control device 110 can transmit information regarding the house 101 to an external power company or the like via the Internet.
- the power hub 108 performs processing such as branching of power lines and DC / AC conversion.
- Communication methods of the information network 112 connected to the control device 110 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 110 is connected to an external server 113.
- the server 113 may be managed by any one of the house 101, the power company, and the service provider.
- the information transmitted and received by the server 113 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 in the home (for example, a television receiver), but 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, such as a television receiver, a mobile phone, or a PDA (Personal Digital Assistants).
- a display function such as a television receiver, a mobile phone, or a PDA (Personal Digital Assistants).
- the control device 110 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 103 in this example.
- the control device 110 is connected to the power storage device 103, the home power generation device 104, the power consumption device 105, the various sensors 111, the server 113 and the information network 112, and adjusts, for example, the amount of commercial power used and the amount of power generation. It has a function. In addition, you may provide the function etc. which carry out an electric power transaction in an electric power market.
- electric power is generated not only from the centralized power system 102 such as the thermal power generation 102a, the nuclear power generation 102b, and the hydroelectric power generation 102c but also from the home power generation device 104 (solar power generation, wind power generation) to the power storage device 103.
- the home power generation device 104 solar power generation, wind power generation
- the electric power obtained by solar power generation is stored in the power storage device 103, and midnight power with a low charge is stored in the power storage device 103 at night, and the power stored by the power storage device 103 is discharged during a high daytime charge. You can also use it.
- control device 110 is stored in the power storage device 103 .
- control device 110 may be stored in the smart meter 107 or may be configured independently.
- the power storage system 100 may be used for a plurality of homes in an apartment house, or may be used for a plurality of detached houses.
- FIG. 16 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 200 includes an engine 201, a generator 202, a power driving force conversion device 203, driving wheels 204a, driving wheels 204b, wheels 205a, wheels 205b, a battery 208, a vehicle control device 209, various sensors 210, and a charging port 211. Is installed.
- the nonaqueous electrolyte battery of the present technology described above is applied to the battery 208.
- Hybrid vehicle 200 travels using electric power / driving force conversion device 203 as a power source.
- An example of the power driving force conversion device 203 is a motor.
- the electric power / driving force converter 203 is operated by the electric power of the battery 208, and the rotational force of the electric power / driving force converter 203 is transmitted to the driving wheels 204a and 204b.
- DC-AC DC-AC
- AC-DC conversion AC-DC conversion
- the power driving force converter 203 can be applied to either an AC motor or a DC motor.
- the various sensors 210 control the engine speed via the vehicle control device 209, and control the opening (throttle opening) of a throttle valve (not shown).
- the various sensors 210 include a speed sensor, an acceleration sensor, an engine speed sensor, and the like.
- the rotational force of the engine 201 is transmitted to the generator 202, and the electric power generated by the generator 202 by the rotational force can be stored in the battery 208.
- the resistance force at the time of deceleration is applied as a rotational force to the power driving force conversion device 203, and the regenerative electric power generated by the power driving force conversion device 203 by this rotational force is used as the battery 208. Accumulated in.
- the battery 208 is connected to a power source external to the hybrid vehicle 200, so that power can be supplied from the external power source using the charging port 211 as an input port, and the received power can be stored.
- an information processing device that performs information processing related to vehicle control based on information related to the nonaqueous electrolyte 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 1-1> to ⁇ Example 1-50> and ⁇ Comparative Example 1-1> to ⁇ Comparative Example 1-16> In the following Example 1-1 to Example 1-50 and Comparative Example 1-1 to Comparative Example 1-16, using a separator in which the heat capacity per unit area of the heat absorption layer and the heat capacity per unit volume are adjusted, The effect of this technology was confirmed.
- Example 1-1 [Production of positive electrode] A mixture of positive electrode active material lithium cobaltate (LiCoO 2 ) 91% by mass, conductive material carbon black 6% by mass, and binder polyvinylidene fluoride (PVdF) 3% by mass. The positive electrode mixture was dispersed in N-methyl-2-pyrrolidone (NMP) as a dispersion medium to obtain a positive electrode mixture slurry. This positive electrode mixture slurry was applied to both surfaces of a positive electrode current collector made of a strip-shaped aluminum foil having a thickness of 12 ⁇ m so that a part of the positive electrode current collector was exposed.
- NMP N-methyl-2-pyrrolidone
- the dispersion medium of the applied positive electrode mixture slurry was evaporated and dried, and compression-molded with a roll press to form a positive electrode active material layer.
- the positive electrode terminal was attached to the exposed portion of the positive electrode current collector to form the positive electrode.
- coated negative mix slurry was evaporated and dried, and the negative electrode active material layer was formed by compression molding with a roll press. Finally, the negative electrode terminal was attached to the exposed portion of the negative electrode current collector to form a negative electrode.
- a heat absorption layer was formed on both sides of the substrate as follows. First, boehmite (specific heat: 1.2 J / gK) having an average particle diameter of 0.8 ⁇ m as endothermic particles and polyvinylidene fluoride (PVdF) as a resin material are mixed so as to have a mass ratio of 9: 1, A resin solution was prepared by dispersing in N-methyl-2-pyrrolidone (NMP).
- NMP N-methyl-2-pyrrolidone
- the substrate coated with the resin solution is immersed in a water bath in which water is vibrated by ultrasonic waves to cause phase separation, and the resin solution N-methyl-2-pyrrolidone (NMP) was removed.
- NMP N-methyl-2-pyrrolidone
- the base material coated with the resin solution was passed through the dryer to remove water and residual NMP, and a separator in which the base material and the heat absorption layer made of the resin material and boehmite were laminated was produced. .
- the amount of boehmite per unit area was adjusted by the coating thickness of the resin solution. Specifically, the thickness is adjusted so that the amount of boehmite per unit area is 0.0005 g / cm 2 on both sides of the substrate, and the total heat capacity per unit area of the heat absorption layer is 0.0006 J / Kcm. 2 (0.0005 [g / cm 2 ] ⁇ 1.2 [J / gK]).
- the filling amount of boehmite per unit volume was adjusted by the ultrasonic energy applied at the time of phase separation of the heat absorption layer and the solid content ratio of the resin solution.
- the total thickness of the heat absorption layers on both sides of the substrate is 15 ⁇ m (0.0005 [g / cm 2 ] so that boehmite per unit volume is 0.33 g / cm 3 on both sides of the substrate. ⁇ 0.33 [g / cm 3 ])
- the total heat capacity per unit volume of the heat absorption layer is 0.4 J / Kcm 3 (0.33 [g / cm 3 ] ⁇ 1.2 [J / gK]).
- the thickness of the heat absorption layer after applying ultrasonic vibration becomes larger than the thickness when the resin solution is applied.
- the heat capacity per unit volume can be adjusted while adjusting the thickness of the heat absorption layer after completion and keeping the heat capacity per unit area constant.
- EC ethylene carbonate
- VC vinylene carbonate
- DEC diethyl carbonate
- a positive electrode, a negative electrode, and a separator having a heat-adsorbing layer formed on both sides are laminated in the order of the positive electrode, the separator, the negative electrode, and the separator, and are wound many times in the longitudinal direction, and then the winding end portion is fixed with an adhesive tape.
- a wound electrode body was formed.
- the positive electrode terminal was bonded to the safety valve bonded to the battery lid, and the negative electrode lead was connected to the negative electrode can.
- a center pin was inserted into the center of the wound electrode body.
- a non-aqueous electrolyte was injected into the inside of the cylindrical battery can from above the insulating plate.
- a safety valve mechanism including a safety valve, a disk holder, and a shut-off disk, a PTC element, and a battery lid were sealed in the open portion of the battery can by caulking through an insulating sealing gasket.
- Example 1-2> to ⁇ Example 1-7> At the time of forming the heat absorption layer of the separator, the thickness of the heat absorption layer was adjusted by adjusting the intensity of the ultrasonic wave so that the heat capacity per unit volume of the heat absorption layer became the value shown in Table 1. .
- the thermal capacity per unit area is 0.0006J / Kcm 2
- the thermal capacity per unit volume respectively 0.2J / Kcm 3, 0.3J / Kcm 3, 1.0J / Kcm 3, 1.5J /
- the separators of Examples 1-2 to 1-7 having heat absorption layers of Kcm 3 , 2.5 J / Kcm 3 and 3.0 J / Kcm 3 were respectively produced. Cylindrical batteries of Examples 1-2 to 1-7 were produced using each of these separators.
- Example 1-13> to ⁇ Example 1-24> silicon powder was used as the negative electrode active material instead of graphite.
- a negative electrode mixture is prepared by mixing 85% by mass of silicon (Si) particles as a negative electrode active material, 10% by mass of carbon black as a conductive material, and 5% by mass of polyvinylidene fluoride (PVdF) as a binder. Then, this negative electrode mixture was dispersed in N-methyl-2-pyrrolidone (NMP) as a dispersion medium to obtain a negative electrode mixture slurry.
- NMP N-methyl-2-pyrrolidone
- Cylindrical batteries of Examples 1-13 to 1-24 were produced in the same manner as in Examples 1-1 to 1-12, except that this negative electrode mixture slurry was used.
- a carbon tin composite material was used as the negative electrode active material instead of graphite.
- the carbon-tin composite material contains tin (Sn), cobalt (Co), and carbon (C) as constituent elements, and the composition is tin content of 22% by mass, cobalt content of 55% by mass, carbon
- An SnCoC-containing material having a content of 23% by mass and a ratio of tin to the total of tin and cobalt (Co / (Sn + Co)) of 71.4% by mass was used.
- a negative electrode mixture was prepared by mixing 80% by mass of SnCoC-containing material powder as a negative electrode active material, 12% by mass of graphite as a conductive agent, and 8% by mass of polyvinylidene fluoride (PVdF) as a binder. Subsequently, the negative electrode mixture was dispersed in N-methyl-2-pyrrolidone to prepare a paste-like negative electrode mixture slurry. Cylindrical batteries of Examples 1-25 to 1-36 were produced in the same manner as in Examples 1-1 to 1-12, except that this negative electrode mixture slurry was used.
- lithium titanate (Li 4 Ti 5 O 12 ) was used as the negative electrode active material instead of graphite.
- a negative electrode mixture prepared by mixing 85% by mass of lithium titanate (Li 4 Ti 5 O 12 ) as a negative electrode active material, 10% by mass of graphite as a conductive agent, and 5% by mass of polyvinylidene fluoride (PVdF) as a binder. It was. Subsequently, the negative electrode mixture was dispersed in N-methyl-2-pyrrolidone to prepare a paste-like negative electrode mixture slurry. Cylindrical batteries of Examples 1-37 to 1-48 were produced in the same manner as in Examples 1-1 to 1-12 except that this negative electrode mixture slurry was used.
- Example 1-49 As the base material, a cellulose permeable membrane having a thickness of 9 ⁇ m and a porosity of 60%, which is paper, was used. The same resin solution as in Example 1-1 was uniformly applied to both surfaces of the substrate. At this time, the coating material was also impregnated into the voids of the cellulose gas permeable membrane as the base material. Thereafter, the substrate coated with the resin solution was immersed in a water bath in which water was vibrated with ultrasonic waves to cause phase separation, and then N-methyl-2-pyrrolidone (NMP) in the resin solution was removed.
- NMP N-methyl-2-pyrrolidone
- the base material coated with the resin solution was passed through a drier to remove water and residual NMP, thereby forming a heat absorption layer made of a resin material and boehmite.
- the intensity of the ultrasonic wave was adjusted so that the porosity in the cellulose gas permeable membrane as the base material was 35%.
- the coating amount was adjusted so that the thickness of the heat absorption layer was the same as in Example 1-1.
- Example 1-49 having a heat absorption layer having a heat capacity per unit area of 0.00142 J / Kcm 2 and a heat capacity per unit volume of 1.0 J / Kcm 3 was produced.
- This separator is provided with a heat absorption layer partly included in a void in the base material on one surface side and the other surface side of the base material.
- a cylindrical battery of Example 1-49 was produced using this separator.
- Example 1-50> A polyethylene terephthalate (PET) permeable membrane having a thickness of 9 ⁇ m and a porosity of 80% was used as the substrate.
- PET polyethylene terephthalate
- the same resin solution as in Example 1-1 was uniformly applied to both surfaces of the substrate.
- the coating material was also impregnated into the voids of the polyethylene terephthalate gas-permeable membrane as the base material.
- the substrate coated with the resin solution was immersed in a water bath in which water was vibrated with ultrasonic waves to cause phase separation, and then N-methyl-2-pyrrolidone (NMP) in the resin solution was removed.
- NMP N-methyl-2-pyrrolidone
- the base material coated with the resin solution was passed through a drier to remove water and residual NMP, thereby forming a heat absorption layer made of a resin material and boehmite.
- the intensity of the ultrasonic wave was adjusted so that the porosity in the polyethylene terephthalate permeable membrane as the base material was 35%.
- the coating amount was adjusted so that the thickness of the heat absorption layer was the same as in Example 1-1.
- Example 1-50 including a heat absorption layer having a heat capacity per unit area of 0.00208 J / Kcm 2 and a heat capacity per unit volume of 1.6 J / Kcm 3 was produced.
- This separator is provided with a heat absorption layer partly included in a void in the base material on one surface side and the other surface side of the base material.
- a cylindrical battery of Example 1-50 was produced using this separator.
- Comparative Example 1-1 A cylindrical battery of Comparative Example 1-1 was produced in the same manner as in Example 1-1 except that a polyethylene microporous film having a thickness of 23 ⁇ m was used as a separator.
- Comparative Example 1-2 was performed in the same manner as Example 1-1, except that a separator in which the coating amount of the resin solution was adjusted so that the heat capacity per unit area of the heat absorption layer of the separator was 0.00005 J / Kcm 2 was used. A cylindrical battery was prepared.
- Comparative Example 1-3 A cylindrical battery of Comparative Example 1-3 was produced in the same manner as Example 1-1, except that a separator having a heat absorption layer formed without applying ultrasonic waves to the bathtub during phase separation was used. In Comparative Example 1-3, since no ultrasonic wave was applied when forming the heat absorption layer, the heat capacity per unit volume was not reduced, and the heat capacity per unit volume was 3.5 J / Kcm 3 .
- ⁇ Comparative Example 1-4> The separator in which the heat absorption layer is adjusted without adjusting the coating amount of the resin solution so that the heat capacity per unit area of the heat absorption layer of the separator is 0.00005 J / Kcm 2, and without applying ultrasonic waves to the bathtub during phase separation.
- a cylindrical battery of Comparative Example 1-4 was produced in the same manner as Example 1-1 except that was used. In Comparative Example 1-4, since no ultrasonic wave was applied when forming the heat absorption layer, the heat capacity per unit volume was not reduced, and the heat capacity per unit volume was 3.5 J / Kcm 3 .
- Comparative Example 1-5 A cylindrical battery of Comparative Example 1-1 was produced in the same manner as Comparative Example 1-1 except that silicon was used as the negative electrode active material and the negative electrode mixture slurry had the same configuration as in Example 1-13.
- Comparative Example 1-6 to Comparative Example are the same as Comparative Example 1-2 to Comparative Example 1-4, except that silicon is used as the negative electrode active material and the negative electrode mixture slurry has the same configuration as that of Example 1-13. Cylindrical batteries of 1-8 were produced respectively.
- Comparative Example 1-9 A cylindrical battery of Comparative Example 1-1 was fabricated in the same manner as Comparative Example 1-1 except that a carbon-tin composite material was used as the negative electrode active material and the negative electrode mixture slurry had the same configuration as in Example 1-25. did.
- Comparative Example 1-10 is the same as Comparative Example 1-2 to Comparative Example 1-4 except that a carbon-tin composite material is used as the negative electrode active material and the negative electrode mixture slurry has the same configuration as that of Example 1-25. Each cylindrical battery of Comparative Example 1-12 was produced.
- Comparative Example 1 was the same as Comparative Example 1-1 except that lithium titanate (Li 4 Ti 5 O 12 ) was used as the negative electrode active material, and the negative electrode mixture slurry had the same configuration as Example 1-37. 1 cylindrical battery was produced.
- lithium titanate Li 4 Ti 5 O 12
- the safety valve mechanism will work, but the separator will not shut down or the battery will not break, so the safety valve mechanism will remain in its normal state when the battery temperature drops. It is more preferable because the battery can be used continuously.
- Example 1-1 In Example 1-50, it was confirmed that the battery was in a safe state in the short-circuit test.
- Comparative Example 1-2 in which the heat capacity per unit area of the heat absorption layer of the separator is less than 0.0001 J / Kcm 2
- Comparative Example 1-3 in which the heat capacity per unit volume exceeds 3.0 J / Kcm 3
- Comparative Example 1-4 in which the heat capacity per unit volume and the heat capacity per unit volume are out of the above ranges, it was found that the battery was in a dangerous state in the short circuit test.
- Example 2-1> to ⁇ Example 2-175> and ⁇ Comparative Example 2-1> the effect of the present technology was confirmed by replacing the heat-absorbing particles constituting the heat-absorbing layer of the separator and the resin material.
- Example 2-1> In the same manner as in Example 1-1, boehmite (specific heat 1.2 J / gK) was used as the endothermic particles and polyvinylidene fluoride (PVdF) as the resin material on a polyethylene microporous film having a thickness of 9 ⁇ m.
- Heat absorption layer having a single-sided thickness of 7.5 ⁇ m (both-side thickness of 15 ⁇ m) prepared so that the total heat capacity per area is 0.0006 J / Kcm 2 and the total heat capacity per unit volume is 0.4 J / Kcm 3
- a cylindrical battery using graphite as a negative electrode active material was prepared.
- Example 2-2 A cylindrical battery was fabricated in the same manner as in Example 2-1, except that polyimide was used instead of polyvinylidene fluoride as the resin material used for the heat absorption layer of the separator.
- Example 2-3 A cylindrical battery was fabricated in the same manner as in Example 2-1, except that wholly aromatic polyamide (aramid) was used instead of polyvinylidene fluoride as the resin material used for the heat absorption layer of the separator.
- wholly aromatic polyamide aramid
- Example 2-4 A cylindrical battery was fabricated in the same manner as in Example 2-1, except that polyacrylonitrile was used instead of polyvinylidene fluoride as the resin material used for the heat absorption layer of the separator.
- Example 2-5 A cylindrical battery was fabricated in the same manner as in Example 2-1, except that polyvinyl alcohol was used instead of polyvinylidene fluoride as the resin material used for the heat absorption layer of the separator.
- Example 2-6> A cylindrical battery was fabricated in the same manner as in Example 2-1, except that polyether was used instead of polyvinylidene fluoride as the resin material used for the heat absorption layer of the separator.
- Example 2-7 A cylindrical battery was fabricated in the same manner as in Example 2-1, except that an acrylic resin was used instead of polyvinylidene fluoride as the resin material used for the heat absorption layer of the separator.
- the total heat capacity per unit area of the heat absorption layer is 0.0006 J / Kcm 2 (0.00086 [g / cm 2 ] ⁇ 0.7 [J / gK]).
- the heat capacity per unit area of the heat absorption layer was made constant by adjusting the coating amount of the endothermic particles in the same manner.
- Example 2-15> to ⁇ Example 2-21> Cylindrical type as in Examples 2-1 to 2-7, except that boron nitride (specific heat: 0.8 J / gK) was used instead of boehmite as the endothermic particles used in the heat absorption layer of the separator. A battery was produced.
- boron nitride specific heat: 0.8 J / gK
- Example 2-22> to ⁇ Example 2-28> Cylindrical type as in Example 2-1 to Example 2-7, except that silicon carbide (specific heat: 0.7 J / gK) was used instead of boehmite as the endothermic particles used in the heat absorption layer of the separator. A battery was produced.
- silicon carbide specific heat: 0.7 J / gK
- Example 2-36> to ⁇ Example 2-42> Except that Li 2 O 4 (specific heat: 0.8 J / gK) was used instead of boehmite as the endothermic particles used in the heat absorption layer of the separator, the same as Example 2-1 to Example 2-7, respectively.
- a cylindrical battery was produced.
- Example 2-43> to ⁇ Example 2-49> Except that Li 3 PO 4 (specific heat: 0.8 J / gK) was used instead of boehmite as the endothermic particles used in the heat absorption layer of the separator, the same as Example 2-1 to Example 2-7, respectively. A cylindrical battery was produced.
- Li 3 PO 4 specific heat: 0.8 J / gK
- Example 2-64> to ⁇ Example 2-70> Cylindrical type as in Examples 2-1 to 2-7, except that zirconium oxide (specific heat: 0.7 J / gK) was used instead of boehmite as the endothermic particles used in the heat absorption layer of the separator. A battery was produced.
- zirconium oxide specific heat: 0.7 J / gK
- Example 2-71> to ⁇ Example 2-77> Cylindrical type as in Examples 2-1 to 2-7, except that yttrium oxide (specific heat: 0.5 J / gK) was used instead of boehmite as the endothermic particles used in the heat absorption layer of the separator. A battery was produced.
- yttrium oxide specific heat: 0.5 J / gK
- Example 2-78> to ⁇ Example 2-84> Cylindrical cylinders similar to Examples 2-1 to 2-7, respectively, except that barium titanate (specific heat: 0.8 J / gK) was used instead of boehmite as the endothermic particles used in the heat absorption layer of the separator. A type battery was produced.
- barium titanate specific heat: 0.8 J / gK
- Example 2-85> to ⁇ Example 2-91> Cylindrical cylinders as in Examples 2-1 to 2-7, except that strontium titanate (specific heat: 0.8 J / gK) was used instead of boehmite as the endothermic particles used in the heat absorption layer of the separator. A type battery was produced.
- strontium titanate specific heat: 0.8 J / gK
- Example 2-92> to ⁇ Example 2-98> Cylindrical type as in Examples 2-1 to 2-7, except that silicon oxide (specific heat: 0.8 J / gK) was used instead of boehmite as the endothermic particles used in the heat absorption layer of the separator. A battery was produced.
- silicon oxide specific heat: 0.8 J / gK
- Example 2-106> to ⁇ Example 2-112> Cylindrical type as in Examples 2-1 to 2-7, except that barium sulfate (specific heat: 0.9 J / gK) was used instead of boehmite as the endothermic particles used in the heat absorption layer of the separator. A battery was produced.
- barium sulfate specific heat: 0.9 J / gK
- Example 2-113> to ⁇ Example 2-119> Cylindrical type as in Example 2-1 to Example 2-7, except that titanium oxide (specific heat: 0.8 J / gK) was used instead of boehmite as the endothermic particles used in the heat absorption layer of the separator. A battery was produced.
- Example 2-120> to ⁇ Example 2-126> Cylindrical type as in Example 2-1 to Example 2-7, except that magnesium oxide (specific heat: 1.0 J / gK) was used instead of boehmite as the endothermic particles used in the heat absorption layer of the separator. A battery was produced.
- magnesium oxide specific heat: 1.0 J / gK
- Example 2-134> Cylindrical type as in Examples 2-1 to 2-7, except that carbon nanotubes (specific heat: 0.8 J / gK) were used instead of boehmite as the endothermic particles used in the heat absorption layer of the separator. A battery was produced.
- carbon nanotubes specific heat: 0.8 J / gK
- Example 2-141> to ⁇ Example 2-147> Cylindrical cylinders as in Examples 2-1 to 2-7, except that aluminum hydroxide (specific heat: 1.5 J / gK) was used instead of boehmite as the endothermic particles used in the heat absorption layer of the separator. A type battery was produced.
- aluminum hydroxide specific heat: 1.5 J / gK
- Example 2-148> to ⁇ Example 2-154> Cylindrical type as in Example 2-1 to Example 2-7, except that boron carbide (specific heat: 1.0 J / gK) was used instead of boehmite as the endothermic particles used in the heat absorption layer of the separator. A battery was produced.
- boron carbide specific heat: 1.0 J / gK
- Example 2-155> to ⁇ Example 2-161> Cylindrical type as in Example 2-1 to Example 2-7, except that silicon nitride (specific heat: 0.7 J / gK) was used instead of boehmite as the endothermic particles used in the heat absorption layer of the separator. A battery was produced.
- Example 2-162> to ⁇ Example 2-168> Cylindrical type as in Examples 2-1 to 2-7, except that titanium nitride (specific heat: 0.6 J / gK) was used instead of boehmite as the endothermic particles used in the heat absorption layer of the separator. A battery was produced.
- Example 2-169> to ⁇ Example 2-175> Cylindrical type as in Example 2-1 to Example 2-7, except that zinc oxide (specific heat: 0.5 J / gK) was used instead of boehmite as the endothermic particles used in the heat absorption layer of the separator. A battery was produced.
- zinc oxide specific heat: 0.5 J / gK
- Example 2-1 A cylindrical battery was produced in the same manner as in Example 2-1, except that a polyethylene microporous film having a thickness of 23 ⁇ m was used as a separator.
- the negative electrode mixture slurry for forming the negative electrode active material layer had the same composition as in Example 1-13.
- Example 4 was carried out in the same manner as in Examples 2-1 to 2-175 and Comparative Example 2-1, except that the same carbon-tin composite material as in Example 1-25 was used instead of graphite as the negative electrode active material.
- the cylindrical batteries of -1 to Example 4-175 and Comparative Example 4-1 were produced.
- the negative electrode mixture slurry for forming the negative electrode active material layer had the same composition as in Example 1-25.
- Example 5 was repeated in the same manner as in Example 2-1 to Example 2-175 and Comparative Example 2-1, except that the same lithium titanate as in Example 1-37 was used instead of graphite as the negative electrode active material. Cylindrical batteries of Examples 1 to 175 and Comparative Example 5-1 were produced.
- the negative electrode mixture slurry for forming the negative electrode active material layer had the same composition as in Example 1-37.
- Examples 6-1 to 6-60> batteries were fabricated by changing the battery configuration, the negative electrode active material, and the position of the heat absorption layer of the separator, and the effects of the present technology were confirmed.
- Example 6-1 A cylindrical battery similar to that of Example 1-1 was produced, and the cylindrical battery of Example 6-1 was obtained. That is, the battery configuration was a cylindrical outer can for the battery outer casing and graphite for the negative electrode active material.
- the separator has a heat of 7.5 ⁇ m (both sides thickness: 15 ⁇ m) on one side made of boehmite as an endothermic particle and polyvinylidene fluoride as a resin material on both sides of a polyethylene microporous film having a thickness of 9 ⁇ m. It was set as the structure which provided the absorption layer.
- Example 6-1 except that a separator provided with a heat absorption layer having a thickness of 15 ⁇ m on one side was used only on the positive electrode side surface (the surface facing the positive electrode during battery production) of a polyethylene microporous film having a thickness of 9 ⁇ m. Similarly, a cylindrical battery was produced.
- Example 6-3 Example 6-1 except that a separator having a heat absorption layer with a thickness of 15 ⁇ m on one side was used only on the negative electrode side surface (the surface facing the negative electrode when the battery was produced) of a polyethylene microporous film having a thickness of 9 ⁇ m. Similarly, a cylindrical battery was produced.
- Examples 6-4 to 6 are similar to Examples 6-1 to 6-3 except that silicon is used as the negative electrode active material and the negative electrode mixture slurry has the same configuration as that of Example 1-13. 6-6 cylindrical batteries were produced.
- Example 6-7 was carried out in the same manner as Example 6-1 to Example 6-3, except that a carbon tin composite material was used as the negative electrode active material and the negative electrode mixture slurry had the same structure as in Example 1-25. Each of the cylindrical batteries of Examples 6-9 was produced.
- Example 6-13> A prismatic battery having the same configuration as that of Example 6-1 was prepared for each of the positive electrode, the negative electrode, the separator, and the nonaqueous electrolytic solution. That is, the battery configuration was a rectangular outer can for the battery outer and graphite for the negative electrode active material.
- the separator has a heat of 7.5 ⁇ m (both sides thickness: 15 ⁇ m) on one side made of boehmite as an endothermic particle and polyvinylidene fluoride as a resin material on both sides of a polyethylene microporous film having a thickness of 9 ⁇ m. It was set as the structure which provided the absorption layer.
- a method for assembling the prismatic battery will be described.
- a positive electrode, a negative electrode, and a separator with a heat-adsorbing layer formed on both sides are laminated in the order of the positive electrode, separator, negative electrode, and separator, wound in a flat shape many times in the longitudinal direction, and then the end of winding is adhered.
- a wound electrode body was formed by fixing with a tape.
- the wound electrode body was accommodated in a rectangular battery can.
- the battery can is sealed with the battery lid, and the nonaqueous electrolyte is injected from the electrolyte inlet. And sealed with a sealing member.
- a prismatic battery shown in FIG. 6 having a battery shape of 5.2 mm in thickness, 34 mm in width, 36 mm in height (523436 size), and a battery capacity of 1000 mAh was produced.
- Example 6-14> to ⁇ Example 6-24> The prismatic batteries of Examples 6-14 to 6-24 were made in the same manner as in Examples 6-2 to 6-12 except that the battery configuration was the same as that of Example 6-13. Each was produced.
- Example 6-25> The configuration of each of the positive electrode, the negative electrode, the separator, and the non-aqueous electrolyte was the same as in Example 6-1, and a laminated film type battery in which the laminated electrode body was packaged with a soft laminated film was produced. That is, the battery configuration was a laminate film for the battery exterior, a laminated type for the electrode body, and graphite for the negative electrode active material.
- the separator has a heat of 7.5 ⁇ m (both sides thickness: 15 ⁇ m) on one side made of boehmite as an endothermic particle and polyvinylidene fluoride as a resin material on both sides of a polyethylene microporous film having a thickness of 9 ⁇ m. It was set as the structure which provided the absorption layer.
- a method for assembling the laminated film type battery will be described.
- a rectangular positive electrode and a negative electrode and a separator having a heat adsorption layer formed on both surfaces were laminated in the order of the positive electrode, the separator, the negative electrode, and the separator to form a laminated electrode body.
- the laminated electrode body is covered with a laminate film having a soft aluminum layer, and the lead-out side of the positive electrode terminal and the negative electrode terminal around the laminated electrode body and the other two sides are heat-sealed to form a laminate film into a bag shape. did.
- Example 6-26> to ⁇ Example 6-36> The laminated film type of Examples 6-26 to 6-36 is the same as Example 6-2 to Example 6-12 except that the battery configuration is the same as the laminated film type battery as in Example 6-25. Each battery was produced.
- Example 6-37 The configuration of each of the positive electrode, the negative electrode, the separator, and the non-aqueous electrolyte is the same as that of Example 6-1, and a laminate film type battery in which a gel-like non-aqueous electrolyte and a wound electrode body are packaged with a soft laminate film is produced. did. That is, the battery configuration was a laminate film for the battery exterior, a laminated type for the electrode body, and graphite for the negative electrode active material.
- the separator has a heat of 7.5 ⁇ m (both sides thickness: 15 ⁇ m) on one side made of boehmite as an endothermic particle and polyvinylidene fluoride as a resin material on both sides of a polyethylene microporous film having a thickness of 9 ⁇ m. It was set as the structure which provided the absorption layer.
- a method for assembling the laminated film type battery will be described.
- EC ethylene carbonate
- PC propylene carbonate
- VC vinylene carbonate
- PVdF polyvinylidene fluoride
- a sol precursor solution was prepared by mixing with dimethyl carbonate (DMC).
- DMC dimethyl carbonate
- the precursor solution was applied to both surfaces of the positive electrode and the negative electrode and dried to remove the plasticizer. Thereby, a gel electrolyte layer was formed on the surfaces of the positive electrode and the negative electrode.
- a positive electrode and a negative electrode on which both sides of the gel electrolyte layer are formed and a separator on which the heat-adsorbing layer is formed on both sides are laminated in the order of the positive electrode, the separator, the negative electrode, and the separator. Then, the wound electrode body was formed by fixing the winding end portion with an adhesive tape.
- the wound electrode body is covered with a laminate film having a soft aluminum layer, and the lead-out side of the positive electrode terminal and the negative electrode terminal around the wound electrode body and the other two sides are heat-sealed under reduced pressure and sealed. Stopped and sealed.
- a laminated film type battery shown in FIG. 7 having a battery shape of 5.2 mm in thickness, 34 mm in width, 36 mm in height (523436 size), and a battery capacity of 1000 mAh was produced.
- Example 6-38> to ⁇ Example 6-48> The laminated film type of Examples 6-38 to 6-48 is the same as Example 6-2 to Example 6-12, except that the battery configuration is the same as the laminated film type battery of Example 6-25. Each battery was produced.
- Example 6-49 The configuration of each of the positive electrode, the negative electrode, the separator, and the non-aqueous electrolyte is the same as that of Example 6-1, and a laminate film type battery in which a gel-like non-aqueous electrolyte and a wound electrode body are packaged with a soft laminate film is produced. did. That is, the battery configuration was a laminate film for the battery exterior, a flat wound type for the electrode body, and graphite for the negative electrode active material.
- the separator has a heat of 7.5 ⁇ m (both sides thickness: 15 ⁇ m) on one side made of boehmite as an endothermic particle and polyvinylidene fluoride as a resin material on both sides of a polyethylene microporous film having a thickness of 9 ⁇ m. It was set as the structure which provided the absorption layer.
- a method for assembling the laminated film type battery will be described.
- a positive electrode, a negative electrode, and a separator with a heat-adsorbing layer formed on both sides are laminated in the order of the positive electrode, separator, negative electrode, and separator, wound in a flat shape many times in the longitudinal direction, and then the end of winding is adhered.
- a wound electrode body was formed by fixing with a tape.
- the both surfaces of the positive electrode and the negative electrode were coated with a nonaqueous electrolyte formed into a gel by holding a nonaqueous electrolyte in a polymer material.
- the wound electrode body is covered with a soft laminate film having a soft aluminum layer and a hard laminate film having a hard aluminum layer, and the positive electrode terminal and the negative electrode terminal around the wound electrode body are covered.
- the lead-out side and the other three sides were heat-sealed under reduced pressure and sealed and sealed.
- both ends of the hard laminate film are molded into an elliptical cross section so that the short sides of the hard laminate film are in contact with each other, and the opposing portions of the hard laminate film and the soft laminate film are attached to the battery cell. did.
- the positive electrode lead connected to the positive electrode and the negative electrode lead connected to the negative electrode were connected to the circuit board, and the circuit board was accommodated in the top cover.
- top cover and the bottom cover are respectively inserted and adhered to the battery cell, and the battery shape is 5.2 mm thick, 34 mm wide, 36 mm high (523436 size), and the battery capacity is 1000 mAh, as shown in FIG. A laminate film type battery was produced.
- Example 6-50> to ⁇ Example 6-60> Except for the laminated film type battery similar to that of Example 6-25, the laminated film type of Examples 6-50 to 6-60 was the same as Example 6-2 to Example 6-12. Each battery was produced.
- Example 6-1 to Example 6-3 a battery using a separator provided with a heat absorption layer on both surfaces of the substrate has the highest safety, and a heat absorption layer is provided on one surface of the substrate. In this case, it was found that it is more effective to provide the heat absorption layer on the negative electrode side surface of the substrate than to provide the heat absorption layer on the positive electrode side surface of the substrate.
- Example 7-1> to ⁇ Example 7-76> ⁇ Example 7-1>
- the ratio of the particle shape (“long axis length” / "short axis length") was determined as follows. Fifty particles were randomly selected, and each selected inorganic particle was observed three-dimensionally with a scanning electron microscope.
- a cylindrical battery was produced in the same manner as in Example 7-1.
- a cylindrical battery was fabricated in the same manner as in Example 7-1 except for the above.
- a cylindrical battery was fabricated in the same manner as in Example 7-1 except for the above.
- a cylindrical battery was fabricated in the same manner as in Example 7-1 except for the above.
- a cylindrical battery was fabricated in the same manner as in Example 7-1 except for the above.
- a cylindrical battery was fabricated in the same manner as in Example 7-1 except for the above.
- a cylindrical battery was fabricated in the same manner as in Example 7-1 except for the above.
- a cylindrical battery was fabricated in the same manner as in Example 7-1 except for the above.
- a cylindrical battery was fabricated in the same manner as in Example 7-1 except for the above.
- a cylindrical battery was fabricated in the same manner as in Example 7-1 except for the above.
- a cylindrical battery was fabricated in the same manner as in Example 7-1 except for the above.
- a cylindrical battery was fabricated in the same manner as in Example 7-1 except for the above.
- a cylindrical battery was fabricated in the same manner as in Example 7-1 except for the above.
- a cylindrical battery was fabricated in the same manner as in Example 7-1 except for the above.
- a cylindrical battery was fabricated in the same manner as in Example 7-1 except for the above.
- a cylindrical battery was fabricated in the same manner as in Example 7-1 except for the above.
- a cylindrical battery was fabricated in the same manner as in Example 7-1 except for the above.
- a cylindrical battery was fabricated in the same manner as in Example 7-1 except for the above.
- a cylindrical battery was fabricated in the same manner as in Example 7-1 except for the above.
- a cylindrical battery was produced in the same manner as in Example 7-1.
- a cylindrical battery was fabricated in the same manner as in Example 7-1 except for the above.
- a cylindrical battery was fabricated in the same manner as in Example 7-1 except for the above.
- a cylindrical battery was fabricated in the same manner as in Example 7-1 except for the above.
- a cylindrical battery was fabricated in the same manner as in Example 7-1 except for the above.
- a cylindrical battery was fabricated in the same manner as in Example 7-1 except for the above.
- a cylindrical battery was fabricated in the same manner as in Example 7-1 except for the above.
- the nonaqueous electrolyte battery may be a primary battery.
- a separator having a heat absorption layer provided on the surface of the substrate is used.
- the heat absorption layer may be present at the boundary between the substrate and at least one of the positive electrode and the negative electrode.
- the separator may have a conventional configuration, and a heat absorption layer may be formed on at least one of the positive electrode surface or the negative electrode surface.
- a predetermined amount of a resin solution in which inorganic particles and a resin material are dissolved is applied to the positive electrode surface and the negative electrode surface so that the heat capacity per area is within the range of the present technology.
- the heat absorption layer may be formed by adjusting the energy of ultrasonic waves so as to be within the technical range.
- this technique can also take the following structures.
- a substrate A layer having a heat capacity per unit area of 0.0001 J / Kcm 2 or more and a heat capacity per unit volume of 3.0 J / Kcm 3 or less formed on at least one surface of the base material;
- the layer contains particles and a resin material,
- the particles are boehmite, yttrium oxide, titanium oxide, magnesium oxide, zirconium oxide, silicon oxide, zinc oxide, aluminum nitride, boron nitride, silicon nitride, titanium nitride, silicon carbide, boron carbide, barium titanate, strontium titanate,
- a separator containing at least one selected from barium sulfate, porous aluminosilicate, layered silicate, Li 2 O 4 , Li 3 PO 4 , LiF, aluminum hydroxide, graphite, carbon nanotube, and diamond.
- a substrate It is formed on at least one surface side of the base material, at least a part is included in the voids in the base material, the heat capacity per unit area is 0.0001 J / Kcm 2 or more, and the heat capacity per unit volume is A layer that is 3.0 J / Kcm 3 or less,
- the layer contains particles and a resin material, The particles are boehmite, yttrium oxide, titanium oxide, magnesium oxide, zirconium oxide, silicon oxide, zinc oxide, aluminum nitride, boron nitride, silicon nitride, titanium nitride, silicon carbide, boron carbide, barium titanate, strontium titanate, A separator containing at least one selected from barium sulfate, porous aluminosilicate, layered silicate, Li 2 O 4 , Li 3 PO 4 , LiF, aluminum hydroxide, graphite, carbon nanotube, and diamond.
- the layer contains particles and a resin material, The particles are boehmite, yttrium oxide, titanium oxide, magnesium oxide, zirconium oxide, silicon oxide, zinc oxide, aluminum nitride, boron nitride, silicon nitride, titanium nitride, silicon carbide, boron carbide, barium titanate, strontium titanate, A battery containing at least one selected from barium sulfate, porous aluminosilicate, layered silicate
- the negative electrode active material contained in the negative electrode is made of a material containing at least one of a metal element and a metalloid element as a constituent element.
- the layer contains particles and a resin material,
- the particles are boehmite, yttrium oxide, titanium oxide, magnesium oxide, zirconium oxide, silicon oxide, zinc oxide, aluminum nitride, boron nitride, silicon nitride, titanium nitride, silicon carbide, boron carbide, barium titanate, strontium titanate,
- the power storage device further including a power information control device that transmits and receives signals to and from other devices via a network, and that performs charge / discharge control of the battery based on information received by the power information control device.
- a power information control device that transmits and receives signals to and from other devices via a network, and that performs charge / discharge control of the battery based on information received by the power information control device.
- a power system that receives power from the battery according to any one of [17], or that supplies power to the battery from a power generation device or a power network.
- negative electrode lead, 30 nonaqueous electrolyte battery, 31 ... outer can, 32 ... battery lid 33 ... Electrode pin, 34 ... Insulator, 35 ... Through-hole, 36 ... Internal pressure release mechanism, 36a ... First opening groove, 36b ... Second opening groove, 37 ... Electrolyte injection port, 38 ... Sealing member 40 ... wound electrode body, 41 ... positive electrode terminal, 5 DESCRIPTION OF SYMBOLS ... Winding electrode body, 51 ... Positive electrode lead, 52 ... Negative electrode lead, 53 ... Positive electrode, 53A ... Positive electrode collector, 53B ... Positive electrode active material layer, 54 ... Negative electrode, 54A ... Negative electrode collector, 54B ... Negative electrode active material Layer, 55 ...
- Electric power driving force converter 204a, 204b ... Driving wheel, 205a, 205b ... Wheel, 208 ... Battery, 209 ... Vehicle control device, 210 ... Various sensors, 211 ... Charging port, 301 ... assembled battery, 301a ... secondary battery, 302a ... charge control switch, 3 02b ... Diode 303a ... Discharge control switch 303b ... Diode 304 ... Switch unit 307 ... Current detection resistor 308 ... Temperature detection element 310 ... Control unit 311 ... Voltage detection unit 313 ... Current measurement unit 314 ... Switch control unit, 317 ... memory, 318 ... temperature detection unit, 321 ... positive terminal, 322 ... negative terminal
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Abstract
Description
1.第1の実施の形態(本技術のセパレータの例)
2.第2の実施の形態(本技術のセパレータを用いた円筒型電池の例)
3.第3の実施の形態(本技術のセパレータを用いた角型電池の例)
4.第4の実施の形態(本技術のセパレータを用いたラミネートフィルム型電池の例)
5.第5の実施の形態(本技術のセパレータを用いたラミネートフィルム型電池の電池パックの例)
6.第6の実施の形態(電池を用いた電池パックの例)
7.第7の実施の形態(電池を用いた蓄電システム等の例)
第1の実施の形態に係るセパレータは、基材の少なくとも一方の面に熱吸収層を形成したものである。以下、本技術のセパレータについて詳細に説明する。
第1の実施の形態に係るセパレータ1は、図1に示すように、多孔質膜からなる基材2と、基材2の少なくとも一方の面に形成される熱吸収層3とを備える。セパレータ1は、電池内において正極と負極とを隔離し、両極の接触による電流の短絡を防止するとともに、非水電解質が含浸される。セパレータ1の熱吸収層3は、一方の電極で発生した熱を吸収する吸熱効果を有し、かつこの熱が他方の電極に伝わることを防止する断熱効果を有する。
基材2は、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膜から構成される多孔質膜である。非水電解質電池にセパレータ1が適用された場合には、基材2の空孔に非水電解液が保持される。基材2は、セパレータ1の主要部として所定の機械的強度を有する一方で、非水電解液に対する耐性が高く、反応性が低く、膨張しにくいという特性を要する。また、巻回構造を有する電極体に用いられる場合には、柔軟性も必要とされる。
微多孔膜は、樹脂等の材料が薄く延伸されたものであり、且つ、多孔構造を有するものである。例えば、微多孔膜は、樹脂等の材料を延伸開孔法、相分離法などで成形することにより得たものである。例えば、延伸開口法では、まず、溶融ポリマーをTダイやサーキュラーダイから押し出し、さらに熱処理を施し規則性の高い結晶構造を形成する。その後、低温延伸、更には高温延伸して結晶界面を剥離させてラメラ間に間隔部分を作り、多孔構造を形成する。相分離法では、ポリマーと溶剤とを高温で混合して調製した均一溶液を、Tダイ法、インフレーション法などでフィルム化した後、溶剤を別の揮発性溶剤で抽出することにより、微多孔膜を得ることができる。なお、微孔膜の製造方法は、これらに限定されるものではなく、従来提案されている方法を広く用いることができる。
不織布は、繊維を織ったり編んだりしないで、機械的、化学的、若しくは、溶剤、またはこれらを組み合わせて、繊維間を接合若しくは絡合、または接合および絡合によって作られた構造物であり、後述の紙を除いたものをいう。不織布の原料には繊維に加工できるほとんどの物質を使用することができ、繊維長や太さなどの形状を調整することで、目的、用途に応じた機能を持たせることができる。不織布の製造方法は、典型的には、フリースと呼ばれる繊維の集積層を形成する工程と、フリースの繊維間を結合する結合工程との2段階がある。それぞれの段階において、様々な製造方法があり、不織布の原料、目的、用途に応じて選択される。例えば、フリースを形成する工程としては、乾式法、湿式法、スパンボンド法、メルトブロー法等を用いることができる。フリースの繊維間を結合する結合工程としては、サーマルボンド法、ケミカルボンド法、ニードルパンチ法、スパンレース法(水流絡合法)、ステッチボンド法、スチームジェット法等を用いることができる。
紙は、狭義の紙のことをいい、例えば、パルプを用いて抄造されたものをいう。パルプとは、木材その他の植物等から、機械的、または化学的処理によって抽出した植物繊維の集合体のことをいう。パルプ以外の材料(例えば、タルク等の鉱物等)を混合して抄造された混抄紙も、紙に含まれる。紙としては、セルロースパルプを用いて抄造されたセルロース透気性膜などを用いることができる。なお、湿式法を用いた湿式不織布と紙とを区別する場合には、ISO 9092の定義に準じて区別する。すなわち、長さ対直径の比(アスペクト比)が300以上の繊維が質量比で50%以上であるもの、あるいは、密度が0.4g/cc以下の場合、長さ対直径の比が300以上の繊維が質量比で30%以上であるものを湿式不織布とし、それ以外は紙と区別する。
熱吸収層3は、基材2の少なくとも一方の面に形成された層であり、主として負極で発生した熱を吸収し、かつ負極で発生した熱が正極に伝わらないようにする機能を有する多孔質層である。非水電解質電池にセパレータ1が適用された場合には、熱吸収層3の空孔に非水電解液が保持される。熱吸収層3は、耐熱性を有する樹脂材料と、耐熱性および耐酸化性に優れる吸熱粒子として機能する無機粒子および有機粒子の少なくとも何れか等の固体粒子等の粒子とを含有する。熱吸収層3は、熱を伝わりにくくすることを目的として、粒子が分散して存在するようにすることが好ましい。なお、本技術において、分散とは、粒子もしくは二次粒子化した粒子群が連結されずに点在する状態を示すが、粒子もしくは二次粒子化した粒子群の一部は連結された状態であってもよい。すなわち、熱吸収層3全体として、粒子が分散した状態が好ましい。
以下、熱吸収層3を設けたセパレータ1の製造方法について説明する。
熱吸収層3を構成する樹脂材料と粒子とを所定の質量比で混合し、N-メチル-2-ピロリドン等の分散溶媒に添加し、樹脂材料を溶解させて樹脂溶液を得る。続いて、この樹脂溶液を、基材2の少なくとも一方の面に塗布もしくは転写する。なお、単位面積あたりの熱容量の総和が0.0001J/Kcm2以上という本技術の条件を満たすように単位面積あたりの粒子量を調整して樹脂溶液を塗布もしくは転写する。樹脂溶液の塗布方法としては、バーコータ等により塗布する方法が挙げられる。また、樹脂溶液の転写方法としては、表面に凹凸形状を有するローラ等の表面に樹脂溶液を塗布して基材2の表面に樹脂溶液を転写する方法等が挙げられる。ここで、表面に凹凸形状を有する樹脂溶液転写用のローラ等の表面形状は、図3に一例を示す種々の形状とすることができる。
樹脂溶液は、樹脂溶液中における固形分(粒子と樹脂材料と合計量)の濃度を、所望の濃度に調整する。樹脂溶液中における固形分の比率が少ないほど、完成後の熱吸収層3をより疎な状態とすることができる。
樹脂溶液の塗布方法として、バーコータ等により塗布する方法を用いる場合には、基材2上に略均一な樹脂溶液の層が形成される。ここで、必要に応じて、樹脂溶液の層の表面に凹凸形状を設けてもよい。樹脂溶液の層の表面に凹凸形状を設ける場合には、例えば、霧状の水(貧溶媒)を塗布された樹脂溶液の表面に接触させる。これにより、塗布された樹脂溶液のうち、霧状の水と接触した部分が凹状となり、その周辺部が凸状となることにより、樹脂溶液表面が斑紋状に変形するとともに、水と接触した一部分で水と分散溶媒の置換が生じて斑紋状の表面形状に固定される。この後、樹脂溶液を塗布した基材2を水浴に浸漬して塗布した樹脂溶液全体を相分離させることにより、表面に凹凸形状を有する熱吸収層3を形成することができる。
表面に凹凸形状を有するローラ等の表面に樹脂溶液を塗布して基材2の表面に樹脂溶液を転写する方法を用いる場合には、凸部の面積割合が少ないほどより疎な状態とすることができる。凸部の面積割合は、ローラ等の表面の凹凸形状を変えることで調整することができる。また、凸部の高さ(凸部と凹部との高低差)が大きいほどより疎な状態とすることができる。凸部の高さは、ローラ等の表面の凹凸形状と、樹脂溶液の粘度によって調整することができる。樹脂溶液の粘度は、樹脂溶液中における固形分比率によって調整することができる。
樹脂溶液が塗布された基材2を水浴に浸漬して樹脂溶液を相分離させる際に、浴槽に超音波を加えることが好ましい。この際の超音波のエネルギーが大きいほど、完成後の熱吸収層3をより疎な状態とすることができる。なお、樹脂溶液を相分離させる際に、浴槽に超音波を加えることにより、粒子もしくは二次粒子化した粒子群が互いに独立して分散状態にすることができるためより好ましい。また、相分離の速度を調整することによっても、熱吸収層3の状態を制御することができる。相分離の速度は、例えば、相分離時に用いる、分散溶媒に対して良溶媒である水等の溶媒中に、N-メチル-2-ピロリドン等の分散溶媒を少量添加することで調整可能である。例えば、水に混合するN-メチル-2-ピロリドンの混合量が多いほど、相分離の速度が遅くなり、水のみを用いて相分離を行った場合にはもっとも急激に相分離が生じる。相分離の速度が遅いほど完成後の熱吸収層3をより疎な状態とすることができる。
熱吸収層3を構成する樹脂材料と粒子とを所定の質量比で混合し、2-ブタノン(メチルエチルケトン;MEK)、N-メチル-2-ピロリドン(NMP)等の分散溶媒に添加し、溶解させて、樹脂溶液を得る。続いて、この樹脂溶液を、基材2の少なくとも一方の面に塗布する。なお、単位面積あたりの熱容量の総和が0.0001J/Kcm2以上という本技術の条件を満たすように単位面積あたりの粒子量を調整して樹脂溶液を塗布する。
本技術の熱吸収層3は、基材2と正極および負極の少なくとも一方との境界に存在する層であればよく、必ずしもセパレータ1の一部の層(表面層)である必要はない。すなわち、本技術の他の例として、従来の構成(基材2のみからなる構成)を有するセパレータを用い、正極表面もしくは負極表面の少なくとも一方に熱吸収層を形成することも考えられる。正極表面もしくは負極表面の少なくとも一方に熱吸収層を形成する場合には、1枚のセパレータを介して対向する正極および負極の少なくとも一方に必ず熱吸収層3が形成されるようにする。このような構成の場合には、電極表面への熱吸収層の形成方法として、第2の製造方法を適用することができる。
第2の実施の形態では、第1の実施の形態にかかるセパレータを用いた円筒型非水電解質電池について説明する。
[非水電解質電池の構造]
図4は、第2の実施の形態にかかる非水電解質電池10の一例を示す断面図である。非水電解質電池10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る。この非水電解質電池10は、いわゆる円筒型と呼ばれるものであり、ほぼ中空円柱状の電池缶11の内部に、図示しない液体状の非水電解質(以下、非水電解液と適宜称する)とともに帯状の正極21と負極22とがセパレータ23を介して巻回された巻回電極体20を有している。巻回電極体20は、活物質層の膨張・収縮によって、セパレータの巻回方向に引張応力がかかりやすい。このため、本技術のセパレータは、巻回電極体20を有する非水電解質電池10に適用することが好ましい。
正極21は、正極活物質を含有する正極活物質層21Bが、正極集電体21Aの両面上に形成されたものである。正極集電体21Aとしては、例えばアルミニウム(Al)箔、ニッケル(Ni)箔あるいは、ステンレス(SUS)箔等の金属箔を用いることができる。
負極22は、例えば、対向する一対の面を有する負極集電体22Aの両面に負極活物質層22Bが設けられた構造を有している。なお、図示はしないが、負極集電体22Aの片面のみに負極活物質層22Bを設けるようにしてもよい。負極集電体22Aは、例えば、銅箔等の金属箔により構成されている。
セパレータ23は、第1の実施の形態にかかるセパレータ1と同様である。
非水電解液は、電解質塩と、この電解質塩を溶解する非水溶媒とを含む。
[正極の製造方法]
正極活物質と、導電剤と、結着剤とを混合して正極合剤を調製し、この正極合剤をN-メチル-2-ピロリドン等の溶剤に分散させてペースト状の正極合剤スラリーを作製する。次に、この正極合剤スラリーを正極集電体21Aに塗布し溶剤を乾燥させ、ロールプレス機等により圧縮成型することにより正極活物質層21Bを形成し、正極21を作製する。
負極活物質と、結着剤とを混合して負極合剤を調製し、この負極合剤をN-メチル-2-ピロリドン等の溶剤に分散させてペースト状の負極合剤スラリーを作製する。次に、この負極合剤スラリーを負極集電体22Aに塗布し溶剤を乾燥させ、ロールプレス機等により圧縮成型することにより負極活物質層22Bを形成し、負極22を作製する。
非水電解液は、非水溶媒に対して電解質塩を溶解させて調製する。
正極集電体21Aに正極リード25を溶接等により取り付けると共に、負極集電体22Aに負極リード26を溶接等により取り付ける。その後、正極21と負極22とを本技術のセパレータ23を介して巻回し巻回電極体20とする。正極リード25の先端部を安全弁機構に溶接すると共に、負極リード26の先端部を電池缶11に溶接する。この後、巻回電極体20の巻回面を一対の絶縁板12,13で挟み、電池缶11の内部に収納する。巻回電極体20を電池缶11の内部に収納したのち、非水電解液を電池缶11の内部に注入し、セパレータ23に含浸させる。そののち、電池缶11の開口端部に電池蓋13、安全弁14等からなる安全弁機構および熱感抵抗素子17をガスケット18を介してかしめることにより固定する。これにより、図4に示した本技術の非水電解質電池10が形成される。
本技術のセパレータを用いた円筒型非水電解質電池では、負極での発熱、特に、金属元素および半金属元素のうちの少なくとも1種を構成元素として含む負極活物質を用いた負極での発熱を、熱吸収層で吸収するとともに、熱吸収層で断熱することができる。このため、負極での発熱が正極に伝わりにくくなり、正極の熱分解反応を抑制することができる。また、高温での発熱によるセパレータの溶融時においても、熱吸収層により絶縁性を維持することができる。
第3の実施の形態では、第1の実施の形態にかかるセパレータを用いた角型非水電解質電池について説明する。
図6は、第3の実施の形態にかかる非水電解質電池30の構成を表すものである。この非水電解質電池は、いわゆる角型電池といわれるものであり、巻回電極体40を角型の外装缶31内に収容したものである。
セパレータは、第1の実施の形態におけるセパレータ1と同様の構成とすることができる。
非水電解液は、第2の実施の形態に記載されたものを用いることができる。また、第2の実施の形態で記載したような、非水電解液を高分子化合物に保持させたゲル電解質を用いてもよい。
この非水電解質電池は、例えば、次のようにして製造することができる。
正極および負極は、第2の実施の形態と同様の方法により作製することができる。
正極と負極と、本技術のセパレータとを順に積層および巻回し、小判型に細長く巻回された巻回電極体40を作製する。続いて、巻回電極体40を外装缶31内に収容する。
第3の実施の形態は、第2の実施の形態と同様の効果を得ることができる。
第4の実施の形態では、第1の実施の形態にかかるセパレータを用いたラミネートフィルム型非水電解質電池について説明する。
図7は、第4の実施の形態にかかる非水電解質電池62の構成を表すものである。この非水電解質電池62は、いわゆるラミネートフィルム型といわれるものであり、正極リード51および負極リード52が取り付けられた巻回電極体50をフィルム状の外装部材60の内部に収容したものである。
正極53は、正極集電体53Aの片面あるいは両面に正極活物質層53Bが設けられた構造を有している。正極集電体53A、正極活物質層53Bの構成は、上述した第2の実施の形態の正極集電体21Aおよび正極活物質層21Bと同様である。
負極54は、負極集電体54Aの片面あるいは両面に負極活物質層54Bが設けられた構造を有しており、負極活物質層54Bと正極活物質層53Bとが対向するように配置されている。負極集電体54A、負極活物質層54Bの構成は、上述した第2の実施の形態の負極集電体22Aおよび負極活物質層22Bと同様である。
セパレータ55は、第1の実施の形態にかかるセパレータ1と同様である。
ゲル電解質56は非水電解質であり、非水電解液と非水電解液を保持する保持体となる高分子化合物とを含み、いわゆるゲル状となっている。ゲル状の電解質は高いイオン伝導率を得ることができると共に、電池の漏液を防止することができるので好ましい。なお、第4の実施の形態における非水電解質電池62においては、ゲル電解質56の代わりに第2の実施の形態と同様の非水電解液を用いてもよい。
この非水電解質電池62は、例えば、次のようにして製造することができる。
正極53および負極54は、第2の実施の形態と同様の方法により作製することができる。
正極53および負極54のそれぞれの両面に、非水電解液と、高分子化合物と、混合溶剤とを含む前駆溶液を塗布し、混合溶剤を揮発させてゲル電解質56を形成する。そののち、正極集電体53Aの端部に正極リード51を溶接により取り付けると共に、負極集電体54Aの端部に負極リード52を溶接により取り付ける。
第4の実施の形態では、巻回電極体50が外装部材60で外装された非水電解質電池62について説明したが、図9A~図9Cに示すように、巻回電極体50の代わりに積層電極体70を用いてもよい。図9Aは、積層電極体70を収容した非水電解質電池62の外観図である。図9Bは、外装部材60に積層電極体70が収容される様子を示す分解斜視図である。図9Cは、図9Aに示す非水電解質電池62の底面側からの外観を示す外観図である。
第4の実施の形態では、第2の実施の形態と同様の効果を得ることができる。
第5の実施の形態では、第1の実施の形態にかかるセパレータを用いたラミネートフィルム型非水電解質電池の電池パックの例について説明する。
図10は、第5の実施の形態にかかる電池パック90の一構成例を示す斜視図である。図11は、電池セル80の構造を示す分解斜視図である。図12は、第5の実施の形態にかかる電池セル80の製造途中の状態を示す上面図および側面図である。図13は、電池セル80における断面構造を示す断面図である。
図11および図12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4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4の実施の形態と同様の構成とすることができる。また、第4の実施の形態の他の例で説明した積層電極体70を用いてもよい。
電池セル80に注液される非水電解液もしくは正極53および負極54の表面に形成されるゲル電解質は、第2の実施の形態と同様の構成とすることができる。
セパレータ55は、本技術のセパレータ1を用いることができる。また、第1の実施の形態における基材2をセパレータとし、熱吸収層3を正極53および負極54の表面に設ける構成としてもよい。
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。
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5の実施の形態では、第2の実施の形態と同様の効果を得ることができる。
第6の実施の形態では、第1の実施の形態にかかるセパレータを用いた非水電解質電池が備えられた電池パックについて説明する。
第7の実施の形態では、第2~第4の実施の形態にかかる非水電解質電池および第5および第6の実施の形態にかかる電池パックを搭載した電子機器、電動車両および蓄電装置等の機器について説明する。第2~第5の実施の形態で説明した非水電解質電池および電池パックは、電子機器や電動車両、蓄電装置等の機器に電力を供給するために使用することができる。
本技術の非水電解質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15を参照して説明する。例えば住宅101用の蓄電システム100においては、火力発電102a、原子力発電102b、水力発電102c等の集中型電力系統102から電力網109、情報網112、スマートメータ107、パワーハブ108等を介し、電力が蓄電装置103に供給される。これと共に、家庭内発電装置104等の独立電源から電力が蓄電装置103に供給される。蓄電装置103に供給された電力が蓄電される。蓄電装置103を使用して、住宅101で使用する電力が給電される。住宅101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16を参照して説明する。図16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。
下記の実施例1-1~実施例1-50及び比較例1-1~比較例1-16では、熱吸収層の単位面積あたり熱容量と、単位体積あたり熱容量とを調整したセパレータを用いて、本技術の効果を確認した。
[正極の作製]
正極活物質であるコバルト酸リチウム(LiCoO2)91質量%と、導電材であるカーボンブラック6質量%と、結着剤であるポリフッ化ビニリデン(PVdF)3質量%とを混合して正極合剤を調製し、この正極合剤を分散媒である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とした。この正極合剤スラリーを厚さ12μmの帯状アルミニウム箔からなる正極集電体の両面に、正極集電体の一部が露出するようにして塗布した。この後、塗布した正極合剤スラリーの分散媒を蒸発・乾燥させ、ロールプレスにて圧縮成型することにより、正極活物質層を形成した。最後に、正極端子を正極集電体露出部に取り付け、正極を形成した。
負極活物質である平均粒径20μmの粒状黒鉛粉末96質量%と、結着剤としてスチレン-ブタジエン共重合体のアクリル酸変性体1.5質量%と、増粘剤としてカルボキシメチルセルロース1.5質量%とを混合して負極合剤とし、さらに適量の水を加えて攪拌することにより、負極合剤スラリーを調製した。この負極合剤スラリーを厚さ15μmの帯状銅箔からなる負極集電体の両面に、負極集電体の一部が露出するようにして塗布した。この後、塗布した負極合剤スラリーの分散媒を蒸発・乾燥させ、ロールプレスにて圧縮成型することにより、負極活物質層を形成した。最後に、負極端子を負極集電体露出部に取り付け、負極を形成した。
基材として厚さ9μm、空孔率35%のポリエチレン(PE)製微多孔性フィルムを用いた。この基材の両面に、下記の様にして熱吸収層を形成した。まず、吸熱粒子である平均粒径0.8μmのベーマイト(比熱:1.2J/gK)と、樹脂材料であるポリフッ化ビニリデン(PVdF)とを質量比で9:1となるように混合し、N-メチル-2-ピロリドン(NMP)に分散させて樹脂溶液を作製した。続いて、この樹脂溶液を、基材の両面に同じ厚みかつ均一に塗布した後、樹脂溶液が塗布された基材を超音波により水を振動させた水浴に浸漬して相分離させ、樹脂溶液中のN-メチル-2-ピロリドン(NMP)を除去した。
炭酸エチレン(EC)と炭酸ビニレン(VC)と炭酸ジエチル(DEC)とを、質量比30:10:60で混合した非水溶媒に対して、電解質塩として六フッ化リン酸リチウム(LiPF6)を1mol/dm3の濃度で溶解させることにより、非水電解液を調製した。
正極および負極と、熱吸着層が両面に形成されたセパレータとを、正極、セパレータ、負極、セパレータの順に積層し、長手方向に多数回巻回させた後、巻き終わり部分を粘着テープで固定することにより巻回電極体を形成した。次に、正極端子を電池蓋と接合された安全弁に接合すると共に、負極リードを負極缶に接続した。巻回電極体を一対の絶縁板で挟んで電池缶の内部に収納した後、巻回電極体の中心にセンターピンを挿入した。
セパレータの熱吸収層形成時において、超音波の強さを調整することにより、熱吸収層の厚みを調整して、熱吸収層の単位体積あたりの熱容量が表1に示す値となるようにした。これにより、単位面積あたりの熱容量が0.0006J/Kcm2であり、単位体積あたりの熱容量がそれぞれ0.2J/Kcm3、0.3J/Kcm3、1.0J/Kcm3、1.5J/Kcm3、2.5J/Kcm3および3.0J/Kcm3である熱吸収層を備える実施例1-2~実施例1-7のセパレータをそれぞれ作製した。このセパレータをそれぞれ用いて、実施例1-2~実施例1-7の円筒型電池を作製した。
基材に対する樹脂溶液塗布時において、樹脂溶液の塗布厚みによって熱吸収層の単位面積あたりの熱容量を調節した。具体的には、熱吸収層の単位面積あたりの熱容量がそれぞれ0.0001J/Kcm2、0.0002J/Kcm2、0.0010J/Kcm2、0.0013J/Kcm2、0.0015J/Kcm2となるようにした。続いて、セパレータの熱吸収層形成時において、超音波のエネルギーを調整することにより、熱吸収層の厚みをそれぞれ調整して、熱吸収層の単位体積あたりの熱容量が0.4J/Kcm3となるようにし、実施例1-8~実施例1-12のセパレータをそれぞれ作製した。このセパレータをそれぞれ用いて、実施例1-8~実施例1-12の円筒型電池を作製した。
負極活物質層形成時に、負極活物質として黒鉛の代わりにシリコン粉末を用いた。負極活物質であるシリコン(Si)粒子85質量%と、導電材であるカーボンブラック10質量%と、結着剤であるポリフッ化ビニリデン(PVdF)5質量%とを混合して負極合剤を調製し、この負極合剤を分散媒であるN-メチル-2-ピロリドン(NMP)に分散させて負極合剤スラリーとした。この負極合剤スラリーを用いた以外は実施例1-1~実施例1-12と同様にして実施例1-13~実施例1-24の円筒型電池をそれぞれ作製した。
負極活物質層形成時に、負極活物質として黒鉛の代わりに炭素スズ複合材料を用いた。炭素スズ複合材料としては、スズ(Sn)とコバルト(Co)と炭素(C)とを構成元素として含み、組成がスズの含有量が22質量%、コバルトの含有量が55質量%、炭素の含有量が23質量%、スズおよびコバルトの合計に対するスズの割合(Co/(Sn+Co))が71.4質量%であるSnCoC含有材料を用いた。
負極活物質層形成時に、負極活物質として黒鉛の代わりにチタン酸リチウム(Li4Ti5O12)を用いた。負極活物質としてチタン酸リチウム(Li4Ti5O12)85質量%と、導電剤として黒鉛10質量%と、結着剤としてポリフッ化ビニリデン(PVdF)5質量%とを混合して負極合剤とした。続いて、N-メチル-2-ピロリドンに負極合剤を分散させて、ペースト状の負極合剤スラリーを調製した。この負極合剤スラリーを用いた以外は実施例1-1~実施例1-12と同様にして実施例1-37~実施例1-48の円筒型電池をそれぞれ作製した。
基材として、厚さ9μm、紙である空孔率60%のセルロース透気性膜を用いた。実施例1-1と同様の樹脂溶液を、基材の両面に同じ厚みかつ均一に塗布した。この際、基材であるセルロース透気性膜の空隙にも、塗料を含浸させた。その後、樹脂溶液が塗布された基材を超音波により水を振動させた水浴に浸漬して相分離させ、その後、樹脂溶液中のN-メチル-2-ピロリドン(NMP)を除去した。その後、樹脂溶液が塗布された基材を乾燥機中にくぐらせることにより、水と残留NMPを除去し、樹脂材料およびベーマイトからなる熱吸収層を形成した。セパレータの熱吸収層形成時には、基材であるセルロース透気性膜内の空孔率が35%となるように超音波の強さを調整した。また、熱吸収層の厚みが実施例1-1と同じになるよう塗料の塗布量を調整した。
基材として、厚さ9μm、不織布である空孔率80%のポリエチレンテレフタレート(PET)透気性膜を用いた。実施例1-1と同様の樹脂溶液を、基材の両面に同じ厚みかつ均一に塗布した。この際、基材であるポリエチレンテレフタレート透気性膜の空隙にも、塗料を含浸させた。その後、樹脂溶液が塗布された基材を超音波により水を振動させた水浴に浸漬して相分離させ、その後、樹脂溶液中のN-メチル-2-ピロリドン(NMP)を除去した。その後、樹脂溶液が塗布された基材を乾燥機中にくぐらせることにより、水と残留NMPを除去し、樹脂材料およびベーマイトからなる熱吸収層を形成した。セパレータの熱吸収層形成時には、基材であるポリエチレンテレフタレート透気性膜内の空孔率が35%となるように超音波の強さを調整した。また、熱吸収層の厚みが実施例1-1と同じになるよう塗料の塗布量を調整した。
厚さ23μmのポリエチレン製微多孔性フィルムをセパレータとして用いた以外は実施例1-1と同様にして比較例1-1の円筒型電池を作製した。
セパレータの熱吸収層の単位面積あたりの熱容量が0.00005J/Kcm2となるように樹脂溶液の塗布量を調整したセパレータを用いた以外は実施例1-1と同様にして比較例1-2の円筒型電池を作製した。
相分離時に浴槽に超音波を加えずに熱吸収層を形成したセパレータを用いた以外は実施例1-1と同様にして比較例1-3の円筒型電池を作製した。比較例1-3では、熱吸収層形成時に超音波を加えなかったため、単位体積あたりの熱容量が小さくならず、単位体積あたりの熱容量が3.5J/Kcm3となった。
セパレータの熱吸収層の単位面積あたりの熱容量が0.00005J/Kcm2となるように樹脂溶液の塗布量を調整するとともに、相分離時に浴槽に超音波を加えずに熱吸収層を形成したセパレータを用いた以外は実施例1-1と同様にして比較例1-4の円筒型電池を作製した。比較例1-4では、熱吸収層形成時に超音波を加えなかったため、単位体積あたりの熱容量が小さくならず、単位体積あたりの熱容量が3.5J/Kcm3となった。
負極活物質としてシリコンを用い、負極合剤スラリーを実施例1-13と同様の構成とした以外は、比較例1-1と同様にして比較例1-1の円筒型電池を作製した。
負極活物質としてシリコンを用い、負極合剤スラリーを実施例1-13と同様の構成とした以外は、比較例1-2~比較例1-4と同様にして比較例1-6~比較例1-8の円筒型電池をそれぞれ作製した。
負極活物質として炭素スズ複合材料を用い、負極合剤スラリーを実施例1-25と同様の構成とした以外は、比較例1-1と同様にして比較例1-1の円筒型電池を作製した。
負極活物質として炭素スズ複合材料を用い、負極合剤スラリーを実施例1-25と同様の構成とした以外は、比較例1-2~比較例1-4と同様にして比較例1-10~比較例1-12の円筒型電池をそれぞれ作製した。
負極活物質としてチタン酸リチウム(Li4Ti5O12)を用い、負極合剤スラリーを実施例1-37と同様の構成とした以外は、比較例1-1と同様にして比較例1-1の円筒型電池を作製した。
負極活物質としてチタン酸リチウム(Li4Ti5O12)を用い、負極合剤スラリーを実施例1-37と同様の構成とした以外は、比較例1-2~比較例1-4と同様にして比較例1-14~比較例1-16の円筒型電池をそれぞれ作製した。
作製した各実施例および各比較例の円筒型電池について、電池外部にて正極および負極を電気的に短絡させ、円筒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、円筒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、円筒型電池がもつ安全弁機構の作用、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、安全弁機構が作用するものの、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安全弁機構が通常時の状態に回復し、電池が引き続き使用可能であるためより好ましい。
実施例2-1~実施例2-175および比較例2-1では、セパレータの熱吸収層を構成する吸熱粒子と樹脂材料とを代えて本技術の効果を確認した。
実施例1-1と同様にして、厚さ9μmのポリエチレン製微多孔性フィルム上に、吸熱粒子としてベーマイト(比熱1.2J/gK)を、樹脂材料としてポリフッ化ビニリデン(PVdF)を用い、単位面積あたりの熱容量の総和が0.0006J/Kcm2、単位体積あたりの熱容量の総和が0.4J/Kcm3となるように作製した片面厚さ7.5μm(両面厚さ15μm)の熱吸収層を有するセパレータを用い、負極活物質として黒鉛を用いた円筒型電池を作製した。
セパレータの熱吸収層に用いる樹脂材料として、ポリフッ化ビニリデンの代わりにポリイミドを用いた以外は実施例2-1と同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる樹脂材料として、ポリフッ化ビニリデンの代わりに全芳香族ポリアミド(アラミド)を用いた以外は実施例2-1と同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる樹脂材料として、ポリフッ化ビニリデンの代わりにポリアクリロニトリルを用いた以外は実施例2-1と同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる樹脂材料として、ポリフッ化ビニリデンの代わりにポリビニルアルコールを用いた以外は実施例2-1と同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる樹脂材料として、ポリフッ化ビニリデンの代わりにポリエーテルを用いた以外は実施例2-1と同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる樹脂材料として、ポリフッ化ビニリデンの代わりにアクリル酸樹脂を用いた以外は実施例2-1と同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる吸熱粒子として、アルミナの代わりに窒化アルミニウム(比熱0.7J/gK)を用いた以外は、実施例2-1~実施例2-7とそれぞれ同様にして円筒型電池を作製した。なお、窒化アルミニウムとベーマイトとは比熱が異なり、窒化アルミニウムの比熱はベーマイトの比熱よりも小さい。このため、単位面積あたりの熱容量の総和を0.0006J/Kcm2とするために、単位面積あたりの窒化アルミニウム量を実施例2-1~実施例2-7の単位面積あたりのベーマイト量よりも多くすることにより調整した。
セパレータの熱吸収層に用いる吸熱粒子として、ベーマイトの代わりに窒化ホウ素(比熱:0.8J/gK)を用いた以外は、実施例2-1~実施例2-7とそれぞれ同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる吸熱粒子として、ベーマイトの代わりに炭化ケイ素(比熱:0.7J/gK)を用いた以外は、実施例2-1~実施例2-7とそれぞれ同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる吸熱粒子として、ベーマイトの代わりにタルク(比熱:1.1J/gK)を用いた以外は、実施例2-1~実施例2-7とそれぞれ同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる吸熱粒子として、ベーマイトの代わりにLi2O4(比熱:0.8J/gK)を用いた以外は、実施例2-1~実施例2-7とそれぞれ同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる吸熱粒子として、ベーマイトの代わりにLi3PO4(比熱:0.8J/gK)を用いた以外は、実施例2-1~実施例2-7とそれぞれ同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる吸熱粒子として、ベーマイトの代わりにLiF(比熱:0.9J/gK)を用いた以外は、実施例2-1~実施例2-7とそれぞれ同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる吸熱粒子として、ベーマイトの代わりにダイヤモンド(比熱:0.5J/gK)を用いた以外は、実施例2-1~実施例2-7とそれぞれ同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる吸熱粒子として、ベーマイトの代わりに酸化ジルコニウム(比熱:0.7J/gK)を用いた以外は、実施例2-1~実施例2-7とそれぞれ同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる吸熱粒子として、ベーマイトの代わりに酸化イットリウム(比熱:0.5J/gK)を用いた以外は、実施例2-1~実施例2-7とそれぞれ同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる吸熱粒子として、ベーマイトの代わりにチタン酸バリウム(比熱:0.8J/gK)を用いた以外は、実施例2-1~実施例2-7とそれぞれ同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる吸熱粒子として、ベーマイトの代わりにチタン酸ストロンチウム(比熱:0.8J/gK)を用いた以外は、実施例2-1~実施例2-7とそれぞれ同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる吸熱粒子として、ベーマイトの代わりに酸化ケイ素(比熱:0.8J/gK)を用いた以外は、実施例2-1~実施例2-7とそれぞれ同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる吸熱粒子として、ベーマイトの代わりにゼオライト(比熱:1.0J/gK)を用いた以外は、実施例2-1~実施例2-7とそれぞれ同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる吸熱粒子として、ベーマイトの代わりに硫酸バリウム(比熱:0.9J/gK)を用いた以外は、実施例2-1~実施例2-7とそれぞれ同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる吸熱粒子として、ベーマイトの代わりに酸化チタン(比熱:0.8J/gK)を用いた以外は、実施例2-1~実施例2-7とそれぞれ同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる吸熱粒子として、ベーマイトの代わりに酸化マグネシウム(比熱:1.0J/gK)を用いた以外は、実施例2-1~実施例2-7とそれぞれ同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる吸熱粒子として、ベーマイトの代わりに黒鉛(比熱:0.8J/gK)を用いた以外は、実施例2-1~実施例2-7とそれぞれ同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる吸熱粒子として、ベーマイトの代わりにカーボンナノチューブ(比熱:0.8J/gK)を用いた以外は、実施例2-1~実施例2-7とそれぞれ同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる吸熱粒子として、ベーマイトの代わりに水酸化アルミニウム(比熱:1.5J/gK)を用いた以外は、実施例2-1~実施例2-7とそれぞれ同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる吸熱粒子として、ベーマイトの代わりに炭化ホウ素(比熱:1.0J/gK)を用いた以外は、実施例2-1~実施例2-7とそれぞれ同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる吸熱粒子として、ベーマイトの代わりに窒化ケイ素(比熱:0.7J/gK)を用いた以外は、実施例2-1~実施例2-7とそれぞれ同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる吸熱粒子として、ベーマイトの代わりに窒化チタン(比熱:0.6J/gK)を用いた以外は、実施例2-1~実施例2-7とそれぞれ同様にして円筒型電池を作製した。
セパレータの熱吸収層に用いる吸熱粒子として、ベーマイトの代わりに酸化亜鉛(比熱:0.5J/gK)を用いた以外は、実施例2-1~実施例2-7とそれぞれ同様にして円筒型電池を作製した。
厚さ23μmのポリエチレン製微多孔性フィルムをセパレータとして用いた以外は実施例2-1と同様にして円筒型電池を作製した。
作製した各実施例および各比較例の円筒型電池について、実施例1-1と同様にして短絡試験を行った。
負極活物質として黒鉛の代わりに実施例1-13と同様のシリコンを用いた以外は実施例2-1~実施例2-175および比較例2-1と同様にして、実施例3-1~実施例3-175および比較例3-1の円筒型電池をそれぞれ作製した。なお、負極活物質層を形成する負極合剤スラリーは、実施例1-13と同様の組成とした。
作製した各実施例および各比較例の円筒型電池について、実施例1-1と同様にして短絡試験を行った。
負極活物質として黒鉛の代わりに実施例1-25と同様の炭素スズ複合材料を用いた以外は実施例2-1~実施例2-175および比較例2-1と同様にして、実施例4-1~実施例4-175および比較例4-1の円筒型電池をそれぞれ作製した。なお、負極活物質層を形成する負極合剤スラリーは、実施例1-25と同様の組成とした。
作製した各実施例および各比較例の円筒型電池について、実施例1-1と同様にして短絡試験を行った。
負極活物質として黒鉛の代わりに実施例1-37と同様のチタン酸リチウムを用いた以外は実施例2-1~実施例2-175および比較例2-1と同様にして、実施例5-1~実施例5-175および比較例5-1の円筒型電池をそれぞれ作製した。なお、負極活物質層を形成する負極合剤スラリーは、実施例1-37と同様の組成とした。
作製した各実施例および各比較例の円筒型電池について、実施例1-1と同様にして短絡試験を行った。
実施例6-1~実施例6-60では、電池構成、負極活物質、セパレータの熱吸収層の位置を変えて電池を作製し、本技術の効果を確認した。
実施例1-1と同様の円筒型電池を作製し、実施例6-1の円筒型電池とした。すなわち、電池構成は電池外装が円筒型外装缶、負極活物質は黒鉛とした。また、セパレータは、厚さ9μmのポリエチレン製微多孔性フィルムの両面に、吸熱粒子であるベーマイトと、樹脂材料であるポリフッ化ビニリデンとからなる片面厚さ7.5μm(両面厚さ15μm)の熱吸収層を設けた構成とした。
厚さ9μmのポリエチレン製微多孔性フィルムの正極側面(電池作製時において正極と対向する面)のみに、片面厚さ15μmの熱吸収層を設けたセパレータを用いた以外は実施例6-1と同様にして円筒型電池を作製した。
厚さ9μmのポリエチレン製微多孔性フィルムの負極側面(電池作製時において負極と対向する面)のみに、片面厚さ15μmの熱吸収層を設けたセパレータを用いた以外は実施例6-1と同様にして円筒型電池を作製した。
負極活物質としてシリコンを用い、負極合剤スラリーを実施例1-13と同様の構成とした以外は、実施例6-1~実施例6-3と同様にして実施例6-4~実施例6-6の円筒型電池をそれぞれ作製した。
負極活物質として炭素スズ複合材料を用い、負極合剤スラリーを実施例1-25と同様の構成とした以外は、実施例6-1~実施例6-3と同様にして実施例6-7~実施例6-9の円筒型電池をそれぞれ作製した。
負極活物質としてチタン酸リチウムを用い、負極合剤スラリーを実施例1-37と同様の構成とした以外は、実施例6-1~実施例6-3と同様にして実施例6-10~実施例6-12の円筒型電池をそれぞれ作製した。
正極、負極、セパレータおよび非水電解液のそれぞれの構成が実施例6-1と同様である角型電池を作製した。すなわち、電池構成は電池外装が角型外装缶、負極活物質は黒鉛とした。また、セパレータは、厚さ9μmのポリエチレン製微多孔性フィルムの両面に、吸熱粒子であるベーマイトと、樹脂材料であるポリフッ化ビニリデンとからなる片面厚さ7.5μm(両面厚さ15μm)の熱吸収層を設けた構成とした。以下、角型電池の組み立て方法を説明する。
正極および負極と、熱吸着層が両面に形成されたセパレータとを、正極、セパレータ、負極、セパレータの順に積層し、長手方向に多数回、扁平形状に巻回させた後、巻き終わり部分を粘着テープで固定することにより巻回電極体を形成した。次に、図6に示すように、巻回電極体を角型の電池缶に収容した。続いて、電池蓋に設けられた電極ピンと、巻回電極体から導出された正極端子とを接続した後、電池缶を電池蓋にて封口し、電解液注入口から非水電解液を注入して封止部材にて封止し、密閉した。これにより、電池形状が厚さ5.2mm、幅34mm、高さ36mm(523436サイズ)、電池容量が1000mAhである、図6に示す角型電池を作製した。
電池構成を実施例6-13と同様の角型電池とした以外は、実施例6-2~実施例6-12と同様にして実施例6-14~実施例6-24の角型電池をそれぞれ作製した。
正極、負極、セパレータおよび非水電解液のそれぞれの構成が実施例6-1と同様であり、積層電極体とを軟質ラミネートフィルムで外装したラミネートフィルム型電池を作製した。すなわち、電池構成は電池外装がラミネートフィルム、電極体は積層型、負極活物質は黒鉛とした。また、セパレータは、厚さ9μmのポリエチレン製微多孔性フィルムの両面に、吸熱粒子であるベーマイトと、樹脂材料であるポリフッ化ビニリデンとからなる片面厚さ7.5μm(両面厚さ15μm)の熱吸収層を設けた構成とした。以下、ラミネートフィルム型電池の組み立て方法を説明する。
矩形状の正極および負極と、熱吸着層が両面に形成されたセパレータとを、正極、セパレータ、負極、セパレータの順に積層して積層電極体を形成した。次に、積層電極体を軟質アルミニウム層を有するラミネートフィルムで外装し、積層電極体周辺の正極端子および負極端子の導出辺と、他の二辺とを熱融着してラミネートフィルムを袋状とした。続いて、熱融着されていない開口部から非水電解液を注入した後、減圧下で熱融着されていない一辺を熱融着して封止し、密閉した。これにより、電池形状が厚さ5.2mm、幅34mm、高さ36mm(523436サイズ)、電池容量が1000mAhである、図9に示すラミネートフィルム型電池を作製した。
電池構成を実施例6-25と同様のラミネートフィルム型電池とした以外は、実施例6-2~実施例6-12と同様にして実施例6-26~実施例6-36のラミネートフィルム型電池をそれぞれ作製した。
正極、負極、セパレータおよび非水電解液のそれぞれの構成が実施例6-1と同様であり、ゲル状の非水電解質と巻回電極体とを軟質ラミネートフィルムで外装したラミネートフィルム型電池を作製した。すなわち、電池構成は電池外装がラミネートフィルム、電極体は積層型、負極活物質は黒鉛とした。また、セパレータは、厚さ9μmのポリエチレン製微多孔性フィルムの両面に、吸熱粒子であるベーマイトと、樹脂材料であるポリフッ化ビニリデンとからなる片面厚さ7.5μm(両面厚さ15μm)の熱吸収層を設けた構成とした。以下、ラミネートフィルム型電池の組み立て方法を説明する。
炭酸エチレン(EC)と炭酸プロピレン(PC)と炭酸ビニレン(VC)とを、質量比49:49:2で混合した非水溶媒に対して、電解質塩として六フッ化リン酸リチウム(LiPF6)を1mol/dm3の濃度で溶解させることにより、非水電解液を調製した。続いて、非水電解液を保持する高分子化合物として、セパレータの熱吸収層を構成する樹脂材料と同様にポリフッ化ビニリデン(PVdF)を用い、非水電解液と、ポリフッ化ビニリデンと、可塑剤である炭酸ジメチル(DMC)とを混合してゾル状の前駆体溶液を調製した。続いて、正極および負極の両面に、前駆体溶液を塗布し、乾燥させて可塑剤を除去した。これにより、正極および負極の表面にゲル電解質層を形成した。
ゲル電解質層が両面に形成された正極および負極と、熱吸着層が両面に形成されたセパレータとを、正極、セパレータ、負極、セパレータの順に積層し、長手方向に多数回、扁平形状に巻回させた後、巻き終わり部分を粘着テープで固定することにより巻回電極体を形成した。
電池構成を実施例6-25と同様のラミネートフィルム型電池とした以外は、実施例6-2~実施例6-12と同様にして実施例6-38~実施例6-48のラミネートフィルム型電池をそれぞれ作製した。
正極、負極、セパレータおよび非水電解液のそれぞれの構成が実施例6-1と同様であり、ゲル状の非水電解質と巻回電極体とを軟質ラミネートフィルムで外装したラミネートフィルム型電池を作製した。すなわち、電池構成は電池外装がラミネートフィルム、電極体は扁平巻回型、負極活物質は黒鉛とした。また、セパレータは、厚さ9μmのポリエチレン製微多孔性フィルムの両面に、吸熱粒子であるベーマイトと、樹脂材料であるポリフッ化ビニリデンとからなる片面厚さ7.5μm(両面厚さ15μm)の熱吸収層を設けた構成とした。以下、ラミネートフィルム型電池の組み立て方法を説明する。
正極および負極と、熱吸着層が両面に形成されたセパレータとを、正極、セパレータ、負極、セパレータの順に積層し、長手方向に多数回、扁平形状に巻回させた後、巻き終わり部分を粘着テープで固定することにより巻回電極体を形成した。このとき、正極および負極の両面には、高分子材料に非水電解液を保持させることによってゲル状とされた非水電解質を塗布したものを用いた。
電池構成を実施例6-25と同様のラミネートフィルム型電池とした以外は、実施例6-2~実施例6-12と同様にして実施例6-50~実施例6-60のラミネートフィルム型電池をそれぞれ作製した。
作製した各実施例および各比較例の電池について、実施例1-1と同様にして短絡試験を行った。
<実施例7-1>
実施例1-1と同様にして、吸熱体粒子として、粒子形状が球状のべーマイト(「長軸の長さ」/「短軸の長さ」=1倍)を用いた円筒型電池を作製した。なお、粒子形状の比率(「長軸の長さ」/「短軸の長さ」)は、以下のように求めたものである。50個の粒子をランダムに選択して、選択した各無機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、各無機粒子の最長部分の長さ(長軸の長さ)と、長軸に直交する各無機粒子の最短部分の長さ(短軸の長さ(厚みまたは太さ))とから、各無機粒子の比率(「長軸の長さ」/「短軸の長さ」)を得た。そして、これらの平均値を実施例7-1の粒子形状の比率(「長軸の長さ」/「短軸の長さ」)とした。(以下の各実施例においても同様)
吸熱体粒子として、粒子形状が板状のベーマイト(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた以外は、実施例7-1と同様にして円筒型電池を作製した。
吸熱体粒子として、粒子形状が針状のベーマイト(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた以外は、実施例7-1と同様にして円筒型電池を作製した。
実施例7-4では、吸熱体粒子として、粒子形状が球状の窒化アルミニウム(「長軸の長さ」/「短軸の長さ」=1倍)用いた。実施例7-5では、吸熱体粒子として、粒子形状が板状の窒化アルミニウム(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。実施例7-6では、吸熱体粒子として、粒子形状が針状の窒化アルミニウム(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。以上のこと以外は、実施例7-1と同様にして円筒型電池を作製した。
実施例7-7では、吸熱体粒子として、粒子形状が球状の窒化ホウ素(「長軸の長さ」/「短軸の長さ」=1倍)用いた。実施例7-8では、吸熱体粒子として、粒子形状が板状の窒化ホウ素(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。実施例7-9では、吸熱体粒子として、粒子形状が針状の窒化ホウ素(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。以上のこと以外は、実施例7-1と同様にして円筒型電池を作製した。
実施例7-10では、吸熱体粒子として、粒子形状が球状の炭化ケイ素(「長軸の長さ」/「短軸の長さ」=1倍)用いた。実施例7-11では、吸熱体粒子として、粒子形状が板状の炭化ケイ素(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。実施例7-12では、吸熱体粒子として、粒子形状が針状の炭化ケイ素(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。以上のこと以外は、実施例7-1と同様にして円筒型電池を作製した。
実施例7-13では、吸熱体粒子として、粒子形状が球状のタルク(「長軸の長さ」/「短軸の長さ」=1倍)用いた。実施例7-14では、吸熱体粒子として、粒子形状が板状のタルク(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。実施例7-15では、吸熱体粒子として、粒子形状が針状のタルク(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。以上のこと以外は、実施例7-1と同様にして円筒型電池を作製した。
実施例7-16では、吸熱体粒子として、粒子形状が球状のLi2O4(「長軸の長さ」/「短軸の長さ」=1倍)用いた。実施例7-17では、吸熱体粒子として、粒子形状が板状のLi2O4(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。実施例7-18では、吸熱体粒子として、粒子形状が針状のLi2O4(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。以上のこと以外は、実施例7-1と同様にして円筒型電池を作製した。
実施例7-19では、吸熱体粒子として、粒子形状が球状のLi3PO4(「長軸の長さ」/「短軸の長さ」=1倍)用いた。実施例7-20では、吸熱体粒子として、粒子形状が板状のLi3PO4(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。実施例7-21では、吸熱体粒子として、粒子形状が針状のLi3PO4(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。以上のこと以外は、実施例7-1と同様にして円筒型電池を作製した。
実施例7-22では、吸熱体粒子として、粒子形状が球状のLiF(「長軸の長さ」/「短軸の長さ」=1倍)用いた。実施例7-23では、吸熱体粒子として、粒子形状が板状のLiF(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。実施例7-24では、吸熱体粒子として、粒子形状が針状のLiF(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。以上のこと以外は、実施例7-1と同様にして円筒型電池を作製した。
実施例7-25では、吸熱体粒子として、粒子形状が球状のダイヤモンド(「長軸の長さ」/「短軸の長さ」=1倍)用いた。実施例7-26では、吸熱体粒子として、粒子形状が板状のダイヤモンド(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。実施例7-27では、吸熱体粒子として、粒子形状が針状のダイヤモンド(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。以上のこと以外は、実施例7-1と同様にして円筒型電池を作製した。
実施例7-28では、吸熱体粒子として、粒子形状が球状のジルコニア(「長軸の長さ」/「短軸の長さ」=1倍)用いた。実施例7-29では、吸熱体粒子として、粒子形状が板状のジルコニア(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。実施例7-30では、吸熱体粒子として、粒子形状が針状のジルコニア(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。以上のこと以外は、実施例7-1と同様にして円筒型電池を作製した。
実施例7-31では、吸熱体粒子として、粒子形状が球状の酸化イットリウム(「長軸の長さ」/「短軸の長さ」=1倍)用いた。実施例7-32では、吸熱体粒子として、粒子形状が板状の酸化イットリウム(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。実施例7-33では、吸熱体粒子として、粒子形状が針状の酸化イットリウム(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。以上のこと以外は、実施例7-1と同様にして円筒型電池を作製した。
実施例7-34では、吸熱体粒子として、粒子形状が球状のチタン酸バリウム(「長軸の長さ」/「短軸の長さ」=1倍)用いた。実施例7-35では、吸熱体粒子として、粒子形状が板状のチタン酸バリウム(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。実施例7-36では、吸熱体粒子として、粒子形状が針状のチタン酸バリウム(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。以上のこと以外は、実施例7-1と同様にして円筒型電池を作製した。
実施例7-37では、吸熱体粒子として、粒子形状が球状のチタン酸ストロンチウム(「長軸の長さ」/「短軸の長さ」=1倍)用いた。実施例7-38では、吸熱体粒子として、粒子形状が板状のチタン酸ストロンチウム(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。実施例7-39では、吸熱体粒子として、粒子形状が針状のチタン酸ストロンチウム(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。以上のこと以外は、実施例7-1と同様にして円筒型電池を作製した。
実施例7-40では、吸熱体粒子として、粒子形状が球状の酸化ケイ素(「長軸の長さ」/「短軸の長さ」=1倍)用いた。実施例7-41では、吸熱体粒子として、粒子形状が板状の酸化ケイ素(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。実施例7-42では、吸熱体粒子として、粒子形状が針状の酸化ケイ素(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。以上のこと以外は、実施例7-1と同様にして円筒型電池を作製した。
実施例7-43では、吸熱体粒子として、粒子形状が球状のゼオライト(「長軸の長さ」/「短軸の長さ」=1倍)用いた。実施例7-44では、吸熱体粒子として、粒子形状が板状のゼオライト(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。実施例7-45では、吸熱体粒子として、粒子形状が針状のゼオライト(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。以上のこと以外は、実施例7-1と同様にして円筒型電池を作製した。
実施例7-46では、吸熱体粒子として、粒子形状が球状の硫酸バリウム(「長軸の長さ」/「短軸の長さ」=1倍)用いた。実施例7-47では、吸熱体粒子として、粒子形状が板状の硫酸バリウム(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。実施例7-48では、吸熱体粒子として、粒子形状が針状の硫酸バリウム(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。以上のこと以外は、実施例7-1と同様にして円筒型電池を作製した。
実施例7-49では、吸熱体粒子として、粒子形状が球状の酸化チタン(「長軸の長さ」/「短軸の長さ」=1倍)用いた。実施例7-50では、吸熱体粒子として、粒子形状が板状の酸化チタン(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。実施例7-51では、吸熱体粒子として、粒子形状が針状の酸化チタン(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。以上のこと以外は、実施例7-1と同様にして円筒型電池を作製した。
実施例7-52では、吸熱体粒子として、粒子形状が球状の酸化マグネシウム(「長軸の長さ」/「短軸の長さ」=1倍)用いた。実施例7-53では、吸熱体粒子として、粒子形状が板状の酸化マグネシウム(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。実施例7-54では、吸熱体粒子として、粒子形状が針状の酸化マグネシウム(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。以上のこと以外は、実施例7-1と同様にして円筒型電池を作製した。
実施例7-55では、吸熱体粒子として、粒子形状が球状の黒鉛(「長軸の長さ」/「短軸の長さ」=1倍)用いた。実施例7-56では、吸熱体粒子として、粒子形状が板状の黒鉛(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。実施例7-57では、吸熱体粒子として、粒子形状が針状の黒鉛(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。以上のこと以外は、実施例7-1と同様にして円筒型電池を作製した。
吸熱体粒子として、粒子形状が針状のカーボンナノチューブ(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=10倍)を用いた以外は、実施例7-1と同様にして円筒型電池を作製した。
実施例7-59では、吸熱体粒子として、粒子形状が球状の水酸化アルミニウム(「長軸の長さ」/「短軸の長さ」=1倍)用いた。実施例7-60では、吸熱体粒子として、粒子形状が板状の水酸化アルミニウム(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。実施例7-61では、吸熱体粒子として、粒子形状が針状の水酸化アルミニウム(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。以上のこと以外は、実施例7-1と同様にして円筒型電池を作製した。
実施例7-62では、吸熱体粒子として、粒子形状が球状の炭化ホウ素(「長軸の長さ」/「短軸の長さ」=1倍)用いた。実施例7-63では、吸熱体粒子として、粒子形状が板状の炭化ホウ素(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。実施例7-64では、吸熱体粒子として、粒子形状が針状の炭化ホウ素(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。以上のこと以外は、実施例7-1と同様にして円筒型電池を作製した。
実施例7-65では、吸熱体粒子として、粒子形状が球状の窒化ケイ素(「長軸の長さ」/「短軸の長さ」=1倍)用いた。実施例7-66では、吸熱体粒子として、粒子形状が板状の窒化ケイ素(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。実施例7-67では、吸熱体粒子として、粒子形状が針状の窒化ケイ素(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。以上のこと以外は、実施例7-1と同様にして円筒型電池を作製した。
実施例7-68では、吸熱体粒子として、粒子形状が球状の窒化チタン(「長軸の長さ」/「短軸の長さ」=1倍)用いた。実施例7-69では、吸熱体粒子として、粒子形状が板状の窒化チタン(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。実施例7-70では、吸熱体粒子として、粒子形状が針状の窒化チタン(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。以上のこと以外は、実施例7-1と同様にして円筒型電池を作製した。
実施例7-71では、吸熱体粒子として、粒子形状が球状の酸化亜鉛(「長軸の長さ」/「短軸の長さ」=1倍)用いた。実施例7-72では、吸熱体粒子として、粒子形状が板状の酸化亜鉛(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。実施例7-73では、吸熱体粒子として、粒子形状が針状の酸化亜鉛(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。以上のこと以外は、実施例7-1と同様にして円筒型電池を作製した。
実施例7-74では、吸熱体粒子として、粒子形状が球状のアルミナ(「長軸の長さ」/「短軸の長さ」=1倍)用いた。実施例7-75では、吸熱体粒子として、粒子形状が板状のアルミナ(長さ:厚み=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。実施例7-76では、吸熱体粒子として、粒子形状が針状のアルミナ(長さ:太さ=3:1、すなわち、「長軸の長さ」/「短軸の長さ」=3倍)を用いた。以上のこと以外は、実施例7-1と同様にして円筒型電池を作製した。
作製した各実施例および各比較例の電池について、実施例1-1と同様にして短絡試験を行った。
基材と、
上記基材の少なくとも一方の面に形成され、単位面積あたりの熱容量が0.0001J/Kcm2以上であり、かつ単位体積あたりの熱容量が3.0J/Kcm3以下である層と
を備え、
上記層は、粒子と、樹脂材料とを含有し、
上記粒子は、ベーマイト、酸化イットリウム、酸化チタン、酸化マグネシウム、酸化ジルコニウム、酸化ケイ素、酸化亜鉛、窒化アルミニウム、窒化ホウ素、窒化ケイ素、窒化チタン、炭化ケイ素、炭化ホウ素、チタン酸バリウム、チタン酸ストロンチウム、硫酸バリウム、多孔質アルミノケイ酸塩、層状ケイ酸塩、Li2O4、Li3PO4、LiF、水酸化アルミニウム、黒鉛、カーボンナノチューブおよびダイヤモンドの中から選ばれた少なくとも1つを含有するセパレータ。
[2]
上記粒子が、上記層中に分散して存在する
[1]に記載のセパレータ。
[3]
上記粒子が、三次元網目構造に形成された上記樹脂材料に分散して担持される
[1]~[2]の何れかに記載のセパレータ。
[4]
上記粒子の比熱が、0.5J/gK以上である
[1]~[3]の何れかに記載のセパレータ。
[5]
上記粒子の形状が、異方性を有する形状である
[1]~[4]の何れかに記載のセパレータ。
[6]
上記粒子の最長部分の長さと、該最長部分に直交する方向における上記粒子の最短部分の長さとの比率(「上記最長部分の長さ」/{上記最短部分の長さ})が、3倍以上である[5]に記載のセパレータ。
[7]
上記樹脂材料の融点およびガラス転移温度の少なくとも一方が、180℃以上である
[1]~[6]の何れかに記載のセパレータ。
[8]
上記樹脂材料がポリフッ化ビニリデンである
[7]に記載のセパレータ。
[9]
上記層の空孔率が、上記基材の空孔率よりも大きく、かつ95%以下である
[1]~[8]の何れかに記載のセパレータ。
[10]
上記基材を構成する上記樹脂材料が、ポレオレフィン系樹脂を含む
[1]~[9]の何れかに記載のセパレータ。
[11]
上記基材の空孔率が、25%以上40%以下である
[1]~[10]の何れかに記載のセパレータ。
[12]
基材と、
上記基材の少なくとも一方の面側に形成され、少なくとも一部が上記基材内の空隙に含まれ、単位面積あたりの熱容量が0.0001J/Kcm2以上であり、かつ単位体積あたりの熱容量が3.0J/Kcm3以下である層と
を備え、
上記層は、粒子と、樹脂材料とを含有し、
上記粒子は、ベーマイト、酸化イットリウム、酸化チタン、酸化マグネシウム、酸化ジルコニウム、酸化ケイ素、酸化亜鉛、窒化アルミニウム、窒化ホウ素、窒化ケイ素、窒化チタン、炭化ケイ素、炭化ホウ素、チタン酸バリウム、チタン酸ストロンチウム、硫酸バリウム、多孔質アルミノケイ酸塩、層状ケイ酸塩、Li2O4、Li3PO4、LiF、水酸化アルミニウム、黒鉛、カーボンナノチューブおよびダイヤモンドの中から選ばれた少なくとも1つを含有するセパレータ。
[13]
上記基材は、不織布またはセルロース透気性膜である[12]に記載のセパレータ。
[14]
正極および負極がセパレータを介して対向する電極体と、
電解質と
を備え、
上記セパレータが、
基材と、
上記基材の少なくとも一方の面に形成され、単位面積あたりの熱容量が0.0001J/Kcm2以上であり、かつ単位体積あたりの熱容量が3.0J/Kcm3以下である層と
を備え、
上記層は、粒子と、樹脂材料とを含有し、
上記粒子は、ベーマイト、酸化イットリウム、酸化チタン、酸化マグネシウム、酸化ジルコニウム、酸化ケイ素、酸化亜鉛、窒化アルミニウム、窒化ホウ素、窒化ケイ素、窒化チタン、炭化ケイ素、炭化ホウ素、チタン酸バリウム、チタン酸ストロンチウム、硫酸バリウム、多孔質アルミノケイ酸塩、層状ケイ酸塩、Li2O4、Li3PO4、LiF、水酸化アルミニウム、黒鉛、カーボンナノチューブおよびダイヤモンドの中から選ばれた少なくとも1つを含有する電池。
[15]
上記負極に含まれる負極活物質が、金属元素および半金属元素のうちの少なくとも1種を構成元素として含む材料からなる
[14]に記載の電池。
[16]
正極および負極がセパレータを介して対向する電極体と、
電解質と
を備え、
上記セパレータが、
基材と、
上記基材の少なくとも一方の面側に形成され、少なくとも一部が上記基材内の空隙に含まれ、単位面積あたりの熱容量が0.0001J/Kcm2以上であり、かつ単位体積あたりの熱容量が3.0J/Kcm3以下である層と
を備え、
上記層は、粒子と、樹脂材料とを含有し、
上記粒子は、ベーマイト、酸化イットリウム、酸化チタン、酸化マグネシウム、酸化ジルコニウム、酸化ケイ素、酸化亜鉛、窒化アルミニウム、窒化ホウ素、窒化ケイ素、窒化チタン、炭化ケイ素、炭化ホウ素、チタン酸バリウム、チタン酸ストロンチウム、硫酸バリウム、多孔質アルミノケイ酸塩、層状ケイ酸塩、Li2O4、Li3PO4、LiF、水酸化アルミニウム、黒鉛、カーボンナノチューブおよびダイヤモンドの中から選ばれた少なくとも1つを含有する電池。
[17]
正極および負極がセパレータを介して対向する電極体と、
電解質と、
上記セパレータと、該セパレータを介して対向する上記正極および上記負極の少なくとも一方との間に、単位面積あたりの熱容量が0.0001J/Kcm2以上であり、かつ単位体積あたりの熱容量が3.0J/Kcm3以下である層と
を備え、
上記層は、粒子と、樹脂材料とを含有し、
上記粒子は、ベーマイト、酸化イットリウム、酸化チタン、酸化マグネシウム、酸化ジルコニウム、酸化ケイ素、酸化亜鉛、窒化アルミニウム、窒化ホウ素、窒化ケイ素、窒化チタン、炭化ケイ素、炭化ホウ素、チタン酸バリウム、チタン酸ストロンチウム、硫酸バリウム、多孔質アルミノケイ酸塩、層状ケイ酸塩、Li2O4、Li3PO4、LiF、水酸化アルミニウム、黒鉛、カーボンナノチューブおよびダイヤモンドの中から選ばれた少なくとも1つを含有する電池。
[18]
[14]~[17]の何れかに記載の電池と、
上記電池を制御する制御部と、
上記電池を内包する外装を有する
電池パック。
[19]
[14]~[17]の何れかに記載の電池を有し、
上記電池から電力の供給を受ける
電子機器。
[20]
[14]~[17]の何れかに記載の電池と、
上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、
上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。
[21]
[14]~[17]の何れかに記載の電池を有し、
上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。
[22]
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
上記電力情報制御装置が受信した情報に基づき、上記電池の充放電制御を行う
[21]に記載の蓄電装置。
[23]
[14]~[17]の何れか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上記電池に電力が供給される
電力システム。
Claims (23)
- 基材と、
上記基材の少なくとも一方の面に形成され、単位面積あたりの熱容量が0.0001J/Kcm2以上であり、かつ単位体積あたりの熱容量が3.0J/Kcm3以下である層と
を備え、
上記層は、粒子と、樹脂材料とを含有し、
上記粒子は、ベーマイト、酸化イットリウム、酸化チタン、酸化マグネシウム、酸化ジルコニウム、酸化ケイ素、酸化亜鉛、窒化アルミニウム、窒化ホウ素、窒化ケイ素、窒化チタン、炭化ケイ素、炭化ホウ素、チタン酸バリウム、チタン酸ストロンチウム、硫酸バリウム、多孔質アルミノケイ酸塩、層状ケイ酸塩、Li2O4、Li3PO4、LiF、水酸化アルミニウム、黒鉛、カーボンナノチューブおよびダイヤモンドの中から選ばれた少なくとも1つを含有するセパレータ。 - 上記粒子が、上記層中に分散して存在する請求項1に記載のセパレータ。
- 上記粒子が、三次元網目構造に形成された上記樹脂材料に分散して担持される
請求項1に記載のセパレータ。 - 上記粒子の比熱が、0.5J/gK以上である
請求項1に記載のセパレータ。 - 上記粒子の形状が、異方性を有する形状である請求項1に記載のセパレータ。
- 上記粒子の最長部分の長さと、該最長部分に直交する方向における上記粒子の最短部分の長さとの比率(「上記最長部分の長さ」/{上記最短部分の長さ})が、3倍以上である請求項5に記載のセパレータ。
- 上記樹脂材料の融点およびガラス転移温度の少なくとも一方が、180℃以上である
請求項1に記載のセパレータ。 - 上記樹脂材料がポリフッ化ビニリデンである
請求項7に記載のセパレータ。 - 上記層の空孔率が、上記基材の空孔率よりも大きく、かつ95%以下である
請求項1に記載のセパレータ。 - 上記基材を構成する上記樹脂材料が、ポレオレフィン系樹脂を含む
請求項1に記載のセパレータ。 - 上記基材の空孔率が、25%以上40%以下である
請求項1に記載のセパレータ。 - 基材と、
上記基材の少なくとも一方の面側に形成され、少なくとも一部が上記基材内の空隙に含まれ、単位面積あたりの熱容量が0.0001J/Kcm2以上であり、かつ単位体積あたりの熱容量が3.0J/Kcm3以下である層と
を備え、
上記層は、粒子と、樹脂材料とを含有し、
上記粒子は、ベーマイト、酸化イットリウム、酸化チタン、酸化マグネシウム、酸化ジルコニウム、酸化ケイ素、酸化亜鉛、窒化アルミニウム、窒化ホウ素、窒化ケイ素、窒化チタン、炭化ケイ素、炭化ホウ素、チタン酸バリウム、チタン酸ストロンチウム、硫酸バリウム、多孔質アルミノケイ酸塩、層状ケイ酸塩、Li2O4、Li3PO4、LiF、水酸化アルミニウム、黒鉛、カーボンナノチューブおよびダイヤモンドの中から選ばれた少なくとも1つを含有するセパレータ。 - 上記基材は、不織布またはセルロース透気性膜である請求項12に記載のセパレータ。
- 正極および負極がセパレータを介して対向する電極体と、
電解質と
を備え、
上記セパレータが、
基材と、
上記基材の少なくとも一方の面に形成され、単位面積あたりの熱容量が0.0001J/Kcm2以上であり、かつ単位体積あたりの熱容量が3.0J/Kcm3以下である層と
を備え、
上記層は、粒子と、樹脂材料とを含有し、
上記粒子は、ベーマイト、酸化イットリウム、酸化チタン、酸化マグネシウム、酸化ジルコニウム、酸化ケイ素、酸化亜鉛、窒化アルミニウム、窒化ホウ素、窒化ケイ素、窒化チタン、炭化ケイ素、炭化ホウ素、チタン酸バリウム、チタン酸ストロンチウム、硫酸バリウム、多孔質アルミノケイ酸塩、層状ケイ酸塩、Li2O4、Li3PO4、LiF、水酸化アルミニウム、黒鉛、カーボンナノチューブおよびダイヤモンドの中から選ばれた少なくとも1つを含有する電池。 - 上記負極に含まれる負極活物質が、金属元素および半金属元素のうちの少なくとも1種を構成元素として含む材料からなる
請求項14に記載の電池。 - 正極および負極がセパレータを介して対向する電極体と、
電解質と
を備え、
上記セパレータが、
基材と、
上記基材の少なくとも一方の面側に形成され、少なくとも一部が上記基材内の空隙に含まれ、単位面積あたりの熱容量が0.0001J/Kcm2以上であり、かつ単位体積あたりの熱容量が3.0J/Kcm3以下である層と
を備え、
上記層は、粒子と、樹脂材料とを含有し、
上記粒子は、ベーマイト、酸化イットリウム、酸化チタン、酸化マグネシウム、酸化ジルコニウム、酸化ケイ素、酸化亜鉛、窒化アルミニウム、窒化ホウ素、窒化ケイ素、窒化チタン、炭化ケイ素、炭化ホウ素、チタン酸バリウム、チタン酸ストロンチウム、硫酸バリウム、多孔質アルミノケイ酸塩、層状ケイ酸塩、Li2O4、Li3PO4、LiF、水酸化アルミニウム、黒鉛、カーボンナノチューブおよびダイヤモンドの中から選ばれた少なくとも1つを含有する電池。 - 正極および負極がセパレータを介して対向する電極体と、
電解質と、
上記セパレータと、該セパレータを介して対向する上記正極および上記負極の少なくとも一方との間に、単位面積あたりの熱容量が0.0001J/Kcm2以上であり、かつ単位体積あたりの熱容量が3.0J/Kcm3以下である層と
を備え、
上記層は、粒子と、樹脂材料とを含有し、
上記粒子は、ベーマイト、酸化イットリウム、酸化チタン、酸化マグネシウム、酸化ジルコニウム、酸化ケイ素、酸化亜鉛、窒化アルミニウム、窒化ホウ素、窒化ケイ素、窒化チタン、炭化ケイ素、炭化ホウ素、チタン酸バリウム、チタン酸ストロンチウム、硫酸バリウム、多孔質アルミノケイ酸塩、層状ケイ酸塩、Li2O4、Li3PO4、LiF、水酸化アルミニウム、黒鉛、カーボンナノチューブおよびダイヤモンドの中から選ばれた少なくとも1つを含有する電池。 - 請求項14に記載の電池と、
上記電池を制御する制御部と、
上記電池を内包する外装を有する
電池パック。 - 請求項14に記載の電池を有し、
上記電池から電力の供給を受ける
電子機器。 - 請求項14に記載の電池と、
上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、
上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14に記載の電池を有し、
上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
上記電力情報制御装置が受信した情報に基づき、上記電池の充放電制御を行う
請求項21に記載の蓄電装置。 - 請求項14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上記電池に電力が供給される
電力システム。
Priority Applications (8)
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EP17202599.1A EP3306708B1 (en) | 2013-03-19 | 2014-03-18 | Separator, battery, battery pack, electronic apparatus, electric vehicle, power storage device, and power system |
EP14770685.7A EP2978047B1 (en) | 2013-03-19 | 2014-03-18 | Separator, battery, battery pack, electronic apparatus, electric vehicle, power storage device, and power system |
KR1020157023873A KR102130867B1 (ko) | 2013-03-19 | 2014-03-18 | 세퍼레이터, 전지, 전지 팩, 전자 기기, 전동 차량, 축전 장치 및 전력 시스템 |
CA2905653A CA2905653C (en) | 2013-03-19 | 2014-03-18 | Separator, battery, battery pack, electronic apparatus, electric vehicle, power storage device, and electric power system |
EP19173849.1A EP3573137B1 (en) | 2013-03-19 | 2014-03-18 | Separator, battery, battery pack, electronic apparatus, electric vehicle, power storage device, and power system |
CN201480014333.8A CN105051941B (zh) | 2013-03-19 | 2014-03-18 | 隔膜、电池、电池组、电子设备、电动车辆、电力储存装置以及电力系统 |
US14/777,356 US10079379B2 (en) | 2013-03-19 | 2014-03-18 | Separator, battery, battery pack, electronic apparatus, electric vehicle, power storage device, and electric power system |
JP2015506606A JP6582979B2 (ja) | 2013-03-19 | 2014-03-18 | セパレータ、電池、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 |
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US (1) | US10079379B2 (ja) |
EP (3) | EP3573137B1 (ja) |
JP (1) | JP6582979B2 (ja) |
KR (1) | KR102130867B1 (ja) |
CN (1) | CN105051941B (ja) |
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WO (1) | WO2014148036A1 (ja) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015122164A1 (ja) * | 2014-02-17 | 2015-08-20 | 三洋電機株式会社 | 非水電解質二次電池用セパレータ |
JPWO2015068325A1 (ja) * | 2013-11-05 | 2017-03-09 | ソニー株式会社 | 電池、セパレータ、電極、塗料、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 |
JP2017126453A (ja) * | 2016-01-13 | 2017-07-20 | トヨタ自動車株式会社 | 非水電解液二次電池 |
JP2018147645A (ja) * | 2017-03-03 | 2018-09-20 | トヨタ自動車株式会社 | 非水電解質二次電池 |
US10374203B2 (en) * | 2015-01-09 | 2019-08-06 | Lg Chem, Ltd. | Heat-diffusible separation film and secondary cell comprising the same |
WO2019225078A1 (ja) * | 2018-05-24 | 2019-11-28 | 株式会社日立製作所 | 絶縁層、電池セルシート、二次電池 |
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JP2020113441A (ja) * | 2019-01-11 | 2020-07-27 | トヨタ自動車株式会社 | リチウムイオン二次電池用の負極 |
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KR20210129132A (ko) | 2019-03-20 | 2021-10-27 | 데이진 가부시키가이샤 | 비수계 이차전지용 세퍼레이터 및 비수계 이차전지 |
WO2022025215A1 (ja) | 2020-07-31 | 2022-02-03 | 帝人株式会社 | 非水系二次電池用セパレータ及び非水系二次電池 |
WO2022045127A1 (ja) * | 2020-08-31 | 2022-03-03 | パナソニックIpマネジメント株式会社 | リチウム二次電池 |
Families Citing this family (40)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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US10650621B1 (en) | 2016-09-13 | 2020-05-12 | Iocurrents, Inc. | Interfacing with a vehicular controller area network |
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EP3695447A2 (en) | 2017-10-13 | 2020-08-19 | Optodot Corporation | Multilayer nanoporous separator |
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US20190123333A1 (en) * | 2017-10-24 | 2019-04-25 | Sumitomo Chemical Company, Limited | Nonaqueous electrolyte secondary battery porous layer |
US20190148692A1 (en) * | 2017-11-16 | 2019-05-16 | Apple Inc. | Direct coated separators and formation processes |
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US11870037B2 (en) | 2018-04-10 | 2024-01-09 | Apple Inc. | Porous ceramic separator materials and formation processes |
US10410950B1 (en) | 2018-05-11 | 2019-09-10 | Micron Technology, Inc. | Heat spreaders for use with semiconductor devices |
US10895606B1 (en) * | 2018-05-25 | 2021-01-19 | The United States Of America As Represented By The Secretary Of The Navy | Multi-short circuit mode electrochemical cell test method |
KR102429590B1 (ko) * | 2019-04-22 | 2022-08-05 | 주식회사 엘지에너지솔루션 | 전극조립체 |
EP3969509A1 (en) * | 2019-05-15 | 2022-03-23 | 3M Innovative Properties Company | (co)polymer matrix composites comprising thermally-conductive particles and intumescent particles and methods of making the same |
DE102019212014A1 (de) * | 2019-08-09 | 2021-02-11 | Volkswagen Ag | Verfahren zur Herstellung eines Schichtsystems einer Batteriezelle |
CN110828753B (zh) * | 2019-11-19 | 2021-11-12 | 肇庆市华师大光电产业研究院 | 一种锂硫电池功能性隔层的制备方法 |
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WO2021241300A1 (ja) * | 2020-05-27 | 2021-12-02 | パナソニックIpマネジメント株式会社 | バリウム化合物構造体及びその製造方法 |
FR3112220B1 (fr) | 2020-07-02 | 2022-07-08 | Lencify | Procede de recherche assistee dans une base de donnees et systeme de recherche associe |
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WO2022110223A1 (zh) * | 2020-11-30 | 2022-06-02 | 宁德时代新能源科技股份有限公司 | 一种隔离膜、含有它的二次电池及其相关的电池模块、电池包和装置 |
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EP4374456A2 (en) * | 2021-08-24 | 2024-05-29 | Celgard, LLC | Heat dissipation separators for high energy batteries |
CN114142156A (zh) * | 2021-12-01 | 2022-03-04 | 上海恩捷新材料科技有限公司 | 一种导热锂离子隔膜及其制备方法 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000030686A (ja) | 1998-04-27 | 2000-01-28 | Sumitomo Chem Co Ltd | 非水電解質電池セパレ―タ―とリチウム二次電池 |
JP2005353582A (ja) | 2004-05-11 | 2005-12-22 | Sony Corp | 電解液および電池 |
JP2007027100A (ja) * | 2005-06-14 | 2007-02-01 | Matsushita Electric Ind Co Ltd | 非水電解質二次電池 |
JP2007188777A (ja) * | 2006-01-13 | 2007-07-26 | Sony Corp | セパレータおよび非水電解質電池 |
JP2011159488A (ja) | 2010-02-01 | 2011-08-18 | Sony Corp | 非水電解質組成物および非水電解質二次電池 |
WO2012169681A1 (en) * | 2010-06-10 | 2012-12-13 | Sk Innovation Co., Ltd. | Microporous composite film with high thermostable organic/inorganic coating layer |
US20130059192A1 (en) * | 2011-09-05 | 2013-03-07 | Sony Corporation | Separator and nonaqueous electrolyte battery |
JP2013054972A (ja) * | 2011-09-05 | 2013-03-21 | Sony Corp | セパレータ、非水電解質電池、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 |
JP2013054973A (ja) * | 2011-09-05 | 2013-03-21 | Sony Corp | セパレータ、非水電解質電池、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 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002527873A (ja) * | 1998-10-13 | 2002-08-27 | ウルトラライフ バッテリーズ インコーポレイテッド | 高性能リチウムイオンポリマー電池及び蓄電池 |
TWI287556B (en) * | 1999-09-13 | 2007-10-01 | Teijin Ltd | Polymetaphenyleneisophthalamide-based polymer porous film, process for preparing same and separator for battery |
KR101002161B1 (ko) * | 2007-11-29 | 2010-12-17 | 주식회사 엘지화학 | 다공성 코팅층이 형성된 세퍼레이터, 그 제조방법 및 이를 구비한 전기화학소자 |
CN102160211B (zh) | 2008-08-19 | 2015-04-22 | 帝人株式会社 | 非水系二次电池用隔板 |
WO2010027203A2 (ko) | 2008-09-03 | 2010-03-11 | 주식회사 엘지화학 | 다공성 코팅층을 구비한 세퍼레이터 및 이를 구비한 전기화학소자 |
JP5308118B2 (ja) * | 2008-10-30 | 2013-10-09 | 帝人株式会社 | 非水系二次電池用セパレータ、その製造方法、および非水系二次電池 |
WO2010101395A2 (ko) * | 2009-03-03 | 2010-09-10 | 주식회사 엘지화학 | 고에너지 밀도의 양극 재료와 유/무기 복합 다공성 분리막을 포함하는 리튬 이차전지 |
JP5670626B2 (ja) * | 2009-07-15 | 2015-02-18 | 日立マクセル株式会社 | 電気化学素子用セパレータ、電気化学素子およびその製造方法 |
JP5799498B2 (ja) | 2009-12-04 | 2015-10-28 | ソニー株式会社 | セパレータおよび電池 |
JP5621286B2 (ja) | 2010-03-16 | 2014-11-12 | 株式会社リコー | 画像処理装置、画像形成装置、情報処理装置、画像処理システム、画像処理方法、画像処理プログラム及び記憶媒体 |
JP2012003938A (ja) * | 2010-06-17 | 2012-01-05 | Hitachi Maxell Ltd | 電池用セパレータおよびリチウム二次電池 |
CN102064300A (zh) * | 2010-12-25 | 2011-05-18 | 佛山塑料集团股份有限公司 | 一种锂离子二次电池用多孔复合隔膜及其制备方法 |
JP5853400B2 (ja) | 2011-04-21 | 2016-02-09 | ソニー株式会社 | セパレータおよび非水電解質電池、ならびに電池パック、電子機器、電動車両、蓄電装置および電力システム |
JP6109467B2 (ja) * | 2011-06-28 | 2017-04-05 | 日産自動車株式会社 | 耐熱絶縁層付セパレータ |
CN102394282B (zh) * | 2011-11-25 | 2014-12-10 | 佛山市金辉高科光电材料有限公司 | 一种锂离子二次电池多孔多层隔膜及其制造方法 |
-
2014
- 2014-03-18 EP EP19173849.1A patent/EP3573137B1/en active Active
- 2014-03-18 CN CN201480014333.8A patent/CN105051941B/zh active Active
- 2014-03-18 KR KR1020157023873A patent/KR102130867B1/ko active IP Right Grant
- 2014-03-18 EP EP14770685.7A patent/EP2978047B1/en active Active
- 2014-03-18 JP JP2015506606A patent/JP6582979B2/ja active Active
- 2014-03-18 WO PCT/JP2014/001523 patent/WO2014148036A1/ja active Application Filing
- 2014-03-18 EP EP17202599.1A patent/EP3306708B1/en active Active
- 2014-03-18 CA CA2905653A patent/CA2905653C/en active Active
- 2014-03-18 US US14/777,356 patent/US10079379B2/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000030686A (ja) | 1998-04-27 | 2000-01-28 | Sumitomo Chem Co Ltd | 非水電解質電池セパレ―タ―とリチウム二次電池 |
JP2005353582A (ja) | 2004-05-11 | 2005-12-22 | Sony Corp | 電解液および電池 |
JP2007027100A (ja) * | 2005-06-14 | 2007-02-01 | Matsushita Electric Ind Co Ltd | 非水電解質二次電池 |
JP2007188777A (ja) * | 2006-01-13 | 2007-07-26 | Sony Corp | セパレータおよび非水電解質電池 |
JP2011159488A (ja) | 2010-02-01 | 2011-08-18 | Sony Corp | 非水電解質組成物および非水電解質二次電池 |
WO2012169681A1 (en) * | 2010-06-10 | 2012-12-13 | Sk Innovation Co., Ltd. | Microporous composite film with high thermostable organic/inorganic coating layer |
US20130059192A1 (en) * | 2011-09-05 | 2013-03-07 | Sony Corporation | Separator and nonaqueous electrolyte battery |
JP2013054972A (ja) * | 2011-09-05 | 2013-03-21 | Sony Corp | セパレータ、非水電解質電池、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 |
JP2013054973A (ja) * | 2011-09-05 | 2013-03-21 | Sony Corp | セパレータ、非水電解質電池、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 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2978047A4 |
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11532853B2 (en) | 2013-11-05 | 2022-12-20 | Murata Manufacturing Co., Ltd. | Transparent particle-containing resin layer, separator, electrode, and battery including the same, and coating material for making the same |
JPWO2015068325A1 (ja) * | 2013-11-05 | 2017-03-09 | ソニー株式会社 | 電池、セパレータ、電極、塗料、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 |
US10665841B2 (en) | 2013-11-05 | 2020-05-26 | Murata Manufacturing Co., Ltd. | Battery, separator, electrode, coating material, battery pack, electronic apparatus, electrically driven vehicle, electrical storage device, and electric power system |
WO2015122164A1 (ja) * | 2014-02-17 | 2015-08-20 | 三洋電機株式会社 | 非水電解質二次電池用セパレータ |
US10374203B2 (en) * | 2015-01-09 | 2019-08-06 | Lg Chem, Ltd. | Heat-diffusible separation film and secondary cell comprising the same |
JP2017126453A (ja) * | 2016-01-13 | 2017-07-20 | トヨタ自動車株式会社 | 非水電解液二次電池 |
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KR20200108418A (ko) | 2018-01-24 | 2020-09-18 | 데이진 가부시키가이샤 | 비수계 이차 전지용 세퍼레이터 및 비수계 이차 전지 |
WO2019225078A1 (ja) * | 2018-05-24 | 2019-11-28 | 株式会社日立製作所 | 絶縁層、電池セルシート、二次電池 |
JP2020068123A (ja) * | 2018-10-24 | 2020-04-30 | 株式会社エンビジョンAescエナジーデバイス | 電池 |
JP7198041B2 (ja) | 2018-10-24 | 2022-12-28 | 株式会社エンビジョンAescジャパン | 電池 |
JP2020113441A (ja) * | 2019-01-11 | 2020-07-27 | トヨタ自動車株式会社 | リチウムイオン二次電池用の負極 |
WO2020189795A1 (ja) | 2019-03-20 | 2020-09-24 | 帝人株式会社 | 非水系二次電池用セパレータ及び非水系二次電池 |
CN113574730A (zh) * | 2019-03-20 | 2021-10-29 | 帝人株式会社 | 非水系二次电池用隔膜及非水系二次电池 |
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WO2022025215A1 (ja) | 2020-07-31 | 2022-02-03 | 帝人株式会社 | 非水系二次電池用セパレータ及び非水系二次電池 |
WO2022045127A1 (ja) * | 2020-08-31 | 2022-03-03 | パナソニックIpマネジメント株式会社 | リチウム二次電池 |
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CN105051941A (zh) | 2015-11-11 |
KR102130867B1 (ko) | 2020-07-08 |
JPWO2014148036A1 (ja) | 2017-02-16 |
CA2905653A1 (en) | 2014-09-25 |
EP2978047B1 (en) | 2017-11-22 |
EP3306708B1 (en) | 2019-07-03 |
EP2978047A1 (en) | 2016-01-27 |
EP3306708A1 (en) | 2018-04-11 |
EP2978047A4 (en) | 2016-11-23 |
JP6582979B2 (ja) | 2019-10-02 |
CN105051941B (zh) | 2017-11-21 |
EP3573137B1 (en) | 2020-12-23 |
KR20150131005A (ko) | 2015-11-24 |
US10079379B2 (en) | 2018-09-18 |
US20160043370A1 (en) | 2016-02-11 |
CA2905653C (en) | 2020-06-23 |
EP3573137A1 (en) | 2019-11-27 |
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