WO2015068325A1 - 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 - Google Patents
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 Download PDFInfo
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- 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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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L50/00—Electric propulsion with power supplied within the vehicle
- B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
- B60L50/60—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells using power supplied by batteries
- B60L50/61—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells using power supplied by batteries by batteries charged by engine-driven generators, e.g. series hybrid electric vehicles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L50/00—Electric propulsion with power supplied within the vehicle
- B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
- B60L50/60—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells using power supplied by batteries
- B60L50/64—Constructional details of batteries specially adapted for electric vehicles
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B60L58/12—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling batteries responding to state of charge [SoC]
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B60L58/15—Preventing overcharging
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- H01M50/202—Casings or frames around the primary casing of a single cell or a single battery
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- 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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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
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Definitions
- This technology relates to batteries, separators, electrodes, paints, battery packs, electronic devices, electric vehicles, power storage devices, and power systems.
- Lithium ion secondary batteries have excellent energy density and are widely used for portable devices.
- a lithium ion secondary battery a battery using a laminate film as an exterior member has been put into practical use because it is lighter, has a higher energy density, and can be manufactured in a very thin shape.
- a battery such as a lithium ion secondary battery using a laminate film as an exterior member has been known to be a polymer battery, using an electrolytic solution and a polymer compound as an electrolyte for the purpose of leakage resistance and the like. Yes.
- a gel electrolyte battery in which the electrolytic solution is held in a polymer compound to form a so-called gel is widely used.
- Patent Document 1 proposes applying a resin to the surface of the separator.
- Patent Document 2 it is proposed to improve the strength of the gel electrolyte by mixing particles such as alumina in the gel electrolyte.
- the thickness of the resin layer containing particles is highly accurate due to the occurrence of white turbidity in the paint for forming the particles. It was difficult to manage.
- an object of the present technology is to provide a battery, a separator, an electrode, a paint, a battery pack, an electronic device, an electric vehicle, a power storage device, and an electric power that can manage the thickness of the resin layer containing particles with high accuracy. To provide a system.
- the present technology includes a positive electrode, a negative electrode, a separator, an electrolytic solution, a particle-containing resin layer containing particles and a resin, the shape of the particles includes a plane, and the particles
- the planarity of the battery is more than 40% and 100% or less, and the refractive index of the particles is 1.3 or more and less than 2.4.
- the present technology includes a separator base material and a particle-containing resin layer that is provided on at least one main surface of the separator base material and includes particles and a resin.
- the shape of the particles includes a flat surface.
- the separator has a rate of more than 40% and not more than 100%, and the refractive index of the particles is 1.3 or more and less than 2.4.
- the present technology includes an electrode and a particle-containing resin layer that is provided on at least one main surface of the electrode and includes particles and a resin, the shape of the particles includes a plane, and the plane rate of the particles is 40%. It is an electrode with a particle-containing resin layer which is ultra 100% or less and the refractive index of the particle is 1.3 or more and less than 2.4.
- the present technology includes particles, a resin, and a solvent, the shape of the particles includes a plane, the plane rate of the particles is more than 40% and 100% or less, and the refractive index of the particles is 1.3 or more.
- the battery pack, electronic device, electric vehicle, power storage device, and power system of the present technology include the above-described battery.
- the thickness of the resin layer containing particles can be managed with high accuracy.
- FIG. 1 is a schematic cross-sectional view of a separator according to an embodiment of the present technology.
- FIG. 2A is an SEM photograph of talc particles.
- FIG. 2B is an SEM photograph of boehmite particles.
- FIG. 3 is a schematic cross-sectional view of an electrode with a particle-containing resin layer according to an embodiment of the present technology.
- FIG. 4 is an exploded perspective view showing the configuration of a laminated film type nonaqueous electrolyte battery according to an embodiment of the present technology.
- FIG. 5 is a cross-sectional view showing a cross-sectional configuration along the line II of the spirally wound electrode body shown in FIG.
- FIG. 6A to 6C are exploded perspective views showing the configuration of a laminated film type non-aqueous electrolyte battery using a laminated electrode body. It is sectional drawing which shows the structure of the cylindrical nonaqueous electrolyte battery by embodiment of this technique. It is sectional drawing which expands and shows a part of winding electrode body accommodated in a cylindrical type nonaqueous electrolyte battery. It is sectional drawing which expands and shows a part of winding electrode body accommodated in a cylindrical type nonaqueous electrolyte battery.
- FIG. 10 is an exploded perspective view showing a configuration example of a simplified battery pack.
- FIG. 11A is a schematic perspective view showing the appearance of a simple battery pack.
- FIG. 11B is a schematic perspective view showing the appearance of a simple battery pack.
- FIG. 12 is a block diagram illustrating a circuit configuration example of the battery pack according to the embodiment of the present technology.
- FIG. 13 is a schematic diagram showing an example applied to a residential power storage system using the nonaqueous electrolyte battery of the present technology.
- FIG. 14 is a schematic diagram schematically illustrating an example of a configuration of a hybrid vehicle that employs a series hybrid system to which the present technology is applied.
- Patent Document 1 Patent No. 4986609 cited in the “Background Art” column
- a resin such as polyvinylidene fluoride or polytetrafluoroethylene is applied to the surface of the separator against deterioration due to oxidation of the separator. Attempts have been made to form a resin layer on the surface of the separator.
- the resin layer formed on the surface of the separator is interposed between the separator and the electrode to prevent the separator from touching the electrode and causing deterioration.
- the formation of the resin layer by this application is effective even when performed on the electrode surface side.
- Patent Document 2 Japanese Patent Laid-Open No. 2010-198757 proposes to improve the strength of the gel electrolyte by mixing particles such as alumina in the gel electrolyte.
- an electrolyte solution, a matrix resin, and particles are mixed in advance and a solvent is added to form a sol on the electrode, and then the solvent is evaporated. By solidifying, a gel electrolyte layer is formed. Thereafter, a method is adopted in which an electrode on which a gel electrolyte layer is formed is laminated or laminated and wound together with a separator to form a power generating element.
- this method has a problem that when the gel electrolyte layer is formed, a highly volatile component or a boiling point below the drying temperature is removed from the electrolyte component.
- particles such as alumina are dispersed in advance in a matrix resin layer provided on the separator or electrode, and the separator and electrode are wound or laminated to form an element.
- a method of forming a gel electrolyte layer by injecting an electrolyte solution into the exterior housing the element and impregnating the matrix resin layer with the electrolyte solution (rear) An injection method) has been attempted.
- the particle-containing resin solution mixed with particles such as alumina is in a state of poor transparency. Therefore, when a resin layer containing particles such as alumina is formed on the surface of the separator and / or electrode, simultaneously with the application of the particle-containing resin solution, the coating thickness is determined by an optical system thickness measuring device such as a laser. It is difficult to measure in real time with high accuracy. For this reason, in the coating process of the particle-containing resin solution, it becomes difficult to accurately manage the coating thickness in real time.
- the separator and the electrode are wound up to form an element, and then the thickness pass / fail is confirmed. It is usual to manage the coating thickness of the particle-containing resin solution by making the determination. However, in such management of the coating thickness, it takes a long time to adjust the coating thickness, or a material loss occurs.
- the transparency of the particle-containing resin solution containing particles is improved. Therefore, the thickness of the particle-containing resin solution layer formed on at least one surface of the electrode and the separator can be accurately measured and adjusted in real time during the particle-containing resin solution coating process. . Thereby, the thickness of the particle-containing resin layer formed by removing the solvent from the particle-containing resin solution can be managed with high accuracy. As a result, a battery including a particle-containing resin layer whose thickness is controlled with high accuracy can be provided. In such a battery, functional deterioration of the particle-containing resin layer due to excessive or insufficient thickness of the particle-containing resin layer is suppressed, so that high safety can be maintained.
- FIG. 1 is a schematic cross-sectional view illustrating a configuration example of a separator according to the first embodiment of the present technology.
- the separator 11 according to the first embodiment of the present technology includes a separator base 11a and a particle-containing resin layer 11b formed on at least one main surface of the separator base 11a.
- the separator base material 11a is a porous film composed of an insulating film having a high ion permeability and a predetermined mechanical strength. A non-aqueous electrolyte is held in the pores of the separator substrate 11a.
- 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 separator base 11a.
- 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 particle-containing resin layer 11b includes particles as a filler and a resin, and has a porous structure in which, for example, a large number of minute holes are formed.
- the separator characteristics such as heat resistance and oxidation resistance can be improved.
- the particle-containing resin layer 11b is formed from a particle-containing resin solution layer formed on the separator substrate 11a and including a resin solution (sometimes referred to as a paint) containing particles, a resin, and a dilution solvent. It is formed by removing the diluting solvent by drying or the like.
- the particle-containing resin layer 11b may contain an electrolytic solution.
- the particle-containing resin layer 11b in a state where the separator 11 is incorporated in the battery, the particle-containing resin layer 11b is impregnated with the electrolytic solution, and the particle-containing resin layer 11b includes the electrolytic solution.
- the particle-containing resin layer 11b containing the electrolytic solution forms the first state or the second state depending on the absorbability of the electrolytic solution of the resin contained in the particle-containing resin layer 11b.
- the absorptivity of the electrolyte solution of the resin can be changed by adjusting the resin type, polymerization degree, molecular weight, and the like.
- the resin in which the particle-containing resin layer 11b including the electrolytic solution forms the first state is referred to as a binder polymer compound, and the particle-containing resin layer 11b including the electrolytic solution forms the second state.
- a matrix polymer compound Is referred to as a matrix polymer compound.
- the electrolytic solution is contained in the particle-containing resin layer 11b in a state in which the electrolytic solution is present in a microporous (void) formed by at least one of the binder polymer compound and the particles.
- the particle-containing resin layer 11b has a function as a separator. That is, for example, the particle-containing resin layer 11b is interposed between the positive electrode and the negative electrode together with the separator base material 11a to prevent contact between the bipolar active materials, and in the same manner as the separator base material 11a, the particle-containing resin layer 11b is electrolyzed in the microporous structure. The liquid is held to form an ion conduction path between the electrodes.
- the electrolyte solution is absorbed in the matrix polymer compound and is included in the particle-containing resin layer 11b.
- the matrix polymer compound absorbs the electrolyte and swells to form a so-called gel state, and the matrix polymer compound holds the electrolyte and particles.
- the porous structure of the particle-containing resin layer 11b may disappear with the swelling of the matrix polymer compound.
- the particle-containing resin layer 11b has a function as an electrolyte. That is, the particle-containing resin layer 11b becomes an electrolyte in which the matrix polymer compound itself that has absorbed the electrolytic solution functions as an ionic conductor.
- resin a matrix polymer compound and a binder polymer compound having a property compatible with a solvent
- resins include fluorine-containing resins such as polyvinylidene fluoride and polytetrafluoroethylene, fluorine-containing rubbers such as vinylidene fluoride-tetrafluoroethylene copolymer and ethylene-tetrafluoroethylene copolymer, and styrene-butadiene copolymer.
- This resin may have, for example, a three-dimensional network structure in which the fibers are fibrillated and the fibrils are continuously connected to each other. Since the filler (particle) is supported on the resin having the three-dimensional network structure, the dispersed state can be maintained without being connected to each other. Further, the surface of the separator base material 11a and the particles may be bound to each other without the resin being fibrillated. In this case, higher binding properties can be obtained.
- the filler contained in the particle-containing resin layer 11b is a shape including a plane,
- particles having a predetermined plane rate and a predetermined refractive index are used.
- white inorganic powders such as alumina particles are formed of colorless and transparent particles, but are white due to light scattering.
- the filler in order to suppress light scattering, which is a factor of whitening, and to improve the transparency of the particle-containing resin solution layer of the precursor of the particle-containing resin layer 11b, the filler has a shape including a plane, and , Particles having a predetermined plane index and a predetermined refractive index are used.
- the particle plane includes at least one of a crystal plane, a fracture plane, and a cleavage plane formed by crystal growth.
- the crushing surface is intended for the purpose of particle size control during particle preparation, for example, when a paint for forming a particle-containing resin solution layer is prepared, or when particles, resin and dilution solvent are mixed. It is formed by splitting.
- the cleavage plane is formed, for example, by intentional cracking or spontaneous cracking at a specific atomic arrangement plane in the single crystal.
- the particles may be, for example, single crystal or polycrystal, and may be a single crystal and polycrystal aggregate.
- FIG. 2A shows an SEM photograph of a talc particle having a shape including a plane observed with a scanning electron microscope (SEM).
- FIG. 2B shows an SEM photograph of boehmite particles having a shape including a plane observed by SEM.
- SEM photograph of FIG. 2A the particle surface centering on the cleavage of talc particles is observed.
- SEM photograph of FIG. 2B the particle surface surrounded by the crystal plane formed by the crystal growth in the hydrothermal synthesis of boehmite is observed.
- the plane rate of the particles is more than 40% and 100% or less from the viewpoint of ensuring the transparency of the particle-containing resin solution layer, and more preferably 45% or more and 100% or less from the viewpoint of further improving the transparency. More preferably, it is 60% or more and 100%.
- the plane rate can be obtained as follows, for example.
- the particle-containing resin layer 11b is observed with an SEM (Scanning Electron Microscope), and the volume-based 50% average particle diameter (D50) is around 50%. Take a picture of 10 particles of typical shape in size.
- the average particle diameter (D50) is measured by putting the powder after removing the resin component and the like from the particle-containing resin layer 11b into a laser diffraction particle size distribution measuring apparatus.
- the projection area of the plane corresponding to the crystal plane, the crushing plane, and the cleavage plane (of the total area if there are multiple planes) is calculated, and the projection of the plane to the projection area of the entire grain
- the percentage of the area is calculated, and the average value of the calculated percentage of each particle is defined as the plane rate.
- Method for producing particles having a shape including a flat surface In order to produce particles having a shape including a flat surface, there are a growing method in which a single crystal is grown to form a smooth crystal surface, a method in which crystal particles are broken by pulverization, and the like. As a method for growing a single crystal, a flux method for growing in a liquid, a hydrothermal growth method, a coprecipitation method and the like are preferable.
- a material having a Mohs hardness of 5 or less is used, or a method of cleaving on a specific lattice plane is used.
- the dispersion of the material and the pulverization of the material may be performed simultaneously by using a dispersion method such as Desperm or bead mill.
- the refractive index of the particles is 1.3 or more and less than 2.4, and preferably 1.3 or more and 2.1 or less. This is to suppress a decrease in transparency due to scattering due to refraction of light coming from the difference in refractive index between the resin solution and the particles (difference that the solid has a high refractive index and the liquid has a low refractive index).
- the lower refractive index is 1.3 or more and less than 2.4, preferably 1.3 or more. Use particles in the range of 2.1 or less.
- inorganic particles and organic particles can be used as the particles.
- the inorganic particles include particles of metal oxide, sulfate compound, carbonate compound, metal hydroxide, metal carbide, metal nitride, metal fluoride, phosphate compound, mineral, and the like.
- particles having electrical insulation properties are typically used.
- the surface of the particles (fine particles) of the conductive material is electrically insulated by performing surface treatment with the electrical insulation material. Sedimented particles (fine particles) may be used.
- metal oxide examples include silicon oxide (SiO 2 , silica (silica powder, quartz glass, glass beads, diatomaceous earth, wet or dry synthetic products, etc.), wet synthetic products such as colloidal silica, and dry synthetic products such as fumed silica.
- Zinc oxide (ZnO), tin oxide (SnO), magnesium oxide (magnesia, MgO), antimony oxide (Sb 2 O 3 ), aluminum oxide (alumina, Al 2 O 3 ), etc. are preferably used. be able to.
- magnesium sulfate (MgSO 4 ), calcium sulfate (CaSO 4 ), barium sulfate (BaSO 4 ), strontium sulfate (SrSO 4 ) and the like can be suitably used.
- carbonate compound magnesium carbonate (MgCO 3 , magnesite), calcium carbonate (CaCO 3 , calcite), barium carbonate (BaCO 3 ), lithium carbonate (Li 2 CO 3 ) and the like can be suitably used.
- metal carbide boron carbide (B 4 C) or the like can be suitably used.
- metal nitride silicon nitride (Si 3 N 4 ), boron nitride (BN), aluminum nitride (AlN), titanium nitride (TiN), or the like can be suitably used.
- lithium fluoride LiF
- aluminum fluoride AlF 3
- calcium fluoride CaF 2
- barium fluoride BaF 2
- magnesium fluoride or the like
- phosphate compound trilithium phosphate (Li 3 PO 4 ), magnesium phosphate, magnesium hydrogen phosphate, ammonium polyphosphate, and the like can be suitably used.
- Examples of minerals include silicate minerals, carbonate minerals, and oxide minerals.
- Silicate minerals are classified into nesosilicate minerals, solosilicate minerals, cyclosilicate minerals, inosilicate minerals, layered (phyllo) silicate minerals, and tectosilicate minerals based on their crystal structures. . Some are classified into fibrous silicate minerals called asbestos based on a classification standard different from the crystal structure.
- the nesosilicate mineral is an island-like tetrahedral silicate mineral made of an independent Si—O tetrahedron ([SiO 4 ] 4 ⁇ ).
- Examples of the nesosilicate mineral include those corresponding to olivines and meteorites.
- olivine a continuous solid solution of Mg 2 SiO 4 (magnerite olivine) and Fe 2 SiO 4 (iron olivine)
- magnesium silicate forsterite (bitter) Earth olivine
- Mg 2 SiO 4 aluminum silicate
- Al 2 SiO 5 aluminum silicate
- Zn 2 SiO 4 zirconium silicate
- mullite 3Al 2 O 3 .2SiO 2 to 2Al 2 O 3 .SiO 2
- the solosilicate mineral is a group structure type silicate mineral composed of a Si—O tetrahedral double bond group ([Si 2 O 7 ] 6 ⁇ , [Si 5 O 16 ] 12 ⁇ ).
- Examples of the silicate mineral include those corresponding to vesuvite and chlorite.
- the cyclosilicate mineral is composed of a Si—O tetrahedral finite (3-6) ring ([Si 3 O 9 ] 6 ⁇ , [Si 4 O 12 ] 8 ⁇ , [Si 6 O 18 ] 12. - ) An annular silicate mineral.
- Examples of the cyclosilicate mineral include beryl and tourmaline.
- Inosilicate minerals have an infinite number of Si—O tetrahedral linkages, and are chain-like ([Si 2 O 6 ] 4 ⁇ ) and belt-like ([Si 3 O 9 ] 6 ⁇ , [Si 4 O 11 ] 6 - , [Si 5 O 15 ] 10- , [Si 7 O 21 ] 14- ).
- Examples of the inosilicate mineral include those corresponding to pyroxenes such as calcium silicate (wollastonite, CaSiO 3 ), and those corresponding to amphibole.
- the layered silicate mineral is a layered silicate mineral that forms a network bond of Si—O tetrahedra ([SiO 4 ] 4 ⁇ ).
- SiO 4 tetrahedra
- the specific example of a layered silicate mineral is mentioned later.
- the tectosilicate mineral is a three-dimensional network structure type silicate mineral in which a Si—O tetrahedron ([SiO 4 ] 4 ⁇ ) forms a three-dimensional network bond.
- the tectosilicates minerals, quartz, feldspars, zeolites, and the like, zeolite (M 2 / n O ⁇ Al 2 O 3 ⁇ xSiO 2 ⁇ yH 2 O, M is a metal element, n represents the valence of M, x ⁇ 2, y ⁇ 0) aluminosilicate zeolite such as (aM 2 O ⁇ bAl 2 O 3 ⁇ cSiO 2 ⁇ dH 2 O, M is as defined above .a, b, c, d are each 1 or more And the like.) And the like.
- ⁇ Asbestos include chrysotile, amosite, anthophinite and the like.
- the carbonate minerals dolomite (dolomite, CaMg (CO 3) 2) , hydrotalcite (Mg 6 Al 2 (CO 3 ) (OH) 16 ⁇ 4 (H 2 O)) and the like.
- oxide mineral examples include spinel (MgAl 2 O 4 ).
- Examples of other minerals include barium titanate (BaTiO 3 ) and strontium titanate (SrTiO 3 ).
- the mineral may be a natural mineral or an artificial mineral.
- clay minerals include a crystalline clay mineral, an amorphous or quasicrystalline clay mineral, and the like.
- crystalline clay minerals include layered silicate minerals, those having a structure similar to layered silicates, silicate minerals such as other silicate minerals, and layered carbonate minerals.
- the layered silicate mineral includes a Si—O tetrahedral sheet and an octahedral sheet such as Al—O and Mg—O combined with the tetrahedral sheet.
- Layered silicates are typically classified by the number of tetrahedral and octahedral sheets, the number of cations in the octahedron, and the layer charge.
- the layered silicate mineral may be one obtained by substituting all or part of metal ions between layers with organic ammonium ions or the like.
- the layered silicate minerals include a kaolinite-serpentine group with a 1: 1 type structure, a pyrophyllite-talc group, a smectite group, a vermiculite group, a mica group with a 2: 1 type structure. And those corresponding to the brittle mica (brittle mica) family, chlorite (chlorite group), and the like.
- Examples of the kaolinite-serpentine family include chrysotile, antigolite, lizardite, kaolinite (Al 2 Si 2 O 5 (OH) 4 ), and dickite.
- Examples of the pyrophyllite-talc family include talc (Mg 3 Si 4 O 10 (OH) 2 ), willemsite, and granite (pyrophyllite, Al 2 Si 4 O 10 (OH) 2. ) And the like.
- smectite group examples include saponite [(Ca / 2, Na) 0.33 (Mg, Fe 2+ ) 3 (Si, Al) 4 O 10 (OH) 2 .4H 2 O], hectorite, Sauconite, montmorillonite ⁇ (Na, Ca) 0.33 (Al, Mg) 2Si 4 O 10 (OH) 2 .nH 2 O, where clay containing montmorillonite as a main component is called bentonite ⁇ , beidellite, nontrite, etc. .
- Examples of the mica (mica) family include, for example, moscovite (muscovite, KAl 2 (AlSi 3 ) O 10 (OH) 2 ) sericite (sericite), phlogopite (phlogopite), biotite, lipidite ( Lithia mica) and the like.
- Examples of those belonging to the brittle mica (brittle mica) family include margarite, clintonite, and anandite.
- Examples of the chlorite (chlorite) family include kukkeite, sudokuite, clinochlore, chamosite, and nimite.
- a hydrous magnesium silicate having a 2: 1 ribbon structure in which a tetrahedron sheet arranged in a ribbon shape is connected to a tetrahedron sheet arranged in an adjacent ribbon shape while reversing the apex.
- the hydrous magnesium silicate include sepiolite (foamstone: Mg 9 Si 12 O 30 (OH) 6 (OH 2 ) 4 .6H 2 O), palygorskite and the like.
- silicate minerals zeolites (M 2 / n O ⁇ Al 2 O 3 ⁇ xSiO 2 ⁇ yH 2 O, M is a metal element, n represents the valence of M, x ⁇ 2, y ⁇ 0) , etc.
- the layered carbonate minerals hydrotalcite (Mg 6 Al 2 (CO 3 ) (OH) 16 ⁇ 4 (H 2 O)) and the like.
- amorphous or quasicrystalline clay mineral examples include bingellite, imogolite (Al 2 SiO 3 (OH)), and allophane.
- These inorganic particles may be used alone or in combination of two or more.
- the particles may be organic particles.
- Materials constituting the organic particles include melamine, melamine cyanurate, melamine polyphosphate, cross-linked polymethyl methacrylate (cross-linked PMMA), polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyvinylidene fluoride, polyamide, polyimide, melamine Resins, phenol resins, epoxy resins and the like can be mentioned. These materials may be used alone or in combination of two or more.
- the mixing ratio between the particles and the resin is such that the refractive index of the resin solution is close to that of the particles, and the transparency of the particle-containing resin solution can be further improved.
- the thickness of the separator 11 can be arbitrarily set as long as it is equal to or greater than a thickness that can maintain a required strength.
- the separator 11 insulates between the positive electrode and the negative electrode, prevents a short circuit and the like, has ion permeability for suitably performing the battery reaction via the separator 11, and contributes to the battery reaction in the battery. It is preferable to set the thickness of the active material layer to be as thick as possible.
- the thickness of the separator 11 is preferably 7 ⁇ m or more and 20 ⁇ m or less, for example. In addition, the thickness of the separator 11 is not limited to this range.
- the particle-containing resin layer 11b is formed on one main surface or both main surfaces of the separator substrate 11a. Thereby, the separator 11 can be obtained.
- the particle-containing resin layer 11b can be formed by, for example, the following first to second examples.
- the resin and the particles are mixed at a predetermined mass ratio, added to a dispersion solvent such as N-methyl-2-pyrrolidone, and the resin is dissolved to obtain a paint (particle-containing resin solution). Then, this coating material is apply
- a dispersion solvent such as N-methyl-2-pyrrolidone
- the thickness of the coating film is measured with an optical film thickness measuring device such as a laser, and if the measured value is different from the target predetermined thickness, the paint The coating thickness of the paint is adjusted by automatically adjusting the discharge amount.
- a paint having improved transparency can be obtained by using particles having a predetermined flatness and a predetermined refractive index.
- the particle-containing resin solution layer can be formed while accurately controlling the coating thickness in real time by an optical film thickness measuring device such as a laser. Therefore, the particle-containing resin layer 11b whose thickness is controlled with high accuracy can be formed. This is the same in the second example described later.
- the separator 11 in which the particle-containing resin layer 11b is formed on the surface of the separator substrate 11a can be obtained by drying the particle-containing resin solution layer with hot air or the like.
- the resin does not have a unique three-dimensional network structure as in the second example described later.
- the resin may be, for example, at least between particles and between the particles and the substrate surface. In other words, the particles bind to each other or bind the particles to the substrate surface.
- the resin and the particles are mixed at a predetermined mass ratio, added to a dispersion solvent such as N-methyl-2-pyrrolidone, and the resin is dissolved to obtain a paint (particle-containing resin solution). Then, this coating material is apply
- a dispersion solvent such as N-methyl-2-pyrrolidone
- the separator substrate 11a on which the particle-containing resin solution layer is formed is immersed in a water bath to phase-separate the particle-containing resin solution, and then dried. That is, the particle-containing resin solution layer formed on the surface of the separator substrate 11a is a poor solvent for the resin that dissolves in the dispersion solvent, and a good solvent for the dispersion solvent that dissolves the resin. After contact and phase separation, dry with hot air or the like. Thereby, the separator 11 in which the particle-containing resin layer 11b made of a resin having a three-dimensional network structure carrying particles is formed on the surface of the separator substrate 11a can be obtained.
- the particle-containing resin layer 11b is formed by a rapid poor solvent-induced phase separation phenomenon, and the particle-containing resin layer 11b is a three-dimensional structure in which the resin is fibrillated and the fibrils are continuously connected to each other.
- Network structure three-dimensional network structure. That is, the solvent exchange is achieved by bringing the particle-containing resin solution in which the resin is dissolved into contact with a solvent such as water that is a poor solvent for the resin and a good solvent for the dispersion solvent that dissolves the resin. Occur. This causes a rapid (fast) phase separation with spinodal decomposition and the resin has a unique three-dimensional network structure.
- the particle-containing resin layer 11b produced in the second example forms a unique porous structure by utilizing an abrupt poor solvent-induced phase separation phenomenon accompanied by spinodal decomposition by a poor solvent.
- FIG. 3 is a schematic cross-sectional view showing a configuration example of an electrode with a particle-containing resin layer according to the first embodiment of the present technology.
- the electrode 21 with particle-containing resin layer includes an electrode 21a and a particle-containing resin layer 21b formed on at least one main surface of the electrode 21a.
- FIG. 3 shows a configuration example in which the particle-containing resin layer 21b is formed on both main surfaces of the electrode 21a, but the particle-containing resin layer 21b is formed only on one main surface of the electrode 21a. It may be.
- the electrode 21a may be a positive electrode or a negative electrode.
- the particle-containing resin layer 21b includes particles and a resin, and the details of the configuration and the formation method are the first implementation except that the electrode 21a is formed instead of the separator substrate 11a. It is the same as the form.
- the particle-containing resin layer 21b is impregnated with an electrolytic solution, and the particle-containing resin layer 21b includes an electrolytic solution.
- the particle-containing resin layer 21b containing the electrolytic solution forms the first state or the second state depending on the absorbability of the electrolytic solution of the resin contained in the particle-containing resin layer 21b.
- the electrolytic solution is contained in the particle-containing resin layer 21b in a state where it exists in a microporous (void) formed by at least one of the binder polymer compound and particles.
- the particle-containing resin layer 21b has a function as a separator.
- the particle-containing resin layer 21b is interposed between the positive electrode and the negative electrode to prevent the contact between the bipolar active materials and to hold the electrolytic solution in the micropore to form an ion conduction path between the electrodes. .
- the electrolytic solution is absorbed by the matrix polymer compound and is included in the particle-containing resin layer 21b.
- the matrix polymer compound absorbs the electrolyte and swells to form a so-called gel state, and the matrix polymer compound holds the electrolyte and particles.
- the porous structure of the particle-containing resin layer 11b may disappear with the swelling of the matrix polymer compound.
- the particle-containing resin layer 21b has a function as an electrolyte. That is, the particle-containing resin layer 21b becomes an electrolyte in which the matrix polymer compound itself that has absorbed the electrolytic solution functions as an ionic conductor.
- This nonaqueous electrolyte battery is, for example, a nonaqueous electrolyte secondary battery that can be charged and discharged, and is, for example, a lithium ion secondary battery.
- the battery according to the third embodiment is a separator similar to that of the first embodiment, and incorporates a matrix polymer compound as the resin of the particle-containing resin layer 11b.
- the separator 55 corresponds to the separator base material 11a
- the gel electrolyte layer 56 corresponds to the particle-containing resin layer 11b containing the electrolytic solution formed on the separator base material 11a.
- FIG. 4 shows a first configuration example of the nonaqueous electrolyte battery 62 according to the third 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. 5 shows a cross-sectional structure taken along line II of the spirally wound electrode body 50 shown in FIG.
- the wound electrode body 50 has a structure in which a belt-like positive electrode 53 and a belt-like negative electrode 54 are laminated and wound via a belt-like separator 55 and a gel electrolyte layer 56.
- the outermost periphery 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 positive electrode 53 is obtained by forming a positive electrode active material layer 53B containing a positive electrode active material on both surfaces of a positive electrode current collector 53A.
- a positive electrode current collector 53A for example, 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 53B is configured to include any one or two or more of positive electrode materials capable of inserting and extracting lithium as a positive electrode active material. Other materials such as a conductive agent 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 53 has a positive electrode lead 51 connected to one end of the positive electrode current collector 53A by spot welding or ultrasonic welding.
- the positive electrode lead 51 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 51 include aluminum (Al) and nickel (Ni).
- 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 negative electrode active material layer 54B may be provided only on one surface of the negative electrode current collector 54A.
- the negative electrode current collector 54A is made of, for example, a metal foil such as a copper foil.
- the negative electrode active material layer 54B includes one or more negative electrode materials capable of occluding and releasing lithium as the negative electrode active material, and the positive electrode active material layer 53B 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 inserting and extracting lithium is larger than the electrochemical equivalent of the positive electrode 53, and theoretically, the negative electrode 54 is in the middle of charging. Lithium metal is prevented from precipitating.
- the nonaqueous electrolyte battery 62 is designed such that the open circuit voltage (that is, the battery voltage) in the fully charged state is in the range of, for example, 2.80 V or more and 6.00 V or less.
- the open circuit voltage in a fully charged state is, for example, 4.20 V or more and 6.00 V. It is designed to be within the following range. In this case, 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.
- anode material capable of inserting and extracting lithium and capable of increasing the capacity
- lithium can be inserted and extracted, and at least one of a metal element and a metalloid element can be used.
- materials containing as a constituent element are also 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. Some of the structures include a solid solution, a eutectic (eutectic mixture), an intermetallic compound, or two or more of them.
- 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 preferably includes a 4B group metal element or metalloid element in the short periodic table as a constituent element, and more preferably includes at least one of silicon (Si) and tin (Sn) as a constituent element. 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).
- Examples of the negative electrode material capable of occluding and releasing lithium include metal oxides and polymer compounds capable of occluding and releasing lithium.
- Examples of the metal oxide include lithium titanium oxide containing titanium and lithium such as lithium titanate (Li 4 Ti 5 O 12 ), iron oxide, ruthenium oxide, or molybdenum oxide.
- Examples of the polymer compound include polyacetylene, polyaniline, polypyrrole, and the like.
- the separator 55 is a porous film made of an insulating film having a high ion permeability and a predetermined mechanical strength. A non-aqueous electrolyte is held in the pores of the separator 55.
- the configuration of the separator 55 is the same as that of the separator substrate 11a of the first embodiment.
- the gel electrolyte layer 56 includes particles as a filler, a matrix polymer compound (resin), and a nonaqueous electrolytic solution (electrolytic solution).
- the particle-containing resin layer formed on at least one main surface of the separator 55 is an electrolytic solution. It is formed by including.
- the particle-containing resin layer formed on at least one main surface of the separator 55 is, for example, a matrix polymer compound that absorbs the electrolytic solution and swells to form a so-called gel.
- the molecule itself becomes the gel electrolyte layer 56 that functions as an ionic conductor. In this case, the porous structure of the particle-containing resin layer may disappear as the matrix polymer compound swells. Since the gel electrolyte layer 56 contains particles, the strength, heat resistance, and oxidation resistance of the gel electrolyte layer 56 are improved, and characteristics such as safety can be improved.
- Nonaqueous electrolyte 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 54 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.
- This nonaqueous electrolyte battery 62 can be manufactured, for example, by the following method.
- This nonaqueous electrolyte battery 62 typically includes, for example, the following positive electrode manufacturing process, negative electrode manufacturing process, particle-containing resin layer forming process (separator manufacturing process), winding process, and battery assembling process. Manufactured sequentially.
- 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.
- the positive electrode mixture slurry is applied to the positive electrode current collector 53A, the solvent is dried, and the positive electrode active material layer 53B is formed by compression molding with a roll press or the like, and the positive electrode 53 is manufactured. Thereafter, the positive electrode lead 51 is attached to the end of the positive electrode current collector 53A by welding.
- 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.
- this negative electrode mixture slurry is applied to the negative electrode current collector 54A, the solvent is dried, and the negative electrode active material layer 54B is formed by compression molding with a roll press machine or the like, and the negative electrode 54 is manufactured. Thereafter, 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 are laminated and wound via a separator 55 having a particle-containing resin layer formed on one or both main surfaces, whereby a wound electrode body 50 having a wound structure. Is made. 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 exterior member 60 made of a laminate film is deep-drawn to form a recess, the wound electrode body 50 is inserted into the recess, the unprocessed portion of the exterior member 60 is folded back to the upper portion of the recess, and the outer periphery of the recess Heat welding is performed except for a part (for example, one side).
- an adhesion film 61 is inserted between the positive electrode lead 51 and the negative electrode lead 52 and the exterior member 60.
- the unwelded portion of the exterior member 60 is sealed by heat fusion or the like.
- the particle-containing resin layer is impregnated with the non-aqueous electrolyte, and the matrix polymer compound (resin) swells to form the gel electrolyte layer 56.
- the nonaqueous electrolyte battery 62 shown in FIGS. 4 and 5 is completed.
- FIG. 6A is an external view of a nonaqueous electrolyte battery 62 that houses the laminated electrode body 70.
- FIG. 6B is an exploded perspective view showing a state in which the laminated electrode body 70 is accommodated in the exterior member 60.
- FIG. 6C is an external view showing an external appearance from the bottom surface side of the nonaqueous electrolyte battery 62 shown in FIG. 6A.
- the laminated electrode body 70 uses a laminated electrode body 70 in which a rectangular positive electrode 73 and a rectangular negative electrode 74 are laminated via a rectangular separator 75 and fixed by a fixing member 76.
- the gel electrolyte layer is provided in contact with the positive electrode 73 and the negative electrode 74.
- a gel electrolyte layer (not shown) is provided between the positive electrode 73 and the separator 75 and between the negative electrode 74 and the separator 75. This gel electrolyte layer is the same as the gel electrolyte layer 56 of the first configuration example.
- a positive electrode lead 71 connected to the positive electrode 73 and a negative electrode lead 72 connected to the negative electrode 74 are led out from the laminated electrode body 70, and the positive electrode lead 71, the negative electrode lead 72, and the exterior member 60 are in close contact with each other.
- a film 61 is provided.
- the formation method of the gel electrolyte layer and the heat fusion method of the exterior member 60 are the same as those in the first configuration example.
- This nonaqueous electrolyte battery is, for example, a nonaqueous electrolyte secondary battery that can be charged and discharged, and is, for example, a lithium ion secondary battery.
- the battery according to the fourth embodiment is an electrode with a particle-containing resin layer similar to that of the second embodiment, in which a battery using a matrix polymer compound is incorporated as the resin of the particle-containing resin layer. Yes.
- the separator 55 is the same as the separator substrate 11a, and the gel electrolyte layer 56 corresponds to the particle-containing resin layer 11b containing the electrolytic solution formed on the electrode.
- the first configuration example of the nonaqueous electrolyte battery 62 according to the fourth embodiment is the same as that of the third embodiment shown in FIGS. 4 and 5 except for the points described below. This is the same as the first configuration example of the nonaqueous electrolyte battery 63. That is, the non-aqueous electrolyte battery 62 does not incorporate the one having the particle-containing resin layer formed on the surface of the separator 55 (the separator according to the first embodiment) as in the third embodiment. Instead, an electrode with a particle-containing resin layer similar to that of the second embodiment, in which a matrix polymer compound is used as the resin of the particle-containing resin layer, is incorporated.
- the gel electrolyte layer 56 is formed because the particle
- the gel electrolyte layer 56 includes particles as a filler, a matrix polymer compound (resin), and a nonaqueous electrolytic solution (electrolytic solution), and is formed on the main surfaces of at least one of the positive electrode 53 and the negative electrode 54.
- the particle-containing resin layer is formed by containing an electrolytic solution.
- the particle-containing resin layer formed on both main surfaces of at least one of the positive electrode 53 and the negative electrode 54 is, for example, a matrix polymer compound that absorbs the electrolyte and swells to form a so-called gel.
- the absorbed gel-like matrix polymer itself becomes a gel electrolyte layer 56 that functions as an ionic conductor.
- the porous structure of the particle-containing resin layer may disappear due to swelling of the matrix polymer compound. Since the gel electrolyte layer 56 contains particles, the strength, heat resistance, and oxidation resistance of the gel electrolyte layer 56 are improved, and characteristics such as safety can be improved.
- this nonaqueous electrolyte battery 62 contains particles after, for example, the same positive electrode preparation step and negative electrode preparation step as those in the third embodiment.
- an electrode with a particle-containing resin layer (positive electrode) in which a particle-containing resin layer is formed on both main surfaces of the positive electrode 53 and an electrode with a particle-containing resin layer in which a particle-containing resin layer is formed on both main surfaces of the negative electrode 54 (Negative electrode) is prepared. Only one of the positive electrode and the negative electrode may be an electrode with a particle-containing resin layer.
- the method for forming the particle-containing resin layer is the same as in the second embodiment.
- the exterior member 60 made of a laminate film is deep-drawn to form a recess, the wound electrode body 50 is inserted into the recess, the unprocessed portion of the exterior member 60 is folded back to the upper portion of the recess, and the outer periphery of the recess Heat welding is performed except for a part (for example, one side).
- an adhesion film 61 is inserted between the positive electrode lead 51 and the negative electrode lead 52 and the exterior member 60.
- the unwelded portion of the exterior member 60 is sealed by heat fusion or the like.
- the non-aqueous electrolyte solution is impregnated into the particle-containing resin layer, and the matrix polymer compound (resin) absorbs the non-aqueous electrolyte solution and swells to form the gel electrolyte layer 56. .
- the nonaqueous electrolyte battery 62 shown in FIGS. 4 and 5 is completed.
- the laminated electrode body 70 uses a laminated electrode body 70 in which a rectangular positive electrode 73 and a rectangular negative electrode 74 are laminated via a rectangular separator 75 and fixed by a fixing member 76.
- the gel electrolyte layer is provided in contact with the positive electrode 73 and the negative electrode 74.
- a gel electrolyte layer (not shown) is provided between the positive electrode 73 and the separator 75 and between the negative electrode 74 and the separator 75. This gel electrolyte layer is the same as the gel electrolyte layer 56 of the first configuration example.
- a positive electrode lead 71 connected to the positive electrode 73 and a negative electrode lead 72 connected to the negative electrode 74 are led out from the laminated electrode body 70, and the positive electrode lead 71, the negative electrode lead 72, and the exterior member 60 are in close contact with each other.
- a film 61 is provided.
- the formation method of the gel electrolyte layer and the heat fusion method of the exterior member 60 are the same as those in the first configuration example.
- the battery according to the fifth embodiment is the same separator as in the first embodiment, and incorporates a binder polymer compound as the resin of the particle-containing resin layer.
- FIG. 7 is a cross-sectional view showing an example of a nonaqueous electrolyte battery according to the fifth embodiment.
- the nonaqueous electrolyte battery 80 is a nonaqueous electrolyte secondary battery that can be charged and discharged, for example.
- This non-aqueous electrolyte battery 80 is a so-called cylindrical type, and is formed in a substantially hollow cylindrical battery can 81 together with a liquid non-aqueous electrolyte (not shown) (hereinafter appropriately referred to as a non-aqueous electrolyte) in a strip shape.
- the positive electrode 91 and the negative electrode 92 have a wound electrode body 90 wound with a separator 93 interposed therebetween.
- the battery can 81 is made of, for example, iron plated with nickel, and has one end closed and the other end open. Inside the battery can 81, a pair of insulating plates 82a and 82b are respectively arranged perpendicular to the winding peripheral surface so as to sandwich the winding electrode body 90 therebetween.
- Examples of the material of the battery can 81 include iron (Fe), nickel (Ni), stainless steel (SUS), aluminum (Al), titanium (Ti), and the like.
- the battery can 81 may be plated with, for example, nickel in order to prevent corrosion due to the electrochemical non-aqueous electrolyte associated with charging / discharging of the non-aqueous electrolyte battery 10.
- a battery lid 83 that is a positive electrode lead plate and a safety valve mechanism and a heat-sensitive resistance element (PTC element: Positive Temperature Coefficient) 87 provided inside the battery lid 83 are provided at the open end of the battery can 81 with an insulating seal. It is attached by caulking through a gasket 88 for
- the battery lid 83 is made of the same material as the battery can 81, for example, and is provided with an opening for discharging gas generated inside the battery.
- a safety valve 84, a disc holder 85, and a shut-off disc 86 are sequentially stacked.
- the protruding portion 84a of the safety valve 84 is connected to the positive electrode lead 95 led out from the wound electrode body 90 through a sub disk 89 disposed so as to cover a hole 86a provided at the center of the shutoff disk 86. .
- the safety valve mechanism is electrically connected to the battery lid 83 via the heat sensitive resistance element 87.
- the safety valve mechanism when the internal pressure of the nonaqueous electrolyte battery 80 becomes a certain level or more due to internal short circuit or heating from the outside of the battery, the safety valve 84 is reversed, and the protrusion 84a, the battery lid 83, and the wound electrode body 90 are reversed. The electrical connection with is disconnected. That is, when the safety valve 84 is reversed, the positive electrode lead 95 is pressed by the shut-off disk 86 and the connection between the safety valve 84 and the positive electrode lead 95 is released.
- the disc holder 85 is made of an insulating material, and when the safety valve 84 is reversed, the safety valve 84 and the shut-off disc 86 are insulated.
- a plurality of gas vent holes are provided around the hole 86a of the shut-off disk 86.
- gas vent holes are provided around the hole 86a of the shut-off disk 86.
- the heat sensitive resistance element 87 increases in resistance value when the temperature rises, interrupts the current by disconnecting the electrical connection between the battery lid 83 and the wound electrode body 90, and generates abnormal heat due to an excessive current.
- the gasket 88 is made of, for example, an insulating material, and asphalt is applied to the surface.
- the wound electrode body 20 accommodated in the nonaqueous electrolyte battery 80 is wound around the center pin 94.
- the wound electrode body 90 is formed by sequentially laminating a positive electrode 91 and a negative electrode 92 with a separator 93 interposed therebetween and wound in the longitudinal direction.
- a positive electrode lead 95 is connected to the positive electrode 91, and a negative electrode lead 96 is connected to the negative electrode 92.
- the positive electrode lead 95 is welded to the safety valve 84 and electrically connected to the battery lid 83, and the negative electrode lead 96 is welded to and electrically connected to the battery can 81.
- FIG. 8 shows an enlarged part of the spirally wound electrode body 90 shown in FIG.
- the positive electrode 91, the negative electrode 92, and the separator 93 will be described in detail.
- a positive electrode active material layer 91B containing a positive electrode active material is formed on both surfaces of the positive electrode current collector 91A.
- 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 91 ⁇ / b> B is configured to include any one or more of positive electrode materials capable of inserting and extracting lithium as a positive electrode active material. Or other materials such as a conductive agent.
- the positive electrode active material, the conductive agent, and the binder can be the same as those in the third embodiment.
- the positive electrode 91 has a positive electrode lead 95 connected to one end of the positive electrode current collector 91A by spot welding or ultrasonic welding.
- the positive electrode lead 95 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 95 include aluminum (Al) and nickel (Ni).
- the negative electrode 92 has, for example, a structure in which a negative electrode active material layer 92B is provided on both surfaces of a negative electrode current collector 92A having a pair of opposed surfaces. Although not shown, the negative electrode active material layer 92B may be provided only on one surface of the negative electrode current collector 92A.
- the negative electrode current collector 92A is made of, for example, a metal foil such as a copper foil.
- the negative electrode active material layer 92B includes one or more negative electrode materials capable of occluding and releasing lithium as the negative electrode active material, and the positive electrode active material layer 91B as necessary. Other materials such as a binder and a conductive agent similar to those described above may be included.
- the negative electrode active material, the conductive agent, and the binder can be the same as those in the third embodiment.
- the separator 93 is the same as the separator 11 according to the first embodiment. That is, as shown in FIG. 8, the particle-containing resin layer 93b is formed on both main surfaces of the separator base material 93a. The particle-containing resin layer 93b may be formed only on one main surface of the separator base material 93a. The particle-containing resin layer 93b improves the strength, heat resistance, and oxidation resistance of the separator 93, and improves safety and other characteristics. As the resin contained in the particle-containing resin layer 93b, typically, a binder polymer compound is used. The separator 93 is impregnated with a non-aqueous electrolyte.
- the particle-containing resin layer 93b is, for example, interposed between the positive electrode 91 and the negative electrode 92 together with the separator base material 93a to prevent contact between the bipolar active materials, and in the same way as the separator base material 93a, electrolysis is performed in the micropores. The liquid is held to form an ion conduction path between the electrodes.
- Non-aqueous electrolyte The non-aqueous electrolyte is the same as in the third embodiment.
- the particle-containing resin layer 93b is formed on at least one main surface of the separator substrate 93a to produce the separator 93.
- the nonaqueous electrolytic solution is prepared by dissolving an electrolyte salt in a nonaqueous solvent.
- a positive electrode lead 95 is attached to the positive electrode current collector 91A by welding or the like, and a negative electrode lead 96 is attached to the negative electrode current collector 92A by welding or the like. Thereafter, the positive electrode 91 and the negative electrode 92 are wound through a separator 93 of the present technology to form a wound electrode body 90.
- the tip of the positive electrode lead 95 is welded to the safety valve mechanism, and the tip of the negative electrode lead 96 is welded to the battery can 81. Thereafter, the wound surface of the wound electrode body 90 is sandwiched between the pair of insulating plates 82 and 83 and stored in the battery can 81.
- a non-aqueous electrolyte is injected into the battery can 81 and impregnated in the separator 93.
- the safety valve mechanism including the battery lid 83 and the safety valve 84 and the heat sensitive resistance element 87 are fixed to the opening end of the battery can 81 by caulking through the gasket 88.
- the nonaqueous electrolyte battery 80 of the present technology shown in FIG. 7 is formed.
- the nonaqueous electrolyte battery 80 when charged, for example, lithium ions are released from the positive electrode active material layer 91B, and the nonaqueous electrolyte solution impregnated in the separator 93 (the separator base material 93a and the particle-containing resin layer 93b) is used. And occluded in the negative electrode active material layer 92B. Further, when the discharge is performed, for example, lithium ions are released from the negative electrode active material layer 92B, and the positive electrode active material layer is passed through the nonaqueous electrolytic solution impregnated in the separator 93 (the separator base material 93a and the particle-containing resin layer 93b). It is occluded by 91B.
- a cylindrical nonaqueous electrolyte battery will be described.
- the battery according to the sixth embodiment is an electrode with a particle-containing resin layer similar to that of the second embodiment, and incorporates a battery using a binder polymer compound as the resin of the particle-containing resin layer.
- each of the particle-containing resin layer 91C and the particle-containing resin layer 92C is interposed between the positive electrode 91 and the negative electrode 92 together with, for example, the separator 93.
- the electrolytic solution is held in the micropore to form an ion conduction path between the electrodes.
- the particle-containing resin layers 91C and 92C can reinforce the strength, heat resistance, and oxidation resistance of the separator 93, and can improve characteristics such as safety.
- the separator 93 typically has a configuration similar to that of the separator base material 93a.
- the separator 93 you may use the separator (Separator base material 93a and particle-containing resin layer 93b) similar to 5th Embodiment.
- the configuration other than the above is the same as that of the fifth embodiment.
- an electrode with a particle-containing resin layer (positive electrode) provided with a particle-containing resin layer 91C on one main surface of the positive electrode 91, and a particle-containing resin layer provided with at least one main surface of the negative electrode 92 with a particle-containing resin layer 92C.
- the electrode with the particle-containing resin layer 91C provided on both main surfaces of the positive electrode 91 and the particle-containing resin layer 92C with one main electrode of the negative electrode 92 may be configured. It is good also as a structure with which the electrode with a particle-containing resin layer provided in the surface was incorporated.
- Nonaqueous electrolyte battery manufacturing method Similarly to the second embodiment, a positive electrode with a particle-containing resin layer is produced. That is, the positive electrode 91 is produced as in the fifth embodiment. Next, a paint (particle-containing resin solution) is applied to both main surfaces or one main surface of the positive electrode 91 to form a particle-containing resin solution layer. Thereafter, the particle-containing resin layer 91C is formed by drying the particle-containing resin solution layer.
- a negative electrode with a particle-containing resin layer is produced. Similar to the fifth embodiment, the negative electrode 92 is produced. Next, a paint (particle-containing resin solution) is applied to both main surfaces or one main surface of the negative electrode 92 to form a particle-containing resin solution layer. Thereafter, the particle-containing resin layer 92C is formed by drying the particle-containing resin solution layer.
- the separator 93 has the same configuration as that of the separator base material 93a.
- the nonaqueous electrolytic solution is prepared by dissolving an electrolyte salt in a nonaqueous solvent.
- a positive electrode lead 95 is attached to the positive electrode current collector 91A by welding or the like, and a negative electrode lead 96 is attached to the negative electrode current collector 92A by welding or the like. Thereafter, the positive electrode 91 with a particle-containing resin layer and the negative electrode 92 with a particle-containing resin layer are wound through a separator 93 to obtain a wound electrode body 90.
- the tip of the positive electrode lead 95 is welded to the safety valve mechanism, and the tip of the negative electrode lead 96 is welded to the battery can 81.
- the wound surface of the wound electrode body 90 is sandwiched between the pair of insulating plates 82 and 83 and stored in the battery can 81.
- a non-aqueous electrolyte is injected into the battery can 81 and impregnated in the separator 93, the particle-containing resin layer 91C, and the particle-containing resin layer 92C.
- the safety valve mechanism including the battery lid 83 and the safety valve 84 and the heat sensitive resistance element 87 are fixed to the opening end of the battery can 81 by caulking through the gasket 88.
- the nonaqueous electrolyte battery 80 of the present technology shown in FIG. 7 is formed.
- the particle-containing resin layer 91C, and the particle-containing resin layer 92C is used. And occluded in the negative electrode active material layer 92B. Further, when discharged, for example, lithium ions are released from the negative electrode active material layer 92B, and the positive electrode active material layer is interposed via the separator 93, the particle-containing resin layer 91C, and the non-aqueous electrolyte impregnated in the particle-containing resin layer 92C. It is occluded by 91B.
- This battery pack is a simple battery pack (also referred to as a soft pack).
- a simple battery pack is built in an electronic device such as a smartphone.
- the battery cell, protection circuit, etc. are fixed with insulating tape, and a part of the battery cell is exposed.
- An output of a connector or the like connected to is provided.
- FIG. 10 is an exploded perspective view showing a configuration example of a simplified battery pack.
- FIG. 11A is a schematic perspective view showing the appearance of a simple battery pack, and
- FIG. 11B is a schematic perspective view showing the appearance of the simple battery pack.
- the simplified battery pack includes a battery cell 101, leads 102a and 102b derived from the battery cell 101, insulating tapes 103a to 103c, an insulating plate 104, A circuit board 105 on which a protection circuit (PCM (Protection Circuit Module)) is formed and a connector 106 are provided.
- the battery cell 101 is the same as the nonaqueous electrolyte secondary battery according to the third or fourth embodiment, for example.
- the insulating plate 104 and the circuit board 105 are disposed on the terrace portion 101 a at the front end of the battery cell 101, and the leads 102 a and the leads 102 b led out from the battery cell 101 are connected to the circuit board 105.
- a connector 106 for output is connected to the circuit board 105.
- Members such as the battery cell 101, the insulating plate 104, and the circuit board 105 are fixed by applying insulating tapes 103a to 103c to predetermined positions.
- FIG. 12 is a block diagram showing a circuit configuration example when the batteries according to the third to sixth embodiments of the present technology (hereinafter appropriately referred to as secondary batteries) are applied to the battery pack.
- the battery pack includes a switch unit 304 including an assembled battery 301, an exterior, a charge control switch 302a, and a discharge control switch 303a, a current detection resistor 307, a temperature detection element 308, and a control unit 310.
- the battery pack includes a positive electrode terminal 321 and a negative electrode lead 322, and at the time of charging, the positive electrode terminal 321 and the negative electrode lead 322 are connected to the positive electrode terminal and the negative electrode terminal of the charger, respectively, and charging is performed. Further, when the electronic device is used, the positive electrode terminal 321 and the negative electrode lead 322 are connected to the positive electrode terminal and the negative electrode terminal of the electronic device, respectively, and discharge is performed.
- the assembled battery 301 is formed by connecting a plurality of secondary batteries 301a in series and / or in parallel.
- the secondary battery 301a is a secondary battery of the present technology.
- 2P3S 2 parallel 3 series
- n parallel m series n and m are integers. Any connection method may be used.
- the switch unit 304 includes a charge control switch 302a and a diode 302b, and a discharge control switch 303a and a diode 303b, and is controlled by the control unit 310.
- the diode 302b has a reverse polarity with respect to the charging current flowing from the positive electrode terminal 321 in the direction of the assembled battery 301 and the forward polarity with respect to the discharging current flowing from the negative electrode lead 322 in the direction of the assembled battery 301.
- the diode 303b has a forward polarity with respect to the charging current and a reverse polarity with respect to the discharging current.
- the switch unit 304 is provided on the + side, but may be provided on the-side.
- the charge control switch 302a is turned off when the battery voltage becomes the overcharge detection voltage, and is controlled by the charge / discharge control unit so that the charge current does not flow in the current path of the assembled battery 301. After the charging control switch 302a is turned off, only discharging is possible via the diode 302b. Further, it is turned off when a large current flows during charging, and is controlled by the control unit 310 so that the charging current flowing in the current path of the assembled battery 301 is cut off.
- the discharge control switch 303 a is turned off when the battery voltage becomes the overdischarge detection voltage, and is controlled by the control unit 310 so that the discharge current does not flow in the current path of the assembled battery 301. After the discharge control switch 303a is turned off, only charging is possible via the diode 303b. Further, it is turned off when a large current flows during discharging, and is controlled by the control unit 310 so as to cut off the discharging current flowing in the current path of the assembled battery 301.
- the temperature detection element 308 is, for example, a thermistor, is provided in the vicinity of the assembled battery 301, measures the temperature of the assembled battery 301, and supplies the measured temperature to the control unit 310.
- the voltage detection unit 311 measures the voltage of the assembled battery 301 and each secondary battery 301a constituting the assembled battery 301, performs A / D conversion on the measured voltage, and supplies it to the control unit 310.
- the current measurement unit 313 measures the current using the current detection resistor 307 and supplies this measurement current to the control unit 310.
- the switch control unit 314 controls the charge control switch 302a and the discharge control switch 303a of the switch unit 304 based on the voltage and current input from the voltage detection unit 311 and the current measurement unit 313.
- the switch control unit 314 sends a control signal to the switch unit 304 when any voltage of the secondary battery 301a falls below the overcharge detection voltage or overdischarge detection voltage, or when a large current flows suddenly. By sending, overcharge, overdischarge, and overcurrent charge / discharge are prevented.
- the overcharge detection voltage is determined to be 4.20 V ⁇ 0.05 V, for example, and the overdischarge detection voltage is determined to be 2.4 V ⁇ 0.1 V, for example. .
- the charge / discharge switch for example, a semiconductor switch such as a MOSFET can be used.
- the parasitic diode of the MOSFET functions as the diodes 302b and 303b.
- the switch control unit 314 supplies control signals DO and CO to the gates of the charge control switch 302a and the discharge control switch 303a, respectively.
- the charge control switch 302a and the discharge control switch 303a are P-channel type, they are turned on by a gate potential that is lower than the source potential by a predetermined value or more. That is, in normal charging and discharging operations, the control signals CO and DO are set to the low level, and the charging control switch 302a and the discharging control switch 303a are turned on.
- control signals CO and DO are set to the high level, and the charge control switch 302a and the discharge control switch 303a are turned off.
- the memory 317 includes a RAM and a ROM, and includes, for example, an EPROM (Erasable Programmable Read Only Memory) that is a nonvolatile memory.
- EPROM Erasable Programmable Read Only Memory
- the numerical value calculated by the control unit 310, the internal resistance value of the battery in the initial state of each secondary battery 301a measured in the manufacturing process, and the like are stored in advance, and can be appropriately rewritten. . (Also, by storing the full charge capacity of the secondary battery 301a, for example, the remaining capacity can be calculated together with the control unit 310.
- the temperature detection unit 318 measures the temperature using the temperature detection element 308, performs charge / discharge control at the time of abnormal heat generation, and performs correction in the calculation of the remaining capacity.
- the batteries according to the third to sixth embodiments and the battery packs according to the seventh to eighth embodiments of the present technology described above are, for example, devices such as electronic devices, electric vehicles, and power storage devices. Can be used to mount or power.
- Examples of electronic devices include notebook computers, PDAs (personal digital assistants), mobile phones, cordless phones, video movies, digital still cameras, electronic books, electronic dictionaries, music players, radios, headphones, game consoles, navigation systems, Memory card, pacemaker, hearing aid, electric tool, electric shaver, refrigerator, air conditioner, TV, stereo, water heater, microwave oven, dishwasher, washing machine, dryer, lighting equipment, toys, medical equipment, robots, road conditioners, traffic lights Etc.
- examples of the electric vehicle include a railway vehicle, a golf cart, an electric cart, an electric vehicle (including a hybrid vehicle), and the like, and these are used as a driving power source or an auxiliary power source.
- Examples of power storage devices include power storage power supplies for buildings such as houses or power generation facilities.
- the first power storage system is a power storage system in which a power storage device is charged by a power generation device that generates power from renewable energy.
- the second power storage system is a power storage system that includes a power storage device and supplies power to an electronic device connected to the power storage device.
- the third power storage system is an electronic device that receives power supply from the power storage device.
- the fourth power storage system includes an electric vehicle having a conversion device that receives power supplied from the power storage device and converts the power into a driving force of the vehicle, and a control device that performs information processing related to vehicle control based on information related to the power storage device. It is.
- the fifth power storage system is a power system that includes a power information transmission / reception unit that transmits / receives signals to / from other devices via a network, and performs charge / discharge control of the power storage device described above based on information received by the transmission / reception unit.
- the sixth power storage system is a power system that receives power from the power storage device described above or supplies power from the power generation device or the power network to the power storage device.
- the power storage system will be described.
- a power storage device using a battery of the present technology is applied to a residential power storage system
- a power storage system 400 for a house 401 power is stored from a centralized power system 402 such as a thermal power generation 402a, a nuclear power generation 402b, and a hydroelectric power generation 402c through a power network 409, an information network 412, a smart meter 407, a power hub 408, and the like.
- a power network 409 an information network 412, a smart meter 407, a power hub 408, and the like.
- power is supplied to the power storage device 403 from an independent power source such as the power generation device 404 in the home.
- the electric power supplied to the power storage device 403 is stored. Electric power used in the house 401 is supplied using the power storage device 403.
- the same power storage system can be used not only for the house 401 but also for buildings.
- the house 401 is provided with a power generation device 404, a power consumption device 405, a power storage device 403, a control device 410 that controls each device, a smart meter 407, and a sensor 411 that acquires various types of information.
- Each device is connected by a power network 409 and an information network 412.
- a solar cell, a fuel cell, or the like is used as the power generation device 404, and the generated power is supplied to the power consumption device 405 and / or the power storage device 403.
- the power consuming device 405 is a refrigerator 405a, an air conditioner 405b, a television receiver 405c, a bath 405d, and the like.
- the electric power consumption device 405 includes an electric vehicle 406.
- the electric vehicle 406 is an electric vehicle 406a, a hybrid car 406b, and an electric motorcycle 406c.
- the battery of the present technology is applied to the power storage device 403.
- the battery of the present technology may be configured by, for example, the above-described lithium ion secondary battery.
- the smart meter 407 has a function of measuring the usage amount of commercial power and transmitting the measured usage amount to an electric power company.
- the power network 409 may be any one or a combination of DC power supply, AC power supply, and non-contact power supply.
- the various sensors 411 are, for example, human sensors, illuminance sensors, object detection sensors, power consumption sensors, vibration sensors, contact sensors, temperature sensors, infrared sensors, and the like. Information acquired by various sensors 411 is transmitted to the control device 410. Based on the information from the sensor 411, the weather condition, the condition of the person, and the like can be grasped, and the power consumption device 405 can be automatically controlled to minimize the energy consumption. Furthermore, the control apparatus 410 can transmit the information regarding the house 401 to an external electric power company etc. via the internet.
- the power hub 408 performs processing such as branching of power lines and DC / AC conversion.
- Communication methods of the information network 412 connected to the control device 410 include a method using a communication interface such as UART (Universal Asynchronous Receiver-Transceiver), wireless communication such as Bluetooth, ZigBee, Wi-Fi, etc.
- a communication interface such as UART (Universal Asynchronous Receiver-Transceiver), wireless communication such as Bluetooth, ZigBee, Wi-Fi, etc.
- Bluetooth method is applied to multimedia communication and can perform one-to-many connection communication.
- ZigBee uses the physical layer of IEEE (Institute of Electrical and Electronics Electronics) (802.15.4).
- IEEE802.15.4 is a name of a short-range wireless network standard called PAN (Personal Area Network) or W (Wireless) PAN.
- the control device 410 is connected to an external server 413.
- the server 413 may be managed by any one of the house 401, the power company, and the service provider.
- the information transmitted and received by the server 413 is, for example, information related to power consumption information, life pattern information, power charges, weather information, natural disaster information, and power transactions. These pieces of information may be transmitted / received from a power consuming device (for example, a television receiver) in the home, or may be transmitted / received from a device outside the home (for example, a mobile phone). Such information may be displayed on a device having a display function, for example, a television receiver, a mobile phone, a PDA (Personal Digital Assistant) or the like.
- the control device 410 that controls each unit includes a CPU (Central Processing Unit), a RAM (Random Access Memory), a ROM (Read Only Memory), and the like, and is stored in the power storage device 403 in this example.
- the control device 410 is connected to the power storage device 403, the domestic power generation device 404, the power consumption device 405, various sensors 411, the server 413 and the information network 412, and adjusts, for example, the amount of commercial power used and the amount of power generation It has a function to do. In addition, you may provide the function etc. which carry out an electric power transaction in an electric power market.
- the power generation device 404 (solar power generation, wind power generation) in the home is used as the power storage device 403. Can be stored. Therefore, even if the generated power of the power generation device 404 in the home fluctuates, it is possible to perform control such that the amount of power transmitted to the outside is constant or discharge is performed as necessary. For example, the power obtained by solar power generation is stored in the power storage device 403, and the nighttime power at a low charge is stored in the power storage device 403 at night, and the power stored by the power storage device 403 is discharged during a high daytime charge. You can also use it.
- control device 410 is stored in the power storage device 403 .
- control device 410 may be stored in the smart meter 407 or may be configured independently.
- the power storage system 400 may be used for a plurality of homes in an apartment house, or may be used for a plurality of detached houses.
- FIG. 14 schematically shows an example of the configuration of a hybrid vehicle that employs a series hybrid system to which the present technology is applied.
- a series hybrid system is a car that runs on an electric power driving force conversion device using electric power generated by a generator driven by an engine or electric power once stored in a battery.
- the hybrid vehicle 500 includes an engine 501, a generator 502, a power driving force conversion device 503, driving wheels 504 a, driving wheels 504 b, wheels 505 a, wheels 505 b, a battery 508, a vehicle control device 509, various sensors 510, and a charging port 511. Is installed.
- the battery of the present technology described above is applied to the battery 508.
- Hybrid vehicle 500 travels using power driving force conversion device 503 as a power source.
- An example of the power / driving force conversion device 503 is a motor.
- the electric power / driving force converter 503 is operated by the electric power of the battery 508, and the rotational force of the electric power / driving force converter 503 is transmitted to the driving wheels 504a and 504b.
- DC-AC DC-AC
- AC-DC conversion AC-DC conversion
- the power driving force converter 503 can be applied to either an AC motor or a DC motor.
- the various sensors 510 control the engine speed through the vehicle control device 509 and control the opening (throttle opening) of a throttle valve (not shown).
- Various sensors 510 include a speed sensor, an acceleration sensor, an engine speed sensor, and the like.
- the rotational force of the engine 501 is transmitted to the generator 502, and the electric power generated by the generator 502 by the rotational force can be stored in the battery 508.
- the resistance force at the time of deceleration is applied as a rotational force to the electric power driving force conversion device 503, and the regenerative electric power generated by the electric power driving force conversion device 503 by this rotational force becomes the battery 508. Accumulated in.
- the battery 508 is connected to an external power source of the hybrid vehicle 500, so that it can receive power from the external power source using the charging port 511 as an input port and store the received power.
- an information processing device that performs information processing related to vehicle control based on information related to the secondary battery may be provided.
- an information processing apparatus for example, there is an information processing apparatus that displays a battery remaining amount based on information on the remaining amount of the battery.
- the present technology is also effective for a parallel hybrid vehicle in which the engine and motor outputs are both driving sources, and the system is switched between the three modes of driving with only the engine, driving with the motor, and engine and motor. Applicable. Furthermore, the present technology can be effectively applied to a so-called electric vehicle that travels only by a drive motor without using an engine.
- Example 1-1 [Production of positive electrode] A positive electrode mixture obtained by mixing 91% by mass of lithium cobaltate (LiCoO 2 ) as a positive electrode active material, 6% by mass of carbon black as a conductive agent, and 3% by mass of polyvinylidene fluoride (PVdF) as a binder.
- the positive electrode mixture was dispersed in N-methyl-2-pyrrolidone (NMP) as a dispersion medium to obtain a positive electrode mixture slurry.
- NMP N-methyl-2-pyrrolidone
- 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.
- 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 positive electrode current collector to form a negative electrode.
- a 9 ⁇ m-thick polyethylene (PE) microporous film (polyethylene separator) was used as the substrate.
- a coating material was applied to both surfaces of the substrate as described below to form a particle-containing resin solution layer (coating film), and then dried to form a particle-containing resin layer.
- boehmite particles having an average particle diameter of 0.8 ⁇ m as filler and polyvinylidene fluoride (PVdF) as matrix polymer compound are dispersed in N-methyl-2-pyrrolidone (NMP).
- NMP N-methyl-2-pyrrolidone
- a paint particle-containing resin solution
- the boehmite content is 5% by mass with respect to the total amount of the paint
- the mass ratio of boehmite to PVdF (boehmite / PVdF) is 50/50
- the solid content (boehmite and PVdF) is the total amount of the paint.
- the amount of each material was adjusted to 20% by mass.
- this paint was uniformly applied to each of both surfaces of the base material with a predetermined paint thickness shown in Table 1 (10.0 ⁇ m in Example 1-1).
- the thickness of the paint film was measured with a laser thickness meter, and when the measured value was different from the predetermined paint thickness, the discharge amount of the paint was automatically adjusted so as to approach the predetermined paint thickness.
- the NMP is removed from the particle-containing resin solution layer by passing the substrate on which the paint is applied in a dryer, and the particles are composed of the substrate and PVdF and boehmite particles formed on both surfaces of the substrate.
- a separator having a containing resin layer was produced.
- a separator having a positive electrode, a negative electrode, and a particle-containing resin layer formed on both sides is laminated in the order of 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 adhesive tape
- the wound electrode body was formed by fixing with.
- the wound electrode body was sandwiched between the exterior members, and the three sides were heat-sealed. Note that a laminate film having a soft aluminum layer was used for the exterior member.
- electrolyte solution was prepared by dissolving lithium hexafluorophosphate (LiPF 6 ) as an electrolyte salt in a non-aqueous solvent in which ethylene carbonate (EC) and dimethyl carbonate (DMC) were mixed.
- LiPF 6 lithium hexafluorophosphate
- the mass ratio of the constituents of the electrolyte (EC / DMC / LiPF 6) (EC / DMC / LiPF 6) is such that the 35/50/15 and adjust the amount of each component.
- a laminated film type battery shown in FIG. 4 having a battery shape of 4.5 mm in thickness, 30 mm in width, and 50 mm in height was produced.
- Example 1-2 to Example 1-55 Comparative Example 1-1 to Comparative Example 1-8>
- Example 1-1 was used except that the filler used was changed.
- a laminate film type battery was produced.
- the flatness was measured as follows. From the direction perpendicular to the main surface of the particle-containing resin layer containing the electrolytic solution, the particle-containing resin layer containing the electrolytic solution is observed by SEM, and a typical size around 50% average particle diameter (D50) based on volume is used. A photograph of 10 shaped particles was taken. The average particle diameter (D50) is obtained by measuring the powder after removing the resin and liquid components from the particle-containing resin layer containing the electrolytic solution using a laser diffraction particle size distribution measuring apparatus.
- the projection area of the plane corresponding to the crystal plane, the crushing plane, and the cleaved plane (the total area if there are multiple planes) is calculated, and the projection of the plane with respect to the projection area of the entire particle is calculated.
- the percentage of the area was calculated, and the average value of the calculated percentage of each particle was defined as the plane rate.
- the thickness of the particle-containing resin layer depends on the volume of the solvent (solvent) contained therein. That is, the thickness of the coating film containing NMP measured with a laser thickness meter and the thickness of the particle-containing resin layer (gel electrolyte layer) containing an electrolyte measured with a contact-type thickness meter are the solvent contained in the particle-containing resin layer. Although the seeds are different, if the amount of solvent (solvent) contained is the same volume, they will have the same thickness.
- the difference between the thickness of the paint film containing NMP measured by the laser thickness meter and the thickness of the particle-containing resin layer (gel electrolyte layer) containing the electrolyte measured by the contact-type thickness meter is within ⁇ 10%.
- the difference between the measured value of the paint film thickness and the measured value of the gel electrolyte layer is within ⁇ 10% as a percentage of the measured value of the paint film thickness. In some cases, it was passed, and in other cases, it was rejected.
- the paint is transparent by including particles having a predetermined range of flatness and a predetermined range of refractive index.
- the pass / fail judgment of the laser measurement was acceptable.
- Comparative Examples 1-1 to 1-8 the coating becomes non-transparent because it contains particles that do not have at least one of a predetermined range of refractive index and a predetermined range of flatness. The measurement pass / fail judgment was rejected.
- Example 2-1> A laminated film type battery was produced in the same manner as in Example 1-1.
- Example 2-2 to Example 2-7 As the filler, boehmite particles having different plane rates were used. The plane rate of the boehmite particles was adjusted to a desired one by increasing the ratio of spherical surfaces by increasing the growth rate during hydrothermal synthesis of boehmite particles or increasing the ratio of planes by decreasing the growth rate. Specifically, in Example 2-2, boehmite particles having a plane rate of 45% were used as the filler. In Example 2-3, boehmite particles having a plane rate of 50% were used as the filler. In Example 2-4, boehmite particles having a plane rate of 60% were used as the filler.
- Example 2-5 boehmite particles having a plane rate of 80% were used as the filler.
- Example 2-6 boehmite particles having a plane rate of 90% were used as the filler.
- Example 2-7 boehmite particles having a plane rate of 100% were used as the filler. Except for the above, a laminated film type battery was produced in the same manner as in Example 2-1.
- Example 2-8> A laminated film type battery was produced in the same manner as Example 1-2.
- Example 2-9 to Example 2-14> As the filler, talc particles having different plane rates were used. In the grinding process using a hammer mill and a roll mill, increase the time ratio of the hammer mill to increase the cleavage plane ratio, increase the roll mill time ratio to decrease the cleavage plane ratio, The flatness was adjusted to the desired one. Specifically, in Example 2-9, talc particles having a plane rate of 45% were used as the filler. In Example 2-10, talc particles having a plane rate of 50% were used as the filler. In Example 2-11, talc particles having a plane rate of 60% were used as the filler. In Example 2-12, talc particles having a plane rate of 80% were used as the filler.
- Example 2-13 talc particles having a plane rate of 90% were used as the filler.
- Example 2-14 talc particles having a plane rate of 100% were used as the filler. Except for the above, a laminated film type battery was produced in the same manner as in Example 2-8.
- Comparative Example 2-1 aluminum oxide particles having different plane rates were used as the filler. Specifically, in Comparative Example 2-1, aluminum oxide particles having a plane rate of 40% were used as the filler. In Comparative Example 2-2, aluminum oxide particles having a plane rate of 30% were used as the filler. In Comparative Example 2-3, aluminum oxide particles having a plane rate of 20% were used as the filler. In Comparative Example 2-4, aluminum oxide particles having a plane rate of 10% were used as the filler. In Comparative Example 2-5, spherical aluminum oxide (plane rate 0%) particles were used as the filler. Except for the above, a laminated film type battery was produced in the same manner as in Example 2-1.
- Table 2 shows the evaluation results.
- the coating material is transparent by including particles having a predetermined range of flatness and a predetermined range of refractive index.
- the pass / fail judgment of the laser measurement was acceptable.
- the paint becomes non-transparent because it contains particles that do not have at least one of a predetermined range of refractive index and a predetermined range of flatness. The measurement pass / fail judgment was rejected.
- Example 3-1 to Example 3-8 a laminate film type was obtained in the same manner as in Example 1-1 except that the mass ratio of the filler (boehmite particles) and the matrix polymer compound (PVdF) was changed. A battery was produced. Specifically, in Example 3-1, the mass ratio (particle / PVdF) was set to 15/85. In Example 3-2, the mass ratio (particle / PVdF) was set to 20/80. In Example 3-3, the mass ratio (particle / PVdF) was set to 30/70. In Example 3-4, as in Example 1-1, the mass ratio (particle / PVdF) was set to 50/50.
- Example 3-5 the mass ratio (particle / PVdF) was set to 70/30. In Example 3-6, the mass ratio (particle / PVdF) was set to 80/20. In Example 3-7, the mass ratio (particle / PVdF) was 85/15. In Example 3-8, the mass ratio (particle / PVdF) was 90/10.
- Example 3-9 to Example 3-15 a laminate film type was obtained in the same manner as in Example 1-2 except that the mass ratio of the filler (talc particles) and the matrix polymer compound (PVdF) was changed.
- a battery was produced.
- the mass ratio (particle / PVdF) was 20/80.
- the mass ratio (particle / PVdF) was 40/60.
- the mass ratio (particle / PVdF) was set to 50/50, as in Example 1-2.
- Example 3-12 the mass ratio (particle / PVdF) was 60/40.
- Example 3-13 the mass ratio (particle / PVdF) was 80/20.
- the mass ratio (particle / PVdF) was 85/15.
- the mass ratio (particle / PVdF) was 90/10.
- Table 3 shows the evaluation results.
- the coating material is transparent by including particles having a predetermined range of flatness and a predetermined range of refractive index.
- the pass / fail judgment of the laser measurement was acceptable. It was also confirmed that the degree of transparency can be changed by changing the ratio (mixing ratio) between the filler and the matrix polymer compound.
- Example 4-1 a laminated film type battery was produced in the same manner as in Example 1-1.
- Example 4-2 to Example 4-3 the type of the matrix polymer compound (resin) constituting the gel electrolyte layer was changed.
- PAN polyacrylonitrile
- Example 4-3 PEG (polyethylene glycol) was used as the matrix polymer compound. Except for the above, a laminated film type battery was produced in the same manner as in Example 4-1.
- Example 4-4 a laminated film type battery was produced in the same manner as in Example 1-2.
- Example 4-5 to Example 4-6 the type of matrix polymer compound constituting the gel electrolyte layer was changed.
- PAN polyacrylonitrile
- PEG polyethylene glycol
- Table 4 shows the evaluation results.
- the coating material is transparent by including particles having a predetermined range of flatness and a predetermined range of refractive index. The pass / fail judgment of the laser measurement was acceptable.
- Example 5-1 to Example 5-2 In Examples 5-1 to 5-2, the simplified type shown in FIGS. 10, 11A, and 11B using the laminate film type battery similar to each of Examples 1-1 to 1-2. A battery pack (soft pack) was prepared.
- Example 5-3 to Example 5-4 a laminate film type battery that is the same as Example 1-1 to Example 1-2, except that the coating material was applied only to one surface on the positive electrode side of the separator.
- Example 5-5 to Example 5-6 a laminated film type battery that is the same as Example 1-1 to Example 1-2, except that the coating material was applied only to one surface on the negative electrode side of the separator.
- Example 5-1 A simple battery pack (soft pack) shown in FIGS. 10, 11A and 11B was produced in the same manner as in Example 5-1, except that the paint did not contain a filler.
- Example 5-2> A simple battery pack (soft pack) shown in FIGS. 10, 11A and 11B was produced in the same manner as in Example 5-5 except that the paint did not contain a filler.
- Table 5 shows the evaluation results.
- Example 5-6 the results of the pressure test and the storage test were good.
- the separator deteriorated, but the result of the storage test was acceptable due to the function of the filler on the negative electrode.
- Comparative Example 5-1 the result of the pressure test was bad
- Comparative Example 5-2 the result of the pressure test and the storage test was bad.
- Example 6-1 [Preparation of positive electrode, formation of particle-containing resin layer] A positive electrode was produced in the same manner as Example 1-1. Moreover, the particle
- boehmite particles having an average particle diameter of 0.8 ⁇ m as filler and polyvinylidene fluoride (PVdF) as matrix polymer compound are dispersed in N-methyl-2-pyrrolidone (NMP).
- NMP N-methyl-2-pyrrolidone
- a paint particle-containing resin solution
- the boehmite content is 5% by mass with respect to the total amount of the paint
- the mass ratio of boehmite to PVdF (boehmite / PVdF) is 50/50
- the solid content (boehmite and PVdF) is the total amount of the paint
- the amount of each material was adjusted to 20% by mass.
- this paint was uniformly applied to each of both surfaces of the positive electrode with a predetermined paint thickness shown in Table 5.
- the thickness of the paint film was measured with a laser thickness meter, and when the measured value was different from the predetermined paint thickness, the discharge amount of the paint was automatically adjusted so as to approach the predetermined paint thickness.
- the NMP was removed from the particle-containing resin solution layer by passing the positive electrode coated with the paint in a dryer, thereby forming a particle-containing resin layer composed of PVdF and boehmite on both sides of the positive electrode.
- a negative electrode was produced in the same manner as in Example 1-1.
- a particle-containing resin layer was formed on both sides of the negative electrode in the same manner as the positive electrode.
- a positive electrode with a particle-containing resin layer formed on both sides, and a negative electrode and a separator with a particle-containing resin layer formed on both sides are laminated in the order of positive electrode, separator, negative electrode and separator, and wound in a flat shape many times in the longitudinal direction. Then, the wound electrode body was formed by fixing the winding end portion with an adhesive tape.
- the wound electrode body was sandwiched between the exterior members, and the three sides were heat-sealed. Note that a laminate film having a soft aluminum layer was used for the exterior member.
- electrolyte solution was prepared by dissolving lithium hexafluorophosphate (LiPF 6 ) as an electrolyte salt in a non-aqueous solvent in which ethylene carbonate (EC) and dimethyl carbonate (DMC) were mixed.
- LiPF 6 lithium hexafluorophosphate
- the mass ratio of the constituents of the electrolyte (EC / DMC / LiPF 6) (EC / DMC / LiPF 6) is such that the 35/50/15 and adjust the amount of each component.
- a laminated film type battery shown in FIG. 4 having a battery shape of 4.5 mm in thickness, 30 mm in width, and 50 mm in height was produced.
- Example 6-2 to Example 6-55 Comparative Example 6-1 to Comparative Example 6-8>
- Example 6-1 was used except that the filler used was changed. Similarly, a laminate film type battery was produced.
- the paint is transparent by including particles having a predetermined range of flatness and a predetermined range of refractive index.
- the pass / fail judgment of the laser measurement was acceptable.
- Comparative Examples 6-1 to 6-8 the coating becomes non-transparent because it contains particles that do not have at least one of a predetermined range of refractive index and a predetermined range of flatness. The measurement pass / fail judgment was rejected.
- Example 7-1 A laminated film type battery was produced in the same manner as in Example 7-1.
- Example 7-2 to Example 7-7> As the filler, boehmite particles having different plane rates were used. The plane rate of the boehmite particles was adjusted to a desired one by increasing the ratio of spherical surfaces by increasing the growth rate during hydrothermal synthesis of boehmite particles or increasing the ratio of planes by decreasing the growth rate. Specifically, in Example 7-2, boehmite particles having a plane rate of 45% were used as the filler. In Example 7-3, boehmite particles having a plane rate of 50% were used as the filler. In Example 7-4, boehmite particles having a plane rate of 60% were used as the filler.
- Example 7-5 boehmite particles having a plane rate of 80% were used as the filler.
- Example 7-6 boehmite particles having a plane rate of 90% were used as the filler.
- Example 7-7 boehmite particles having a plane rate of 100% were used as the filler. Except for the above, a laminated film type battery was produced in the same manner as in Example 7-1.
- Example 7-8> A laminated film type battery was produced in the same manner as Example 1-2.
- Example 7-9 to Example 7-14> As the filler, talc particles having different plane rates were used. In the grinding process using a hammer mill and a roll mill, increase the time ratio of the hammer mill to increase the cleavage plane ratio, increase the roll mill time ratio to decrease the cleavage plane ratio, The flatness was adjusted to the desired one. Specifically, in Examples 7-9, talc particles having a plane rate of 45% were used as the filler. In Examples 7-10, talc particles having a plane rate of 50% were used as the filler. In Example 7-11, talc particles having a plane rate of 60% were used as the filler. In Examples 7-12, talc particles having a plane rate of 80% were used as the filler.
- Example 7 to 13 talc particles having a plane rate of 90% were used as the filler. In Examples 7-14, talc particles having a plane rate of 100% were used as the filler. Except for the above, a laminated film type battery was produced in the same manner as in Example 7-8.
- Comparative Examples 7-1 to 7-5> instead of boehmite particles, aluminum oxide particles having different plane rates were used as the filler. Specifically, in Comparative Example 7-1, aluminum oxide particles having a plane rate of 40% were used as the filler. In Comparative Example 7-2, aluminum oxide particles having a plane rate of 30% were used as the filler. In Comparative Example 7-3, aluminum oxide particles having a plane rate of 20% were used as the filler. In Comparative Example 7-4, aluminum oxide particles having a plane rate of 10% were used as the filler. In Comparative Example 7-5, spherical aluminum oxide (plane rate 0%) particles were used as the filler. Except for the above, a laminated film type battery was produced in the same manner as in Example 7-1.
- Table 7 shows the evaluation results.
- the coating material is transparent by including particles having a predetermined range of flatness and a predetermined range of refractive index.
- the pass / fail judgment of the laser measurement was acceptable.
- Comparative Examples 7-1 to 7-14 the coating becomes non-transparent because it contains particles that do not have at least one of a predetermined range of refractive index and a predetermined range of flatness. The measurement pass / fail judgment was rejected.
- Example 8-1 to Example 8-8 a laminate film type was obtained in the same manner as in Example 1-1 except that the mass ratio of the filler (boehmite particles) and the matrix polymer compound (PVdF) was changed. A battery was produced. Specifically, in Example 8-1, the mass ratio (particle / PVdF) was set to 15/85. In Example 8-2, the mass ratio (particle / PVdF) was set to 20/80. In Example 8-3, the mass ratio (particle / PVdF) was set to 30/70. In Example 8-4, as in Example 1-1, the mass ratio (particle / PVdF) was set to 50/50.
- Example 8-5 the mass ratio (particle / PVdF) was set to 70/30. In Example 8-6, the mass ratio (particle / PVdF) was set to 80/20. In Example 8-7, the mass ratio (particle / PVdF) was 85/15. In Example 8-8, the mass ratio (particle / PVdF) was 90/10.
- Example 8-9 to Example 8-15 a laminate film type was obtained in the same manner as in Example 1-2, except that the mass ratio of the filler (talc particles) and the matrix polymer compound (PVdF) was changed.
- a battery was produced.
- the mass ratio (particle / PVdF) was set to 20/80.
- the mass ratio (particle / PVdF) was 40/60.
- the mass ratio (particle / PVdF) was set to 50/50 as in Example 1-2.
- the mass ratio (particle / PVdF) was 60/40.
- the mass ratio (particle / PVdF) was 80/20.
- the mass ratio (particle / PVdF) was 85/15.
- the mass ratio (particle / PVdF) was 90/10.
- Table 8 shows the evaluation results.
- the paint is transparent by including particles having a predetermined range of flatness and a predetermined range of refractive index.
- the pass / fail judgment of the laser measurement was acceptable. It was also confirmed that the degree of transparency can be changed by changing the ratio (mixing ratio) between the filler and the matrix polymer compound.
- Example 9-1 a laminate film type battery was produced in the same manner as in Example 1-1.
- Example 9-2 to Example 9-3 the type of matrix polymer compound (resin) constituting the gel electrolyte layer was changed.
- PAN polyacrylonitrile
- PEG polyethylene glycol
- Example 9-4 a laminated film type battery was produced in the same manner as in Example 1-2.
- Example 9-5 to Example 9-6 the type of matrix polymer compound constituting the gel electrolyte layer was changed.
- PAN polyacrylonitrile
- PEG polyethylene glycol
- Table 9 shows the evaluation results.
- the paint is transparent by including particles having a predetermined range of flatness and a predetermined range of refractive index. The pass / fail judgment of the laser measurement was acceptable.
- Example 10-1 to Example 10-2 In Example 10-1 to Example 10-2, the simplified type shown in FIGS. 10, 11A, and 11B using a laminate film type battery similar to each of Example 6-1 to Example 6-2. A battery pack (soft pack) was prepared.
- Example 10-3 to Example 10-4 In Examples 10-3 to 10-4, laminated film type batteries similar to those in Examples 6-1 to 6-2 were used except that the paint was applied only on both sides of the positive electrode. A simple battery pack (soft pack) shown in FIGS. 10, 11A and 11B was produced.
- Example 10-5 to Example 10-6 laminated film type batteries similar to those in Examples 6-1 to 6-2 were used except that the paint was applied only on both sides of the negative electrode.
- Example 10-1 A simple battery pack (soft pack) shown in FIGS. 10, 11A and 11B was produced in the same manner as in Example 10-1, except that the paint did not contain a filler.
- Example 10-2 A simple battery pack (soft pack) shown in FIGS. 10, 11A and 11B was produced in the same manner as in Example 10-5 except that the paint did not contain a filler.
- Example 5-1 Battery evaluation: 100 kg pressure test, 60 ° C. 1 month storage test
- the soft packs of each of the examples and comparative examples were subjected to a 100 kg pressure test and a 60 ° C. one month storage test in the same manner as in Example 5-1.
- Table 10 shows the evaluation results.
- Example 10-1 to 10-6 the results of the pressure test and the storage test were good.
- the separator deteriorated, but the result of the storage test was acceptable because the filler on the negative electrode functions.
- Comparative Example 10-1 the result of the pressure test was bad, and in Comparative Example 10-2, the result of the pressure test and the storage test was bad.
- Example 11-1 [Preparation of positive electrode, preparation of negative electrode] A positive electrode and a negative electrode were produced in the same manner as in Example 1-1.
- a 9 ⁇ m-thick polyethylene (PE) microporous film was used as the substrate.
- a coating material was applied to both surfaces of the substrate as described below to form a particle-containing resin solution layer (coating film), and then dried to form a particle-containing resin layer.
- boehmite particles having an average particle diameter of 0.8 ⁇ m as a filler and polyvinylidene fluoride (PVdF) as a binder polymer compound are dispersed in N-methyl-2-pyrrolidone (NMP).
- NMP N-methyl-2-pyrrolidone
- a paint particle-containing resin solution
- the boehmite content is 5% by mass with respect to the total amount of the paint
- the mass ratio of boehmite to PVdF (boehmite / PVdF) is 50/50
- the solid content (boehmite and PVdF) is the total amount of the paint.
- the amount of each material was adjusted to 20% by mass.
- this paint was uniformly applied to each of both surfaces of the base material with a predetermined paint thickness shown in Table 11.
- the thickness of the paint film was measured with a laser thickness meter, and when the measured value was different from the predetermined paint thickness, the discharge amount of the paint was automatically adjusted so as to approach the predetermined paint thickness.
- the NMP is removed from the particle-containing resin solution layer by passing the substrate coated with the coating material in a dryer, and the particle-containing resin comprising PVDF and boehmite formed on both surfaces of the substrate.
- a separator having a layer was prepared.
- a separator having a positive electrode, a negative electrode, and a particle-containing resin layer formed on both sides is laminated in the order of 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 adhesive tape
- the wound electrode body was formed by fixing with.
- the wound electrode body was sandwiched between the exterior members, and the three sides were heat-sealed. Note that a laminate film having a soft aluminum layer was used for the exterior member.
- electrolyte solution was prepared by dissolving lithium hexafluorophosphate (LiPF 6 ) as an electrolyte salt in a non-aqueous solvent in which ethylene carbonate (EC) and dimethyl carbonate (DMC) were mixed.
- EC ethylene carbonate
- DMC dimethyl carbonate
- the mass ratio of the constituents of the electrolyte (EC / DMC / LiPF 6) (EC / DMC / LiPF 6) is such that the 35/50/15 and adjust the amount of each component.
- a laminated film type battery having a battery shape of 4.5 mm in thickness, 30 mm in width, and 50 mm in height was produced.
- Example 11-2 to Example 11-55 Comparative Example 11-1 to Comparative Example 11-8>
- Example 11-2 to Example 11-55 and Comparative Example 11-1 to Comparative Example 11-8 as shown in Table 11 below, except that the filler used was changed, Similarly, a laminate film type battery was produced.
- Table 11 shows the evaluation results.
- the paint is transparent by including particles having a predetermined range of flatness and a predetermined range of refractive index.
- the pass / fail judgment of the laser measurement was acceptable.
- Comparative Examples 11-1 to 11-8 the coating becomes non-transparent because it contains particles that do not have at least one of a predetermined range of refractive index and a predetermined range of flatness. The measurement pass / fail judgment was rejected.
- Example 12-1 A laminated film type battery was produced in the same manner as Example 11-1.
- Example 12-2 to Example 12-7 As the filler, boehmite particles having different plane rates were used.
- the plane rate of the boehmite particles was adjusted to a desired one by increasing the ratio of spherical surfaces by increasing the growth rate during hydrothermal synthesis of boehmite particles or increasing the ratio of planes by decreasing the growth rate.
- boehmite particles having a plane rate of 45% were used as the filler.
- boehmite particles having a plane rate of 50% were used as the filler.
- boehmite particles having a plane rate of 60% were used as the filler.
- Example 12-5 boehmite particles having a plane rate of 80% were used as the filler.
- Example 12-6 boehmite particles having a plane rate of 90% were used as the filler.
- Example 12-7 boehmite particles having a plane rate of 100% were used as the filler. Except for the above, a laminated film type battery was produced in the same manner as in Example 12-1.
- Example 12-8> A laminated film type battery was produced in the same manner as in Example 11-2.
- Example 12-9 to Example 12-14> As the filler, talc particles having different plane rates were used. In the grinding process using a hammer mill and a roll mill, increase the time ratio of the hammer mill to increase the cleavage plane ratio, increase the roll mill time ratio to decrease the cleavage plane ratio, The flatness was adjusted to the desired one. Specifically, in Example 12-9, talc particles having a plane rate of 45% were used as the filler. In Example 12-10, talc particles having a plane rate of 50% were used as the filler. In Example 12-11, talc particles having a plane rate of 60% were used as the filler. In Examples 12-12, talc particles having a plane rate of 80% were used as the filler.
- Example 12-13 talc particles having a plane rate of 90% were used as the filler.
- Examples 12-14 talc particles having a plane rate of 100% were used as the filler. Except for the above, a laminated film type battery was produced in the same manner as in Example 12-8.
- Comparative Example 12-1 to Comparative Example 12-5> aluminum oxide particles having different plane rates were used as the filler. Specifically, in Comparative Example 12-1, aluminum oxide particles having a plane rate of 40% were used as the filler. In Comparative Example 12-2, aluminum oxide particles having a plane rate of 30% were used as the filler. In Comparative Example 12-3, aluminum oxide particles having a plane rate of 20% were used as the filler. In Comparative Example 12-4, aluminum oxide particles having a plane rate of 10% were used as the filler. In Comparative Example 12-5, spherical aluminum oxide (plane rate 0%) particles were used as the filler. Except for the above, a laminated film type battery was produced in the same manner as in Example 12-1.
- Table 12 shows the evaluation results.
- the coating material is transparent by including particles having a predetermined range of flatness and a predetermined range of refractive index.
- the pass / fail judgment of the laser measurement was acceptable.
- Comparative Examples 12-1 to 12-14 the coating becomes non-transparent because it contains particles that do not have at least one of a predetermined range of refractive index and a predetermined range of flatness. The measurement pass / fail judgment was rejected.
- Example 13-1 to Example 13-8 a laminate film type was obtained in the same manner as in Example 11-1, except that the mass ratio of the filler (boehmite particles) and the binder polymer compound (PVdF) was changed.
- a battery was produced. Specifically, in Example 13-1, the mass ratio (particle / PVdF) was 15/85. In Example 13-2, the mass ratio (particle / PVdF) was set to 20/80. In Example 13-3, the mass ratio (particle / PVdF) was set to 30/70. In Example 13-4, the mass ratio (particle / PVdF) was set to 50/50 as in Example 11-1.
- Example 13-5 the mass ratio (particle / PVdF) was set to 70/30. In Example 13-6, the mass ratio (particle / PVdF) was set to 80/20. In Example 13-7, the mass ratio (particle / PVdF) was 85/15. In Example 13-8, the mass ratio (particle / PVdF) was 90/10.
- Example 13-9 to Example 13-15 a laminate film type was used in the same manner as in Example 11-2 except that the mass ratio of the filler (talc particles) and the binder polymer compound (PVdF) was changed.
- a battery was produced.
- the mass ratio (particle / PVdF) was 20/80.
- the mass ratio (particle / PVdF) was 40/60.
- the mass ratio (particle / PVdF) was set to 50/50, as in Example 11-2.
- the mass ratio (particle / PVdF) was 60/40.
- the mass ratio (particle / PVdF) was 80/20.
- the mass ratio (particle / PVdF) was 85/15.
- the mass ratio (particle / PVdF) was 90/10.
- Table 13 shows the evaluation results.
- the paint is transparent by including particles having a predetermined range of flatness and a predetermined range of refractive index.
- the pass / fail judgment of the laser measurement was acceptable. It was also confirmed that the degree of transparency can be changed by changing the ratio (mixing ratio) between the filler and the binder polymer compound.
- Example 14-1 a laminated film type battery was produced in the same manner as in Example 11-1.
- Example 14-2 to Example 14-3 the type of the binder polymer compound (resin) was changed.
- PAN polyacrylonitrile
- PEG polyethylene glycol
- Example 14-4 a laminated film type battery was produced in the same manner as in Example 11-2.
- Example 14-5 to Example 14-6 the type of the binder polymer compound constituting the gel electrolyte layer was changed.
- PAN polyacrylonitrile
- PEG polyethylene glycol
- Table 14 shows the evaluation results.
- the coating material is transparent by containing particles having a predetermined range of flatness and a predetermined range of refractive index. The pass / fail judgment of the laser measurement was acceptable.
- Example 15-1 to Example 15-2 In Examples 15-1 to 15-2, the simplified type shown in FIGS. 10, 11A, and 11B using the laminate film type battery similar to each of Examples 11-1 to 11-2. A battery pack (soft pack) was prepared.
- Example 15-3 to Example 15-4 a laminate film type battery that is the same as Example 11-1 to Example 11-2, except that the coating material was applied only to one surface of the separator on the positive electrode side.
- Example 15-5 to Example 15-6 a laminate film type battery that is the same as Example 11-1 to Example 11-2, except that the coating material was applied only to one surface on the negative electrode side of the separator.
- Example 15-1 A simple battery pack (soft pack) shown in FIGS. 10, 11A and 11B was produced in the same manner as in Example 15-1, except that the paint did not contain a filler.
- Example 15-2 A simple battery pack (soft pack) shown in FIGS. 10, 11A, and 11B was produced in the same manner as in Example 15-5, except that the paint did not contain a filler.
- Example 5-1 Battery evaluation: 100 kg pressure test, 60 ° C. 1 month storage test
- the soft packs of each of the examples and comparative examples were subjected to a 100 kg pressure test and a 60 ° C. one month storage test in the same manner as in Example 5-1.
- Table 15 shows the evaluation results.
- Examples 15-1 to 15-6 the results of the pressure test and the storage test were good.
- Examples 15-5 to 15-6 the separator deteriorated, but the results of the storage test passed because the filler on the negative electrode functions.
- Comparative Example 15-1 the result of the pressure test was bad
- Comparative Example 15-2 the result of the pressure test and the storage test was bad.
- Example 16-1 [Preparation of positive electrode, formation of particle-containing resin layer] A positive electrode was produced in the same manner as in Example 11-1. Moreover, the particle
- boehmite particles having an average particle diameter of 0.8 ⁇ m as a filler and polyvinylidene fluoride (PVdF) as a binder polymer compound are dispersed in N-methyl-2-pyrrolidone (NMP).
- NMP N-methyl-2-pyrrolidone
- a paint particle-containing resin solution
- the boehmite content is 5% by mass with respect to the total amount of the paint
- the mass ratio of boehmite to PVdF (boehmite / PVdF) is 50/50
- the solid content (boehmite and PVdF) is the total amount of the paint.
- the amount of each material was adjusted to 20% by mass.
- this paint was uniformly applied to each of both surfaces of the positive electrode with a predetermined paint thickness shown in Table 16.
- this paint was uniformly applied to each of both surfaces of the base material with a predetermined paint thickness shown in Table 16.
- the thickness of the paint film was measured with a laser thickness meter, and when the measured value was different from the predetermined paint thickness, the discharge amount of the paint was automatically adjusted so as to approach the predetermined paint thickness.
- the NMP was removed from the particle-containing resin solution layer by passing the positive electrode coated with the paint in a dryer, thereby forming a particle-containing resin layer composed of PVdF and boehmite on both sides of the positive electrode.
- a negative electrode was produced in the same manner as Example 11-1.
- a particle-containing resin layer was formed on both sides of the negative electrode in the same manner as the positive electrode.
- a positive electrode with a particle-containing resin layer formed on both sides, and a negative electrode and a separator with a particle-containing resin layer formed on both sides are laminated in the order of positive electrode, separator, negative electrode and separator, and wound in a flat shape many times in the longitudinal direction. Then, the wound electrode body was formed by fixing the winding end portion with an adhesive tape.
- the wound electrode body was sandwiched between the exterior members, and the three sides were heat-sealed. Note that a laminate film having a soft aluminum layer was used for the exterior member.
- electrolyte solution was prepared by dissolving lithium hexafluorophosphate (LiPF 6 ) as an electrolyte salt in a non-aqueous solvent in which ethylene carbonate (EC) and dimethyl carbonate (DMC) were mixed.
- EC ethylene carbonate
- DMC dimethyl carbonate
- the mass ratio of the constituents of the electrolyte (EC / DMC / LiPF 6) (EC / DMC / LiPF 6) is such that the 35/50/15 and adjust the amount of each component.
- a laminated film type battery having a battery shape of thickness 4.5 mm, 30 mm, and height 50 mm was produced.
- Example 16-2 to Example 16-55 Comparative Example 16-1 to Comparative Example 16-8>
- Example 16-2 to Example 16-55 and Comparative Example 16-1 to Comparative Example 16-8 as shown in Table 16 below, except that the filler used was changed, Similarly, a laminate film type battery was produced.
- the paint is transparent by including particles having a predetermined range of flatness and a predetermined range of refractive index.
- the pass / fail judgment of the laser measurement was acceptable.
- Comparative Examples 16-1 to 16-8 the coating becomes non-transparent because it contains particles that do not have at least one of a predetermined range of refractive index and a predetermined range of flatness. The measurement pass / fail judgment was rejected.
- Example 17-1 A laminated film type battery was produced in the same manner as Example 16-1.
- Example 17-2 to Example 17-7> As the filler, boehmite particles having different plane rates were used. The plane rate of the boehmite particles was adjusted to a desired one by increasing the ratio of spherical surfaces by increasing the growth rate during hydrothermal synthesis of boehmite particles or increasing the ratio of planes by decreasing the growth rate. Specifically, in Example 17-2, boehmite particles having a plane rate of 45% were used as the filler. In Example 17-3, boehmite particles having a plane rate of 50% were used as the filler. In Example 17-4, boehmite particles having a plane rate of 60% were used as the filler.
- Example 17-5 boehmite particles having a plane rate of 80% were used as the filler.
- Example 17-6 boehmite particles having a plane rate of 90% were used as the filler.
- Example 17-7 boehmite particles having a plane rate of 100% were used as the filler. Except for the above, a laminated film type battery was produced in the same manner as in Example 17-1.
- Example 17-8> A laminated film type battery was produced in the same manner as in Example 16-2.
- Example 17-9 to Example 17-14> As the filler, talc particles having different plane rates were used. In the grinding process using a hammer mill and a roll mill, increase the time ratio of the hammer mill to increase the cleavage plane ratio, increase the roll mill time ratio to decrease the cleavage plane ratio, The flatness was adjusted to the desired one. Specifically, in Example 17-9, talc particles having a plane rate of 45% were used as the filler. In Example 17-10, talc particles having a plane rate of 50% were used as the filler. In Examples 17-11, talc particles having a plane rate of 60% were used as the filler. In Examples 17-12, talc particles having a plane rate of 80% were used as the filler.
- Example 17-13 talc particles having a plane rate of 90% were used as the filler.
- Examples 17-14 talc particles having a plane rate of 100% were used as the filler. Except for the above, a laminated film type battery was produced in the same manner as in Example 17-8.
- Comparative Example 17-1 aluminum oxide particles having different plane rates were used as the filler. Specifically, in Comparative Example 17-1, aluminum oxide particles having a plane rate of 40% were used as the filler. In Comparative Example 17-2, aluminum oxide particles having a plane rate of 30% were used as the filler. In Comparative Example 17-3, aluminum oxide particles having a plane rate of 20% were used as the filler. In Comparative Example 17-4, aluminum oxide particles having a plane rate of 10% were used as the filler. In Comparative Example 17-5, spherical aluminum oxide (plane rate 0%) particles were used as the filler. Except for the above, a laminated film type battery was produced in the same manner as in Example 17-1.
- Table 17 shows the evaluation results.
- the coating material is transparent by including particles having a predetermined range of flatness and a predetermined range of refractive index.
- the pass / fail judgment of the laser measurement was acceptable.
- the paint becomes non-transparent because it contains particles that do not have at least one of a predetermined range of refractive index and a predetermined range of flatness. The measurement pass / fail judgment was rejected.
- Example 18-1 to Example 18-8 a laminate film type was obtained in the same manner as in Example 16-1, except that the mass ratio of the filler (boehmite particles) and the binder polymer compound (PVdF) was changed. A battery was produced. Specifically, in Example 18-1, the mass ratio (particle / PVdF) was 15/85. In Example 18-2, the mass ratio (particle / PVdF) was set to 20/80. In Example 18-3, the mass ratio (particle / PVdF) was 30/70. In Example 18-4, the mass ratio (particle / PVdF) was set to 50/50 as in Example 16-1.
- Example 18-5 the mass ratio (particle / PVdF) was 70/30. In Example 18-6, the mass ratio (particle / PVdF) was set to 80/20. In Example 18-7, the mass ratio (particle / PVdF) was 85/15. In Example 18-8, the mass ratio (particle / PVdF) was 90/10.
- Example 18-9 to Example 18-15 a laminate film type was obtained in the same manner as in Example 16-2 except that the mass ratio of the filler (talc particles) and the binder polymer compound (PVdF) was changed.
- a battery was produced.
- the mass ratio (particle / PVdF) was 20/80.
- the mass ratio (particle / PVdF) was 40/60.
- the mass ratio (particle / PVdF) was 50/50.
- the mass ratio (particle / PVdF) was 60/40.
- the mass ratio (particle / PVdF) was 80/20.
- the mass ratio (particle / PVdF) was 85/15.
- the mass ratio (particle / PVdF) was 90/10.
- Table 18 shows the evaluation results.
- the coating material is transparent by including particles having a predetermined range of flatness and a predetermined range of refractive index.
- the pass / fail judgment of the laser measurement was acceptable. It was also confirmed that the degree of transparency can be changed by changing the ratio (mixing ratio) between the filler and the binder polymer compound.
- Example 19-1 a laminated film type battery was produced in the same manner as in Example 16-1.
- Example 19-2 to Example 19-3 the type of the binder polymer compound (resin) constituting the gel electrolyte layer was changed.
- PAN polyacrylonitrile
- PEG polyethylene glycol
- Example 19-4 a laminated film type battery was produced in the same manner as in Example 16-2.
- Example 19-5 to Example 19-6 the type of the binder polymer compound constituting the gel electrolyte layer was changed.
- PAN polyacrylonitrile
- PEG polyethylene glycol
- Table 19 shows the evaluation results.
- the paint is transparent by including particles having a predetermined range of flatness and a predetermined range of refractive index. The pass / fail judgment of the laser measurement was acceptable.
- Example 20-1 to Example 20-2 In Examples 20-1 to 20-2, the simplified type shown in FIGS. 10, 11A, and 11B using the laminate film type battery similar to each of Examples 16-1 to 16-2. A battery pack (soft pack) was prepared.
- Example 20-3 to Example 20-4 a laminate film type battery similar to each of Example 16-1 to Example 16-2 was used except that the paint was applied only on both sides of the positive electrode.
- a simple battery pack (soft pack) shown in FIGS. 10, 11A and 11B was produced.
- Example 20-5 to Example 20-6 In Examples 20-5 to 20-6, laminated film type batteries similar to those in Examples 16-1 to 16-2 were used except that the paint was applied only on both sides of the negative electrode. A simple battery pack (soft pack) shown in FIGS. 10, 11A and 11B was produced.
- Example 20-1 A simple battery pack (soft pack) shown in FIGS. 10, 11A and 11B was produced in the same manner as in Example 20-1, except that the paint did not contain a filler.
- Example 20-2 A simple battery pack (soft pack) shown in FIGS. 10, 11A and 11B was produced in the same manner as in Example 20-5 except that the paint did not contain a filler.
- Example 5-1 Battery evaluation: 100 kg pressure test, 60 ° C. 1 month storage test
- the soft packs of each of the examples and comparative examples were subjected to a 100 kg pressure test and a 60 ° C. one month storage test in the same manner as in Example 5-1.
- Table 20 shows the evaluation results.
- Example 20-6 the results of the pressure test and the storage test were good.
- the separator deteriorated, but the result of the storage test was acceptable because the filler on the negative electrode functions.
- Comparative Example 20-1 the result of the pressure test was bad
- Comparative Example 20-2 the result of the pressure test and the storage test was bad.
- the nonaqueous electrolyte battery may be a primary battery.
- the present technology can be similarly applied to a case having other battery structures such as a coin type, a square type, or a button type.
- the separator 55 is the same separator as in the first embodiment, and uses a binder polymer compound as the resin of the particle-containing resin layer. It is good.
- the gel electrolyte layer 56 may have a configuration in which the filler is omitted.
- the electrode may be an electrode with a particle-containing resin layer using a binder polymer compound.
- the gel electrolyte layer 56 may have a configuration in which the filler is omitted.
- this technique can also take the following structures.
- the plane includes at least one of a crystal plane, a crush plane, and a cleavage plane.
- the inorganic particles are silicon oxide, zinc oxide, tin oxide, magnesium oxide, antimony oxide, aluminum oxide, magnesium sulfate, calcium sulfate, barium sulfate, strontium sulfate, magnesium carbonate, calcium carbonate, barium carbonate, lithium carbonate, magnesium hydroxide.
- the organic particles include melamine, melamine cyanurate, melamine polyphosphate, cross-linked polymethyl methacrylate, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyvinylidene fluoride, polyamide, polyimide, melamine resin, phenol resin, and epoxy resin.
- the silicate mineral is talc, calcium silicate, zinc silicate, zirconium silicate, aluminum silicate, magnesium silicate, kaolinite, sepiolite, imogolite, sericite, pyrophyllite, mica, zeolite, mullite, saponite.
- the carbonate mineral is at least one selected from the group consisting of hydrotalcite and dolomite
- the resin is polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride-tetrafluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer.
- Polymer Polymer, styrene-butadiene copolymer and its hydride, acrylonitrile-butadiene copolymer and its hydride, acrylonitrile-butadiene-styrene copolymer and its hydride, methacrylic acid ester-acrylic acid ester copolymer, styrene -Acrylate ester copolymer, Acrylonitrile- Acrylate ester copolymer, Ethylene propylene rubber, Polyvinyl alcohol, Polyvinyl acetate, Ethyl cellulose, Cellulose derivatives, Polyphenylene ether At least one selected from the group consisting of tellurium, polysulfone, polyethersulfone, polyphenylene sulfide, polyetherimide, polyimide, polyamide, polyamideimide, polyacrylonitrile, polyvinyl alcohol, polyether, acrylic resin, polyester, polyethylene glycol The battery according to any one of [1
- a mass ratio (particle / resin) between the particles and the resin is 15/85 or more and 90/10 or less.
- the particle-containing resin layer holds the electrolytic solution with the resin.
- the particle-containing resin layer holds the electrolytic solution in a void formed by at least one of the resin and the particles.
- the particle-containing resin layer includes one main surface and the other main surface of the positive electrode, one main surface and the other main surface of the negative electrode, and one main surface and the other main surface of the separator.
- the battery according to any one of [1] to [9], which is formed on at least one selected main surface.
- Particles, Resin, A solvent The particle shape includes a flat surface, the flatness of the particle is more than 40% and 100% or less, and the refractive index of the particle is 1.3 or more and less than 2.4.
- the battery according to any one of [1] to [10]; A control unit for controlling the battery; A battery pack having an exterior housing the battery.
- a battery pack having an exterior housing the battery.
- An electronic apparatus comprising the battery according to any one of [10] and receiving power supply from the battery.
- a power storage device that includes the battery according to any one of [10] and supplies electric power to an electronic device connected to the battery.
- a power information control device that transmits and receives signals to and from other devices via a network, The power storage device according to [17], wherein charge / discharge control of the battery is performed based on information received by the power information control device.
- a power system that receives power from the battery according to any one of [10], or that supplies power to the battery from a power generation device or a power network.
- protective tape 60 ... exterior member, 61. ..Adhesive film, 70 ... Laminated electrode body, 71 ... Positive electrode lead, 72 ... Negative electrode lead, 73 ... Positive electrode, 74 ... Negative electrode, 75 ... Separator, 76 ...
- Power generation device 405 ... Power consumption device, 405a ... Refrigerator, 405b ... Air conditioning device, 405c ... Television receiver, 405d ... Bath, 406 ... Electric vehicle 406a ... Electric vehicle, 406b ... Hybrid car, 406c ... Electric motorcycle, 407 ... Smart meter, 408 ... Power hub, 409 ... Power network, 410 ... Control device, 411 ⁇ Sensor, 412 ... Information network, 413 ... Server, 500 ... Hybrid vehicle, 501 ... Engine, 502 ... Generator, 503 ... Electric power / driving force conversion device, 504a ... Drive wheel, 504b ... drive wheel, 505a ... wheel, 505b ... wheel, 508 ... battery, 509 ... vehicle control device, 510 ... sensor 511 ... charging port
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Abstract
Description
まず、本技術の理解を容易にするため、本技術の技術的背景について説明する。近年高容量化のため、電池をさらに高い電圧で充電して使用することが試みられている。しかしながら電池の構成材料の一部には、高い電圧で劣化が進行するものもある。特にセパレータの酸化による劣化は、その代表的な事例である。
1.第1の実施の形態(セパレータの例)
2.第2の実施の形態(粒子含有樹脂層付き電極の例)
3.第3の実施の形態(ラミネートフィルム型電池の例)
4.第4の実施の形態(ラミネートフィルム型電池の例)
5.第5の実施の形態(円筒型電池の例)
6.第6の実施の形態(円筒型電池の例)
7.第7の実施の形態(ラミネートフィルム型の電池の電池パックの例)
8.第8の実施の形態(電池パックの例)
9.第9の実施の形態(蓄電システム等の例)
10.他の実施の形態 (変形例)
なお、以下に説明する実施の形態等は本技術の好適な具体例であり、本技術の内容がこれらの実施の形態等に限定されるものではない。また、本明細書に記載された効果はあくまで例示であって限定されるものではなく、また例示した効果と異なる効果が存在することを否定するものではない。
(1-1)セパレータの構成
本技術の第1の実施の形態によるセパレータについて説明する。図1は、本技術の第1の実施の形態によるセパレータの構成例を示す概略断面図である。図1に示すように、本技術の第1の実施の形態によるセパレータ11は、セパレータ基材11aと、セパレータ基材11aの少なくとも一方の主面に形成された粒子含有樹脂層11bとを備える。
セパレータ基材11a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。セパレータ基材11aの空孔には、非水電解液が保持される。
粒子含有樹脂層11bは、フィラーとしての粒子と樹脂とを含み、例えば微小な空孔が多数形成されている等の多孔構造を有するものである。粒子含有樹脂層11bを備えることで、耐熱性、耐酸化性等のセパレータの特性を向上することができる。詳細は後述するが、粒子含有樹脂層11bは、セパレータ基材11a上に形成された、粒子と樹脂と希釈溶媒とを含む樹脂溶液(塗料と称する場合もある)よりなる粒子含有樹脂溶液層から、乾燥等によって希釈溶媒を除去することにより形成されるものである。
第1の状態では、電解液が、バインダー高分子化合物および粒子の少なくとも何れかによって形成された微多孔内(空隙)に存在した状態で、粒子含有樹脂層11bに含まれた状態となる。この場合、粒子含有樹脂層11bは、セパレータとしての機能を有する。すなわち、粒子含有樹脂層11bは、例えば、セパレータ基材11aと共に、正極と負極との間に介在し、両極活物質の接触を防止するとともに、セパレータ基材11aと同様、その微多孔内に電解液を保持して電極間のイオン伝導の通路を形成する。
第2の状態では、電解液が、マトリックス高分子化合物に吸収された状態で、粒子含有樹脂層11bに含まれた状態となる。なお、この状態では、マトリックス高分子化合物は電解液を吸収し膨潤していわゆるゲル状態となり、マトリックス高分子化合物によって電解液および粒子が保持される。粒子含有樹脂層11bの多孔構造は、マトリックス高分子化合物の膨潤とともに消滅してもよい。この場合、粒子含有樹脂層11bは、電解質としての機能を有する。すなわち、粒子含有樹脂層11bは、電解液を吸収したマトリックス高分子化合物自体がイオン伝導体として機能する電解質となる。
樹脂としては、マトリックス高分子化合物およびバインダー高分子化合物として、溶媒に相溶可能な性質を有するものを用いることができる。このような樹脂としては、ポリフッ化ビニリデン、ポリテトラフルオロエチレン等の含フッ素樹脂、フッ化ビニリデン-テトラフルオロエチレン共重合体、エチレン-テトラフルオロエチレン共重合体等の含フッ素ゴム、スチレン-ブタジエン共重合体およびその水素化物、アクリロニトリル-ブタジエン共重合体およびその水素化物、アクリロニトリル-ブタジエン-スチレン共重合体およびその水素化物、メタクリル酸エステル-アクリル酸エステル共重合体、スチレン-アクリル酸エステル共重合体、アクリロニトリル-アクリル酸エステル共重合体、エチレンプロピレンラバー、ポリビニルアルコール、ポリ酢酸ビニル等のゴム類、エチルセルロース、メチルセルロース、ヒドロキシエチルセルロース、カルボキシメチルセルロース等のセルロース誘導体、ポリフェニレンエーテル、ポリスルホン、ポリエーテルスルホン、ポリフェニレンスルフィド、ポリエーテルイミド、ポリイミド、ポリアミド(特にアラミド)、ポリアミドイミド、ポリアクリロニトリル、ポリビニルアルコール、ポリエーテル、アクリル酸樹脂またはポリエステル等の融点およびガラス転移温度の少なくとも一方が180℃以上の樹脂、ポリエチレングリコール等が挙げられる。
粒子含有樹脂層11bに含まれるフィラーとしては、光の散乱を低減させて粒子含有樹脂層11bの前駆体である粒子含有樹脂溶液層の透明性を確保する観点から、平面を含む形状であり、且つ、所定の平面率を有し、且つ、所定の屈折率を有する粒子を用いる。例えば、アルミナ粒子等の白い無機物の粉体は、無色透明な粒子で構成されているが、光の散乱現象により白くなっている。本技術では、白くなる要因である光の散乱を抑制し、粒子含有樹脂層11bの前駆体の粒子含有樹脂溶液層の透明性を向上するために、フィラーとして、平面を含む形状であり、且つ、所定の平面率を有し、且つ所定の屈折率を有する粒子を用いている。
平面を含む形状の粒子の典型的な例の外観を示すため、図2Aに走査型電子顕微鏡(SEM:Scanning Electron Microscope)で観察した平面を含む形状のタルク粒子のSEM写真を示す。図2BにSEMで観察した平面を含む形状のベーマイト粒子のSEM写真を示す。図2AのSEM写真では、タルク粒子の劈開を中心とする粒子表面が観察される。図2BのSEM写真では、ベーマイトの水熱合成での結晶成長で作られた結晶面に囲まれた粒子表面が観察される。
粒子の平面率は、粒子含有樹脂溶液層の透明性を確保する観点から、40%超100%以下であり、透明性をより向上する観点から、45%以上100%以下であることがより好ましく、60%以上100%であることがさらに好ましい。なお、平面率は、例えば、以下のようにして求めることができる。
粒子含有樹脂層11bの主面に対して垂直方向から、SEM(Scanning Electron Microscope、走査型顕微鏡)にて、粒子含有樹脂層11bを観察し、体積基準の50%平均粒径(D50)前後のサイズの典型的形状の粒子10個の写真を撮影する。なお、平均粒径(D50)は、粒子含有樹脂層11bから樹脂成分等を除去した後の粉体を、レーザー回折式粒度分布測定装置に投入して測定したものである。次に、各粒子について、投影面積のうち、結晶面、破砕面、劈開面に相当する平面の投影面積(複数面ある場合はそれらの合計面積)を求め、粒子全体の投影面積に対する平面の投影面積の百分率を算出し、算出した各粒子の百分率の平均値を平面率とする。
平面を含む形状の粒子を作るには、単結晶を育成し平滑な結晶面を形成させる育成方法、結晶粒子を粉砕によって割る方法等がある。単結晶を育成する方法としては、液中で成長させるフラックス法、水熱育成法、共沈法等が好ましい。
粒子の屈折率は、粒子含有樹脂溶液層の透明性を確保する観点から、1.3以上2.4未満であり、1.3以上2.1以下であることが好ましい。樹脂溶液と粒子との屈折率の違い(固体は屈折率が高く、液体は屈折率が低いという違い)からくる光の屈折による散乱による透明性の低下を抑えるためである。固体である粒子の屈折率を、液体である樹脂溶液の屈折率に近づけるため、固体である粒子の中でも、低い方の屈折率である1.3以上2.4未満、好ましくは1.3以上2.1以下の範囲の粒子を用いる。
粒子と樹脂との混合比は、樹脂溶液の屈折率を粒子に近づけ、粒子含有樹脂溶液の透明性をより向上できる観点から、質量比(粒子/樹脂)で粒子/樹脂=15/85以上90/10以下の範囲であることが好ましく、20/80以上90/10以下の範囲であることがより好ましく、粒子/樹脂=20/80以上80/20以下の範囲であることがさらに好ましい。
セパレータ11の厚さは、必要な強度を保つことができる厚さ以上であれば任意に設定可能である。セパレータ11は、正極と負極との間の絶縁を図り、短絡等を防止するとともに、セパレータ11を介した電池反応を好適に行うためのイオン透過性を有し、かつ電池内において電池反応に寄与する活物質層の体積効率をできるだけ高くできる厚さに設定されることが好ましい。具体的に、セパレータ11の厚さは、例えば7μm以上20μm以下であることが好ましい。なお、セパレータ11の厚さは、この範囲に限定されるものではない。
上述した第1の実施の形態によるセパレータ11は、下記のようにして製造することができる。
樹脂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、樹脂を溶解させて塗料(粒子含有樹脂溶液)を得る。続いて、この塗料を、セパレータ基材11aの少なくとも一方の面に塗布し、粒子含有樹脂溶液層を形成する。
第1の例と同様、樹脂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、樹脂を溶解させて塗料(粒子含有樹脂溶液)を得る。続いて、この塗料を、セパレータ基材11aの少なくとも一方の面に塗布し、粒子含有樹脂溶液層を形成する。
本技術の第2の実施の形態による粒子含有樹脂層付き電極について説明する。図3は、本技術の第1の実施の形態による粒子含有樹脂層付き電極の構成例を示す概略断面図である。
粒子含有樹脂層21bは、粒子と、樹脂とを含むものであり、その構成および形成方法の詳細は、セパレータ基材11aに代えて電極21aに対して形成されること以外は、第1の実施の形態と同様である。
第1の状態では、電解液が、バインダー高分子化合物および粒子の少なくとも何れかによって形成された微多孔内(空隙)に存在した状態で、粒子含有樹脂層21bに含まれた状態となる。この場合、粒子含有樹脂層21bは、セパレータとしての機能を有する。すなわち、粒子含有樹脂層21bは、正極と負極との間に介在し、両極活物質の接触を防止するとともに、その微多孔内に電解液を保持して電極間のイオン伝導の通路を形成する。
第2の状態では、電解液が、マトリックス高分子化合物に吸収された状態で、粒子含有樹脂層21bに含まれた状態となる。なお、この状態では、マトリックス高分子化合物は電解液を吸収し膨潤していわゆるゲル状態となり、マトリックス高分子化合物によって電解液および粒子が保持される。粒子含有樹脂層11bの多孔構造は、マトリックス高分子化合物の膨潤とともに消滅してもよい。この場合、粒子含有樹脂層21bは、電解質としての機能を有する。すなわち、粒子含有樹脂層21bは、電解液を吸収したマトリックス高分子化合物自体がイオン伝導体として機能する電解質となる。
本技術の第3の実施の形態では、ラミネートフィルム型の非水電解質電池(電池)について説明する。この非水電解質電池は、例えば充電および放電が可能な非水電解質二次電池であり、また、例えばリチウムイオン二次電池である。
図4は、第3の実施の形態による非水電解質電池62の第1の構成例を表すものである。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。
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。
セパレータ55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。セパレータ55の空孔には、非水電解液が保持される。セパレータ55の構成は、第1の実施の形態のセパレータ基材11aと同様である。
ゲル電解質層56は、フィラーとしての粒子とマトリックス高分子化合物(樹脂)と非水電解液(電解液)とを含み、セパレータ55の少なくとも一方の主面に形成された粒子含有樹脂層が電解液を含むことにより形成されたものである。セパレータ55の少なくとも一方の主面に形成された粒子含有樹脂層は、例えば、マトリックス高分子化合物が電解液を吸収し膨潤していわゆるゲル状となって、電解液を吸収したゲル状のマトリックス高分子自体がイオン伝導体として機能するゲル電解質層56となる。なお、この場合、マトリックス高分子化合物の膨潤とともに、粒子含有樹脂層の多孔構造は消滅してもよい。ゲル電解質層56には、粒子が含まれているので、ゲル電解質層56の強度や耐熱性、耐酸化性が向上し、安全性等の特性を向上することができる。
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。
電解質塩は、例えば、リチウム塩等の軽金属化合物の1種あるいは2種以上を含有している。このリチウム塩としては、例えば、六フッ化リン酸リチウム(LiPF6)、四フッ化ホウ酸リチウム(LiBF4)、過塩素酸リチウム(LiClO4)、六フッ化ヒ酸リチウム(LiAsF6)、テトラフェニルホウ酸リチウム(LiB(C6H5)4)、メタンスルホン酸リチウム(LiCH3SO3)、トリフルオロメタンスルホン酸リチウム(LiCF3SO3)、テトラクロロアルミン酸リチウム(LiAlCl4)、六フッ化ケイ酸二リチウム(Li2SiF6)、塩化リチウム(LiCl)あるいは臭化リチウム(LiBr)等が挙げられる。中でも、六フッ化リン酸リチウム、四フッ化ホウ酸リチウム、過塩素酸リチウムおよび六フッ化ヒ酸リチウムからなる群のうちの少なくとも1種が好ましく、六フッ化リン酸リチウムがより好ましい。
非水溶媒としては、例えば、γ-ブチロラクトン、γ-バレロラクトン、δ-バレロラクトンあるいはε-カプロラクトン等のラクトン系溶媒、炭酸エチレン、炭酸プロピレン、炭酸ブチレン、炭酸ビニレン、炭酸ジメチル、炭酸エチルメチルあるいは炭酸ジエチル等の炭酸エステル系溶媒、1,2-ジメトキシエタン、1-エトキシ-2-メトキシエタン、1,2-ジエトキシエタン、テトラヒドロフランあるいは2-メチルテトラヒドロフラン等のエーテル系溶媒、アセトニトリル等のニトリル系溶媒、スルフォラン系溶媒、リン酸類、リン酸エステル溶媒、またはピロリドン類等の非水溶媒が挙げられる。溶媒は、いずれか1種を単独で用いてもよく、2種以上を混合して用いてもよい。
この非水電解質電池62は、例えば、以下の方法により製造することができる。この非水電解質電池62は、典型的には、例えば、以下の正極作製工程と、負極作製工程と、粒子含有樹脂層形成工程(セパレータ作製工程)と、巻回工程と、電池組み立て工程とを順次行うことにより製造される。
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53A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53Bを形成し、正極53を作製する。その後、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。
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54A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54Bを形成し、負極54を作製する。その後、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。
まず、セパレータ55の一方の主面または両方の主面に粒子含有樹脂層が形成された第1の実施の形態と同様のセパレータを作製する。粒子含有樹脂層形成工程の詳細は、第1の実施の形態と同様である。なお、セパレータ55の構成が、セパレータ基材11aの構成に対応し、これと同様の構成を有する。セパレータ55とセパレータ55の少なくとも一方の主面に形成された粒子含有樹脂層とが、第1の実施の形態によるセパレータ11(セパレータ基材11aとセパレータ基材11aの少なくとも一方の主面に形成された粒子含有樹脂層11bとを含むセパレータ11)に対応し、これと同様の構成を有する。
次に、正極53および負極54を、一方の主面または両方の主面に粒子含有樹脂層が形成されたセパレータ55を介し積層および巻回することにより、巻回構造を有する巻回電極体50を作製する。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。
次に、ラミネートフィルムからなる外装部材60を深絞り加工することで凹部を形成し、巻回電極体50をこの凹部に挿入し、外装部材60の未加工部分を凹部上部に折り返し、凹部の外周の一部(例えば一辺)を除いて熱溶着する。その際、正極リード51および負極リード52と外装部材60との間には密着フィルム61を挿入する。
上述の第1の構成では、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6A~図6C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6A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6B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6Cは、図6A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。
本技術の第4の実施の形態では、ラミネートフィルム型の非水電解質電池(電池)について説明する。この非水電解質電池は、例えば充電および放電が可能な非水電解質二次電池であり、また、例えばリチウムイオン二次電池である。
第4の実施の形態による非水電解質電池62の第1の構成例は、以下に述べる点を除き、図4および図5に示す第3の実施の形態による非水電解質電池63の第1の構成例と同様である。すなわち、この非水電解質電池62は、第3の実施の形態のように、セパレータ55の表面に粒子含有樹脂層が形成されたもの(第1の実施の形態によるセパレータ)が組み込まれていない。その代わりに、第2の実施の形態と同様の粒子含有樹脂層付き電極であって、粒子含有樹脂層の樹脂としてマトリックス高分子化合物を用いたものが組み込まれている。そして、電極の表面に形成された粒子含有樹脂層が電解液を含むことにより、ゲル電解質層56を形成している。以上のこと以外は、第3の実施の形態と同様である。以下では、第3の実施の形態と同一構成の重複する説明は適宜省略し、第3の実施の形態と異なる点を詳細に説明する。
ゲル電解質層56は、フィラーとしての粒子とマトリックス高分子化合物(樹脂)と非水電解液(電解液)とを含み、正極53および負極54の少なくとも一方の電極の両方の主面に形成された粒子含有樹脂層が電解液を含むことにより形成されたものである。正極53および負極54の少なくとも一方の電極の両方の主面に形成された粒子含有樹脂層は、例えば、マトリックス高分子化合物が電解液を吸収し膨潤していわゆるゲル状となって、電解液を吸収したゲル状のマトリックス高分子自体がイオン伝導体として機能するゲル電解質層56となる。なお、この場合、マトリックス高分子化合物の膨潤により、粒子含有樹脂層の多孔構造は消滅してもよい。ゲル電解質層56には、粒子が含まれているので、ゲル電解質層56の強度や耐熱性、耐酸化性が向上し、安全性等の特性を向上することができる。
この非水電解質電池62は、典型的には、例えば、第3の実施の形態と同様の正極作製工程および負極作製工程を行った後、粒子含有樹脂層形成工程(粒子含有樹脂層付き電極作製工程)と、巻回工程と、電池組み立て工程とを順次行うことにより製造される。
まず、正極53の両方の主面に粒子含有樹脂層が形成された粒子含有樹脂層付き電極(正極)および負極54の両方の主面に粒子含有樹脂層が形成された粒子含有樹脂層付き電極(負極)を作製する。なお、正極および負極のうちの一方の電極のみを、粒子含有樹脂層付き電極としてもよい。粒子含有樹脂層の形成方法は、第2の実施の形態と同様である。
次に、粒子含有樹脂層付き正極53および粒子含有樹脂層付き負極54を、セパレータ55を介し積層および巻回することにより、巻回構造を有する巻回電極体50を作製する。
次に、ラミネートフィルムからなる外装部材60を深絞り加工することで凹部を形成し、巻回電極体50をこの凹部に挿入し、外装部材60の未加工部分を凹部上部に折り返し、凹部の外周の一部(例えば一辺)を除いて熱溶着する。その際、正極リード51および負極リード52と外装部材60との間には密着フィルム61を挿入する。
上述の第1の構成例では、巻回電極体50が外装部材60で外装された非水電解質電池62について説明したが、巻回電極体50の代わりに積層電極体70を用いてもよい。第4の実施の形態による非水電解質電池62の第2の構成例は、図6A~図6Cに示す構成と同様である。
第5の実施の形態では、円筒型の非水電解質電池について説明する。第5の実施の形態による電池は、第1の実施の形態と同様のセパレータであって、粒子含有樹脂層の樹脂としてバインダー高分子化合物を用いたものが組み込まれている。
図7は、第5の実施の形態による非水電解質電池の一例を示す断面図である。非水電解質電池80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80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81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91と負極92とがセパレータ93を介して巻回された巻回電極体90を有している。
正極91は、正極活物質を含有する正極活物質層91Bが、正極集電体91Aの両面上に形成されたものである。正極集電体91A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92は、例えば、対向する一対の面を有する負極集電体92Aの両面に負極活物質層92B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92Aの片面のみに負極活物質層92Bを設けるようにしてもよい。負極集電体92A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93は、第1の実施の形態によるセパレータ11と同様である。すなわち、図8に示すように、セパレータ基材93aの両方の主面に粒子含有樹脂層93bが形成されている。セパレータ基材93aの一方の主面のみに粒子含有樹脂層93bが形成されていてもよい。粒子含有樹脂層93bにより、セパレータ93の強度や耐熱性、耐酸化性が向上し、安全性等の特性を向上することができる。なお、粒子含有樹脂層93bに含まれる樹脂としては、典型的には、バインダー高分子化合物を用いる。セパレータ93には、非水電解液が含浸される。粒子含有樹脂層93bは、例えば、セパレータ基材93aと共に、正極91と負極92との間に介在し、両極活物質の接触を防止するとともに、セパレータ基材93aと同様、その微多孔内に電解液を保持して電極間のイオン伝導の通路を形成する。
非水電解液は、第3の実施の形態と同様である。
[正極の製造方法、負極の製造方法]
第3の実施の形態と同様にして、正極91および負極92を作製する。
第1の実施の形態と同様にして、セパレータ基材93aの少なくとも一方の主面に粒子含有樹脂層93bを形成して、セパレータ93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91Aに正極リード95を溶接等により取り付けると共に、負極集電体92Aに負極リード96を溶接等により取り付ける。その後、正極91と負極92とを本技術のセパレータ93を介して巻回し巻回電極体90とする。正極リード95の先端部を安全弁機構に溶接すると共に、負極リード96の先端部を電池缶81に溶接する。この後、巻回電極体90の巻回面を一対の絶縁板82,83で挟み、電池缶81の内部に収納する。巻回電極体90を電池缶81の内部に収納したのち、非水電解液を電池缶81の内部に注入し、セパレータ93に含浸させる。そののち、電池缶81の開口端部に電池蓋83、安全弁84等からなる安全弁機構および熱感抵抗素子87をガスケット88を介してかしめることにより固定する。これにより、図7に示した本技術の非水電解質電池80が形成される。
第6の実施の形態では、円筒型の非水電解質電池について説明する。第6の実施の形態による電池は、第2の実施の形態と同様の粒子含有樹脂層付き電極であって、粒子含有樹脂層の樹脂としてバインダー高分子化合物を用いたものが組み込まれている。
図9に示すように、粒子含有樹脂層91Cおよび粒子含有樹脂層92Cのそれぞれは、例えば、セパレータ93と共に、正極91と負極92との間に介在し、両極活物質の接触を防止するとともに、セパレータ93と同様、その微多孔内に電解液を保持して電極間のイオン伝導の通路を形成する。粒子含有樹脂層91C、92Cにより、セパレータ93の強度や耐熱性、耐酸化性を補強することができ、安全性等の特性を向上することができる。セパレータ93は、典型的にはセパレータ基材93aと同様の構成を有する。なお、セパレータ93としては、第5の実施の形態と同様のセパレータ(セパレータ基材93aおよび粒子含有樹脂層93b)を用いてもよい。以上の構成以外は、第5の実施の形態と同様である。
[正極の製造方法]
第2の実施の形態と同様に、粒子含有樹脂層付き正極を作製する。すなわち、第5の実施の形態と同様に、正極91を作製する。次に、正極91の両方の主面または一方の主面に、塗料(粒子含有樹脂溶液)を塗布して粒子含有樹脂溶液層を形成する。その後、粒子含有樹脂溶液層を乾燥することにより粒子含有樹脂層91Cを形成する。
第2の実施の形態と同様に、粒子含有樹脂層付き負極を作製する。第5の実施の形態と同様に、負極92を作製する。次に、負極92の両方の主面または一方の主面に、塗料(粒子含有樹脂溶液)を塗布して粒子含有樹脂溶液層を形成する。その後、粒子含有樹脂溶液層を乾燥することにより粒子含有樹脂層92Cを形成する。
セパレータ93は、セパレータ基材93aの構成と同様のものを用意する。
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91Aに正極リード95を溶接等により取り付けると共に、負極集電体92Aに負極リード96を溶接等により取り付ける。その後、粒子含有樹脂層付き正極91と粒子含有樹脂層付き負極92とをセパレータ93を介して巻回し巻回電極体90とする。正極リード95の先端部を安全弁機構に溶接すると共に、負極リード96の先端部を電池缶81に溶接する。
第7の実施の形態では、第3の実施の形態または第4の実施の形態と同様のゲル電解質層を備えたラミネートフィルム型の電池(非水電解質電池)の電池パックの例について説明する
図12は、本技術の第3の実施~第6の実施の形態による電池(以下、二次電池と適宜称する)を電池パックに適用した場合の回路構成例を示すブロック図である。電池パックは、組電池301、外装、充電制御スイッチ302aと、放電制御スイッチ303a、を備えるスイッチ部304、電流検出抵抗307、温度検出素子308、制御部310を備えている。
上述した本技術の第3の実施の形態~第6の実施の形態による電池および第7の実施の形態~第8実施の形態による電池パックは、例えば電子機器や電動車両、蓄電装置等の機器に搭載または電力を供給するために使用することができる。
本技術の電池を用いた蓄電装置を住宅用の蓄電システムに適用した例について、図13を参照して説明する。例えば住宅401用の蓄電システム400においては、火力発電402a、原子力発電402b、水力発電402c等の集中型電力系統402から電力網409、情報網412、スマートメータ407、パワーハブ408等を介し、電力が蓄電装置403に供給される。これと共に、家庭内の発電装置404等の独立電源から電力が蓄電装置403に供給される。蓄電装置403に供給された電力が蓄電される。蓄電装置403を使用して、住宅401で使用する電力が給電される。住宅401に限らずビルに関しても同様の蓄電システムを使用できる。
本技術を車両用の蓄電システムに適用した例について、図14を参照して説明する。図14に、本技術が適用されるシリーズハイブリッドシステムを採用するハイブリッド車両の構成の一例を概略的に示す。シリーズハイブリッドシステムはエンジンで動かす発電機で発電された電力、あるいはそれをバッテリーに一旦貯めておいた電力を用いて、電力駆動力変換装置で走行する車である。
[正極の作製]
正極活物質であるコバルト酸リチウム(LiCoO2)91質量%と、導電剤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、負極端子を正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ポリエチレン(PE)製微多孔性フィルム(ポリエチレンセパレータ)を用いた。この基材の両面に、下記の様にして、塗料を塗布して粒子含有樹脂溶液層(塗料膜)を形成した後、これを乾燥し、粒子含有樹脂層を形成した。
正極、負極および粒子含有樹脂層が両面に形成されたセパレータを、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。
実施例1-2~実施例1-55および比較例1-1~比較例1-8では、下掲の表1に示すように、用いるフィラーを変えたこと以外は、実施例1-1と同様にして、ラミネートフィルム型電池を作製した。
上述の実施例および比較例において、フィラーの平面率、塗料の外観は以下のようにして測定または評価したものである。(後述の実施例および比較例も同様)
平面率は以下のように測定した。電解液を含む粒子含有樹脂層の主面に対して垂直方向から、SEMにて電解液を含む粒子含有樹脂層を観察し、体積基準の50%平均粒径(D50)前後のサイズの典型的形状の粒子10個の写真を撮影した。なお、平均粒径(D50)は、電解液を含む粒子含有樹脂層から、樹脂と液体成分等を除去した後の粉体を、レーザー回折式粒度分布測定装置で測定したものである。次に、各粒子について、投影面積のうち、結晶面、破砕面、劈開面に相当する平面の投影面積(複数面ある場合はそれらの合計面積)を求め、粒子全体の投影面積に対する平面の投影面積の百分率を算出し、算出した各粒子の百分率の平均値を平面率とした。
視覚観察により、塗料膜の外観を観察した。なお、透明性の程度で、透明、ほぼ透明、透明に近い、半透明と段階的に評価した。透明、ほぼ透明、透明に近い場合は、いずれも、塗料膜を通して、塗布対象(電極またはセパレータ)の輪郭を完全に視認できた。また、白濁の色の濃さの程度により、薄く白濁、白濁、濃い白濁と段階的に評価した。薄く白濁、白濁、濃い白濁、褐色不透明の場合は、塗料膜を通して、塗布対象(電極またはセパレータ)の輪郭を視認できなかった。
作製した各電池を解体し、粒子含有樹脂層のマトリックス高分子化合物が電解液を吸って膨潤したゲル電解質層の厚みを、接触式厚み計によって確認した。厚みの算定は、ポリエチレンセパレータ(基材)の厚みとゲル電解質を含んだセパレータの厚みとの差を求めることにより行った。
実施例1-1と同様にして、ラミネートフィルム型電池を作製した。
フィラーとして、平面率の異なるベーマイト粒子を用いた。ベーマイト粒子の水熱合成時の成長速度を速くして球面の比率を多くしたり、成長速度を遅くして平面の比率を上げたりすることによりベーマイト粒子の平面率を所望のものに調整した。具体的には、実施例2-2では、フィラーとして、平面率45%のベーマイト粒子を用いた。実施例2-3では、フィラーとして、平面率50%のベーマイト粒子を用いた。実施例2-4では、フィラーとして、平面率60%のベーマイト粒子を用いた。実施例2-5では、フィラーとして、平面率80%のベーマイト粒子を用いた。実施例2-6では、フィラーとして、平面率90%のベーマイト粒子を用いた。実施例2-7では、フィラーとして、平面率100%のベーマイト粒子を用いた。以上のこと以外は、実施例2-1と同様にして、ラミネートフィルム型電池を作製した。
実施例1-2と同様にして、ラミネートフィルム型電池を作製した。
フィラーとして、平面率の異なるタルク粒子を用いた。ハンマーミルおよびロールミルを用いて行う粉砕工程において、ハンマーミルの時間比率を多くして劈開面の比率を上げたり、ロールミルの時間比率を多くして劈開面の比率を下げたりして、タルク粒子の平面率を所望のものに調整した。具体的には、実施例2-9では、フィラーとして、平面率45%のタルク粒子を用いた。実施例2-10では、フィラーとして、平面率50%のタルク粒子を用いた。実施例2-11では、フィラーとして、平面率60%のタルク粒子を用いた。実施例2-12では、フィラーとして、平面率80%のタルク粒子を用いた。実施例2-13では、フィラーとして、平面率90%のタルク粒子を用いた。実施例2-14では、フィラーとして、平面率100%のタルク粒子を用いた。以上のこと以外は、実施例2-8と同様にして、ラミネートフィルム型電池を作製した。
フィラーとして、ベーマイト粒子に代えて、平面率の異なる酸化アルミニウム粒子を用いた。具体的には、比較例2-1では、フィラーとして、平面率40%の酸化アルミニウム粒子を用いた。比較例2-2では、フィラーとして、平面率30%の酸化アルミニウム粒子を用いた。比較例2-3では、フィラーとして、平面率20%の酸化アルミニウム粒子を用いた。比較例2-4では、フィラーとして、平面率10%の酸化アルミニウム粒子を用いた。比較例2-5では、フィラーとして、球状の酸化アルミニウム(平面率0%)粒子を用いた。以上のこと以外は、実施例2-1と同様にして、ラミネートフィルム型電池を作製した。
作製した各実施例および各比較例のラミネートフィルム型電池について、実施例1-1と同様にして、レーザー計測の合否判定を行った。
実施例3-1~実施例3-8では、フィラー(ベーマイト粒子)とマトリックス高分子化合物(PVdF)との質量比を変えたこと以外は、実施例1-1と同様にして、ラミネートフィルム型電池を作製した。具体的には、実施例3-1では質量比(粒子/PVdF)を15/85にした。実施例3-2では質量比(粒子/PVdF)を20/80にした。実施例3-3では質量比(粒子/PVdF)を30/70にした。実施例3-4では、実施例1-1と同様、質量比(粒子/PVdF)を50/50にした。実施例3-5では質量比(粒子/PVdF)を70/30にした。実施例3-6では質量比(粒子/PVdF)を80/20にした。実施例3-7では、質量比(粒子/PVdF)を85/15にした。実施例3-8では質量比(粒子/PVdF)を90/10にした。
実施例3-9~実施例3-15では、フィラー(タルク粒子)とマトリックス高分子化合物(PVdF)との質量比を変えたこと以外は、実施例1-2と同様にして、ラミネートフィルム型電池を作製した。具体的には、実施例3-9では質量比(粒子/PVdF)を20/80にした。実施例3-10では質量比(粒子/PVdF)を40/60にした。実施例3-11では、実施例1-2と同様、質量比(粒子/PVdF)を50/50にした。実施例3-12では質量比(粒子/PVdF)を60/40にした。実施例3-13では質量比(粒子/PVdF)を80/20にした。実施例3-14では質量比(粒子/PVdF)を85/15にした。実施例3-15では質量比(粒子/PVdF)を90/10にした。
作製した各実施例および各比較例のラミネートフィルム型電池について、実施例1-1と同様にして、レーザー計測の合否判定を行った。
実施例4-1では、実施例1-1と同様にしてラミネートフィルム型電池を作製した。
実施例4-2~実施例4-3では、ゲル電解質層を構成するマトリックス高分子化合物(樹脂)の種類を変えた。実施例4-2では、マトリックス高分子化合物としてPAN(ポリアクリロニトリル)を用いた。実施例4-3では、マトリックス高分子化合物として、PEG(ポリエチレングリコール)を用いた。以上のこと以外は、実施例4-1と同様にして、ラミネートフィルム型電池を作製した。
実施例4-4では、実施例1-2と同様にしてラミネートフィルム型電池を作製した。
実施例4-5~実施例4-6では、ゲル電解質層を構成するマトリックス高分子化合物の種類を変えた。実施例4-5では、マトリックス高分子化合物としてPAN(ポリアクリロニトリル)を用いた。実施例4-6では、マトリックス高分子化合物として、PEG(ポリエチレングリコール)を用いた。以上のこと以外は、実施例4-4と同様にして、ラミネートフィルム型電池を作製した。
作製した各実施例および各比較例のラミネートフィルム型電池について、実施例1-1と同様にして、レーザー計測の合否判定を行った。
実施例5-1~実施例5-2では、実施例1-1~実施例1-2のそれぞれと同様であるラミネートフィルム型電池を用いた、図10、図11Aおよび図11Bに示す簡易型の電池パック(ソフトパック)を作製した。
実施例5-3~実施例5-4では、塗料をセパレータの正極側の片面のみに塗布したこと以外は、実施例1-1~実施例1-2のそれぞれと同様であるラミネートフィルム型電池を用いた、図10、図11Aおよび図11Bに示す簡易型の電池パック(ソフトパック)を作製した。
実施例5-5~実施例5-6では、塗料をセパレータの負極側の片面のみに塗布したこと以外は、実施例1-1~実施例1-2のそれぞれと同様であるラミネートフィルム型電池を用いた、図10、図11Aおよび図11Bに示す簡易型の電池パック(ソフトパック)を作製した。
塗料にフィラーを含有しないこと以外は、実施例5-1と同様にして、図10、図11Aおよび図11Bに示す簡易型の電池パック(ソフトパック)を作製した。
塗料にフィラーを含有しないこと以外は、実施例5-5と同様にして、図10、図11Aおよび図11Bに示す簡易型の電池パック(ソフトパック)を作製した。
作製した各実施例および各比較例のソフトパックについて、以下の100kg加圧試験、60℃1ヶ月保存試験を行った。
作製したソフトパックを、23℃の雰囲気下において、1Cの定電流で電池電圧が4.2Vに達するまで定電流充電した後、4.2Vの定電圧で充電時間の合計が2.5時間となるまで定電圧充電した。次に、30mmの間隔で並置された2本の丸棒上に、充電したソフトパックを配置し、ソフトパックのセンター位置に対して、上方から1本の丸棒を押し当てて、荷重100kgを加えた。その際、電圧計(テスター)によりソフトパックの電圧を確認し、1%以上の電圧低下を確認したら短絡有りとし、1%以上の電圧低下を確認しない場合は短絡なしとした。
作製したソフトパックを、23℃の雰囲気下において、1Cの定電流で電池電圧が4.35Vに達するまで定電流充電した後、4.35Vの定電圧で充電時間の合計が2.5時間となるまで定電圧充電した。続いて、充電状態のソフトパックを、60℃の恒温槽中に1ヶ月保存した後、セパレータの劣化を起因とする内部短絡の有無を確認した。
[正極の作製、粒子含有樹脂層の形成]
実施例1-1と同様にして、正極を作製した。また、正極の両面に以下のようにして粒子含有樹脂層を形成した。
まず、フィラーである平均粒径0.8μmのベーマイトの粒子(屈折率1.7)とマトリックス高分子化合物であるポリフッ化ビニリデン(PVdF)とを、N-メチル-2-ピロリドン(NMP)に分散させて、塗料(粒子含有樹脂溶液)を調製した。この際、ベーマイトの含有量は塗料の全体量に対して5質量%とし、ベーマイトとPVdFとの質量比(ベーマイト/PVdF)は50/50とし、固形分(ベーマイトおよびPVdF)が塗料の全体量に対して20質量%となるように、各材料の量を調整した。
実施例1-1と同様にして、負極を作製した。また、正極と同様の手法で、負極の両面に粒子含有樹脂層を形成した。
基材として厚さ9μmポリエチレン(PE)製微多孔性フィルムを用いた。
粒子含有樹脂層が両面に形成された正極、粒子含有樹脂層が両面に形成された負極およびセパレータを、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。
実施例6-2~実施例6-55および比較例6-1~比較例6-8では、下掲の表6に示すように、用いるフィラーを変えたこと以外は、実施例6-1と同様にして、ラミネートフィルム型電池を作製した。
作製した各電池を解体し、粒子含有樹脂層のマトリックス高分子化合物が電解液を吸って膨潤したゲル電解質層の厚みを、接触式厚み計によって確認した。厚みの算定は、電極の厚みとゲル電解質層を含んだ電極の厚みとの差を求めることにより行った。塗料膜の厚さの測定値と、ゲル電解質層の厚さの測定値との差が、塗料膜の厚さの測定値に対する百分率で±10%以内に入っている場合は合格、それ以外の場合は不合格とした。
実施例7-1と同様にして、ラミネートフィルム型電池を作製した。
フィラーとして、平面率の異なるベーマイト粒子を用いた。ベーマイト粒子の水熱合成時の成長速度を速くして球面の比率を多くしたり、成長速度を遅くして平面の比率を上げたりすることによりベーマイト粒子の平面率を所望のものに調整した。具体的には、実施例7-2では、フィラーとして、平面率45%のベーマイト粒子を用いた。実施例7-3では、フィラーとして、平面率50%のベーマイト粒子を用いた。実施例7-4では、フィラーとして、平面率60%のベーマイト粒子を用いた。実施例7-5では、フィラーとして、平面率80%のベーマイト粒子を用いた。実施例7-6では、フィラーとして、平面率90%のベーマイト粒子を用いた。実施例7-7では、フィラーとして、平面率100%のベーマイト粒子を用いた。以上のこと以外は、実施例7-1と同様にして、ラミネートフィルム型電池を作製した。
実施例1-2と同様にして、ラミネートフィルム型電池を作製した。
フィラーとして、平面率の異なるタルク粒子を用いた。ハンマーミルおよびロールミルを用いて行う粉砕工程において、ハンマーミルの時間比率を多くして劈開面の比率を上げたり、ロールミルの時間比率を多くして劈開面の比率を下げたりして、タルク粒子の平面率を所望のものに調整した。具体的には、実施例7-9では、フィラーとして、平面率45%のタルク粒子を用いた。実施例7-10では、フィラーとして、平面率50%のタルク粒子を用いた。実施例7-11では、フィラーとして、平面率60%のタルク粒子を用いた。実施例7-12では、フィラーとして、平面率80%のタルク粒子を用いた。実施例7-13では、フィラーとして、平面率90%のタルク粒子を用いた。実施例7-14では、フィラーとして、平面率100%のタルク粒子を用いた。以上のこと以外は、実施例7-8と同様にして、ラミネートフィルム型電池を作製した。
フィラーとして、ベーマイト粒子に代えて、平面率の異なる酸化アルミニウム粒子を用いた。具体的には、比較例7-1では、フィラーとして、平面率40%の酸化アルミニウム粒子を用いた。比較例7-2では、フィラーとして、平面率30%の酸化アルミニウム粒子を用いた。比較例7-3では、フィラーとして、平面率20%の酸化アルミニウム粒子を用いた。比較例7-4では、フィラーとして、平面率10%の酸化アルミニウム粒子を用いた。比較例7-5では、フィラーとして、球状の酸化アルミニウム(平面率0%)粒子を用いた。以上のこと以外は、実施例7-1と同様にして、ラミネートフィルム型電池を作製した。
作製した各実施例および各比較例のラミネートフィルム型電池について、実施例1-1と同様にして、レーザー計測の合否判定を行った。
実施例8-1~実施例8-8では、フィラー(ベーマイト粒子)とマトリックス高分子化合物(PVdF)との質量比を変えたこと以外は、実施例1-1と同様にして、ラミネートフィルム型電池を作製した。具体的には、実施例8-1では質量比(粒子/PVdF)を15/85にした。実施例8-2では質量比(粒子/PVdF)を20/80にした。実施例8-3では質量比(粒子/PVdF)を30/70にした。実施例8-4では、実施例1-1と同様、質量比(粒子/PVdF)を50/50にした。実施例8-5では質量比(粒子/PVdF)を70/30にした。実施例8-6では質量比(粒子/PVdF)を80/20にした。実施例8-7では、質量比(粒子/PVdF)を85/15にした。実施例8-8では質量比(粒子/PVdF)を90/10にした。
実施例8-9~実施例8-15では、フィラー(タルク粒子)とマトリックス高分子化合物(PVdF)との質量比を変えたこと以外は、実施例1-2と同様にして、ラミネートフィルム型電池を作製した。具体的には、実施例8-9では質量比(粒子/PVdF)を20/80にした。実施例8-10では質量比(粒子/PVdF)を40/60にした。実施例8-11では、実施例1-2と同様、質量比(粒子/PVdF)を50/50にした。実施例8-12では質量比(粒子/PVdF)を60/40にした。実施例8-13では質量比(粒子/PVdF)を80/20にした。実施例8-14では質量比(粒子/PVdF)を85/15にした。実施例8-15では質量比(粒子/PVdF)を90/10にした。
作製した各実施例および各比較例のラミネートフィルム型電池について、実施例1-1と同様にして、レーザー計測の合否判定を行った。
実施例9-1では、実施例1-1と同様にしてラミネートフィルム型電池を作製した。
実施例9-2~実施例9-3では、ゲル電解質層を構成するマトリックス高分子化合物(樹脂)の種類を変えた。実施例9-2では、マトリックス高分子化合物としてPAN(ポリアクリロニトリル)を用いた。実施例9-3では、マトリックス高分子化合物として、PEG(ポリエチレングリコール)を用いた。以上のこと以外は、実施例9-1と同様にして、ラミネートフィルム型電池を作製した。
実施例9-4では、実施例1-2と同様にしてラミネートフィルム型電池を作製した。
実施例9-5~実施例9-6では、ゲル電解質層を構成するマトリックス高分子化合物の種類を変えた。実施例9-5では、マトリックス高分子化合物としてPAN(ポリアクリロニトリル)を用いた。実施例9-6では、マトリックス高分子化合物として、PEG(ポリエチレングリコール)を用いた。以上のこと以外は、実施例9-4と同様にして、ラミネートフィルム型電池を作製した。
作製した各実施例および各比較例のラミネートフィルム型電池について、実施例1-1と同様にして、レーザー計測の合否判定を行った。
実施例10-1~実施例10-2では、実施例6-1~実施例6-2のそれぞれと同様であるラミネートフィルム型電池を用いた、図10、図11Aおよび図11Bに示す簡易型の電池パック(ソフトパック)を作製した。
実施例10-3~実施例10-4では、塗料を正極の両面のみに塗布したこと以外は、実施例6-1~実施例6-2のそれぞれと同様であるラミネートフィルム型電池を用いた、図10、図11Aおよび図11Bに示す簡易型の電池パック(ソフトパック)を作製した。
実施例10-5~実施例10-6では、塗料を負極の両面のみに塗布したこと以外は、実施例6-1~実施例6-2のそれぞれと同様であるラミネートフィルム型電池を用いた、図10、図11Aおよび図11Bに示す簡易型の電池パック(ソフトパック)を作製した。
塗料にフィラーを含有しないこと以外は、実施例10-1と同様にして、図10、図11Aおよび図11Bに示す簡易型の電池パック(ソフトパック)を作製した。
塗料にフィラーを含有しないこと以外は、実施例10-5と同様にして、図10、図11Aおよび図11Bに示す簡易型の電池パック(ソフトパック)を作製した。
作製した各実施例および各比較例のソフトパックについて、実施例5-1と同様にして、100kg加圧試験、60℃1ヶ月保存試験を行った。
[正極の作製、負極の作製]
正極および負極を、実施例1-1と同様にして作製した。
基材として厚さ9μm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、塗料を塗布して粒子含有樹脂溶液層(塗料膜)を形成した後、これを乾燥し、粒子含有樹脂層を形成した。
正極、負極および粒子含有樹脂層が両面に形成されたセパレータを、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。
実施例11-2~実施例11-55および比較例11-1~比較例11-8では、下掲の表11に示すように、用いるフィラーを変えたこと以外は、実施例11-1と同様にして、ラミネートフィルム型電池を作製した。
作製した各電池を解体し電解液を含む粒子含有樹脂層の厚みを、接触式厚み計によって確認した。厚みの算定は、ポリエチレンセパレータ(基材)の厚みと、電解液を含む粒子含有樹脂層を備えたセパレータの厚みとの差からおこなった。塗料膜の厚さの測定値と、電解液を含む粒子含有樹脂層の厚さの測定値との差が、塗料膜の厚さの測定値に対する百分率で±10%以内に入っている場合は合格、それ以外の場合は不合格とした。
実施例11-1と同様にして、ラミネートフィルム型電池を作製した。
フィラーとして、平面率の異なるベーマイト粒子を用いた。ベーマイト粒子の水熱合成時の成長速度を速くして球面の比率を多くしたり、成長速度を遅くして平面の比率を上げたりすることによりベーマイト粒子の平面率を所望のものに調整した。具体的には、実施例12-2では、フィラーとして、平面率45%のベーマイト粒子を用いた。実施例12-3では、フィラーとして、平面率50%のベーマイト粒子を用いた。実施例12-4では、フィラーとして、平面率60%のベーマイト粒子を用いた。実施例12-5では、フィラーとして、平面率80%のベーマイト粒子を用いた。実施例12-6では、フィラーとして、平面率90%のベーマイト粒子を用いた。実施例12-7では、フィラーとして、平面率100%のベーマイト粒子を用いた。以上のこと以外は、実施例12-1と同様にして、ラミネートフィルム型電池を作製した。
実施例11-2と同様にして、ラミネートフィルム型電池を作製した。
フィラーとして、平面率の異なるタルク粒子を用いた。ハンマーミルおよびロールミルを用いて行う粉砕工程において、ハンマーミルの時間比率を多くして劈開面の比率を上げたり、ロールミルの時間比率を多くして劈開面の比率を下げたりして、タルク粒子の平面率を所望のものに調整した。具体的には、実施例12-9では、フィラーとして、平面率45%のタルク粒子を用いた。実施例12-10では、フィラーとして、平面率50%のタルク粒子を用いた。実施例12-11では、フィラーとして、平面率60%のタルク粒子を用いた。実施例12-12では、フィラーとして、平面率80%のタルク粒子を用いた。実施例12-13では、フィラーとして、平面率90%のタルク粒子を用いた。実施例12-14では、フィラーとして、平面率100%のタルク粒子を用いた。以上のこと以外は、実施例12-8と同様にして、ラミネートフィルム型電池を作製した。
フィラーとして、ベーマイト粒子に代えて、平面率の異なる酸化アルミニウム粒子を用いた。具体的には、比較例12-1では、フィラーとして、平面率40%の酸化アルミニウム粒子を用いた。比較例12-2では、フィラーとして、平面率30%の酸化アルミニウム粒子を用いた。比較例12-3では、フィラーとして、平面率20%の酸化アルミニウム粒子を用いた。比較例12-4では、フィラーとして、平面率10%の酸化アルミニウム粒子を用いた。比較例12-5では、フィラーとして、球状の酸化アルミニウム(平面率0%)粒子を用いた。以上のこと以外は、実施例12-1と同様にして、ラミネートフィルム型電池を作製した。
作製した各実施例および各比較例のラミネートフィルム型電池について、実施例11-1と同様にして、レーザー計測の合否判定を行った。
実施例13-1~実施例13-8では、フィラー(ベーマイト粒子)とバインダー高分子化合物(PVdF)との質量比を変えたこと以外は、実施例11-1と同様にして、ラミネートフィルム型電池を作製した。具体的には、実施例13-1では質量比(粒子/PVdF)を15/85にした。実施例13-2では質量比(粒子/PVdF)を20/80にした。実施例13-3では質量比(粒子/PVdF)を30/70にした。実施例13-4では、実施例11-1と同様、質量比(粒子/PVdF)を50/50にした。実施例13-5では質量比(粒子/PVdF)を70/30にした。実施例13-6では質量比(粒子/PVdF)を80/20にした。実施例13-7では、質量比(粒子/PVdF)を85/15にした。実施例13-8では質量比(粒子/PVdF)を90/10にした。
実施例13-9~実施例13-15では、フィラー(タルク粒子)とバインダー高分子化合物(PVdF)との質量比を変えたこと以外は、実施例11-2と同様にして、ラミネートフィルム型電池を作製した。具体的には、実施例13-9では質量比(粒子/PVdF)を20/80にした。実施例13-10では質量比(粒子/PVdF)を40/60にした。実施例13-11では、実施例11-2と同様、質量比(粒子/PVdF)を50/50にした。実施例13-12では質量比(粒子/PVdF)を60/40にした。実施例13-13では質量比(粒子/PVdF)を80/20にした。実施例13-14では質量比(粒子/PVdF)を85/15にした。実施例13-15では質量比(粒子/PVdF)を90/10にした。
作製した各実施例および各比較例のラミネートフィルム型電池について、実施例11-1と同様にして、レーザー計測の合否判定を行った。
実施例14-1では、実施例11-1と同様にしてラミネートフィルム型電池を作製した。
実施例14-2~実施例14-3では、バインダー高分子化合物(樹脂)の種類を変えた。実施例14-2では、バインダー高分子化合物としてPAN(ポリアクリロニトリル)を用いた。実施例14-3では、バインダー高分子化合物として、PEG(ポリエチレングリコール)を用いた。以上のこと以外は、実施例14-1と同様にして、ラミネートフィルム型電池を作製した。
実施例14-4では、実施例11-2と同様にしてラミネートフィルム型電池を作製した。
実施例14-5~実施例14-6では、ゲル電解質層を構成するバインダー高分子化合物の種類を変えた。実施例14-5では、バインダー高分子化合物としてPAN(ポリアクリロニトリル)を用いた。実施例14-6では、バインダー高分子化合物として、PEG(ポリエチレングリコール)を用いた。以上のこと以外は、実施例14-4と同様にして、ラミネートフィルム型電池を作製した。
作製した各実施例および各比較例のラミネートフィルム型電池について、実施例11-1と同様にして、レーザー計測の合否判定を行った。
実施例15-1~実施例15-2では、実施例11-1~実施例11-2のそれぞれと同様であるラミネートフィルム型電池を用いた、図10、図11Aおよび図11Bに示す簡易型の電池パック(ソフトパック)を作製した。
実施例15-3~実施例15-4では、塗料をセパレータの正極側の片面のみに塗布したこと以外は、実施例11-1~実施例11-2のそれぞれと同様であるラミネートフィルム型電池を用いた、図10、図11Aおよび図11Bに示す簡易型の電池パック(ソフトパック)を作製した。
実施例15-5~実施例15-6では、塗料をセパレータの負極側の片面のみに塗布したこと以外は、実施例11-1~実施例11-2のそれぞれと同様であるラミネートフィルム型電池を用いた、図10、図11Aおよび図11Bに示す簡易型の電池パック(ソフトパック)を作製した。
塗料にフィラーを含有しないこと以外は、実施例15-1と同様にして、図10、図11Aおよび図11Bに示す簡易型の電池パック(ソフトパック)を作製した。
塗料にフィラーを含有しないこと以外は、実施例15-5と同様にして、図10、図11Aおよび図11Bに示す簡易型の電池パック(ソフトパック)を作製した。
作製した各実施例および各比較例のソフトパックについて、実施例5-1と同様にして、100kg加圧試験、60℃1ヶ月保存試験を行った。
[正極の作製、粒子含有樹脂層の形成]
実施例11-1と同様にして、正極を作製した。また、正極の両面に以下のようにして粒子含有樹脂層を形成した。
まず、フィラーである平均粒径0.8μmのベーマイトの粒子(屈折率1.7)とバインダー高分子化合物であるポリフッ化ビニリデン(PVdF)とを、N-メチル-2-ピロリドン(NMP)に分散させて、塗料(粒子含有樹脂溶液)を調製した。この際、ベーマイトの含有量は塗料の全体量に対して5質量%とし、ベーマイトとPVdFとの質量比(ベーマイト/PVdF)は50/50とし、固形分(ベーマイトおよびPVdF)が塗料の全体量に対して20質量%となるように、各材料の量を調整した。
実施例11-1と同様にして、負極を作製した。また、正極と同様の手法で、負極の両面に粒子含有樹脂層を形成した。
基材として厚さ9μmポリエチレン(PE)製微多孔性フィルムを用いた。
粒子含有樹脂層が両面に形成された正極、粒子含有樹脂層が両面に形成された負極およびセパレータを、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。
実施例16-2~実施例16-55および比較例16-1~比較例16-8では、下掲の表16に示すように、用いるフィラーを変えたこと以外は、実施例16-1と同様にして、ラミネートフィルム型電池を作製した。
作製した各電池を解体し電解液を含む粒子含有樹脂層の厚みを、接触式厚み計によって確認した。厚みの算定は、電極の厚みと、電解液を含む粒子含有樹脂層を備えた電極の厚みとの差からおこなった。塗料膜の厚さの測定値と、電解液を含む粒子含有樹脂層の厚さの測定値との差が、塗料膜の厚さの測定値に対する百分率で±10%以内に入っている場合は合格、それ以外の場合は不合格とした。
実施例16-1と同様にして、ラミネートフィルム型電池を作製した。
フィラーとして、平面率の異なるベーマイト粒子を用いた。ベーマイト粒子の水熱合成時の成長速度を速くして球面の比率を多くしたり、成長速度を遅くして平面の比率を上げたりすることによりベーマイト粒子の平面率を所望のものに調整した。具体的には、実施例17-2では、フィラーとして、平面率45%のベーマイト粒子を用いた。実施例17-3では、フィラーとして、平面率50%のベーマイト粒子を用いた。実施例17-4では、フィラーとして、平面率60%のベーマイト粒子を用いた。実施例17-5では、フィラーとして、平面率80%のベーマイト粒子を用いた。実施例17-6では、フィラーとして、平面率90%のベーマイト粒子を用いた。実施例17-7では、フィラーとして、平面率100%のベーマイト粒子を用いた。以上のこと以外は、実施例17-1と同様にして、ラミネートフィルム型電池を作製した。
実施例16-2と同様にして、ラミネートフィルム型電池を作製した。
フィラーとして、平面率の異なるタルク粒子を用いた。ハンマーミルおよびロールミルを用いて行う粉砕工程において、ハンマーミルの時間比率を多くして劈開面の比率を上げたり、ロールミルの時間比率を多くして劈開面の比率を下げたりして、タルク粒子の平面率を所望のものに調整した。具体的には、実施例17-9では、フィラーとして、平面率45%のタルク粒子を用いた。実施例17-10では、フィラーとして、平面率50%のタルク粒子を用いた。実施例17-11では、フィラーとして、平面率60%のタルク粒子を用いた。実施例17-12では、フィラーとして、平面率80%のタルク粒子を用いた。実施例17-13では、フィラーとして、平面率90%のタルク粒子を用いた。実施例17-14では、フィラーとして、平面率100%のタルク粒子を用いた。以上のこと以外は、実施例17-8と同様にして、ラミネートフィルム型電池を作製した。
フィラーとして、ベーマイト粒子に代えて、平面率の異なる酸化アルミニウム粒子を用いた。具体的には、比較例17-1では、フィラーとして、平面率40%の酸化アルミニウム粒子を用いた。比較例17-2では、フィラーとして、平面率30%の酸化アルミニウム粒子を用いた。比較例17-3では、フィラーとして、平面率20%の酸化アルミニウム粒子を用いた。比較例17-4では、フィラーとして、平面率10%の酸化アルミニウム粒子を用いた。比較例17-5では、フィラーとして、球状の酸化アルミニウム(平面率0%)粒子を用いた。以上のこと以外は、実施例17-1と同様にして、ラミネートフィルム型電池を作製した。
作製した各実施例および各比較例のラミネートフィルム型電池について、実施例16-1と同様にして、レーザー計測の合否判定を行った。
実施例18-1~実施例18-8では、フィラー(ベーマイト粒子)とバインダー高分子化合物(PVdF)との質量比を変えたこと以外は、実施例16-1と同様にして、ラミネートフィルム型電池を作製した。具体的には、実施例18-1では質量比(粒子/PVdF)を15/85にした。実施例18-2では質量比(粒子/PVdF)を20/80にした。実施例18-3では質量比(粒子/PVdF)を30/70にした。実施例18-4では、実施例16-1と同様、質量比(粒子/PVdF)を50/50にした。実施例18-5では質量比(粒子/PVdF)を70/30にした。実施例18-6では質量比(粒子/PVdF)を80/20にした。実施例18-7では、質量比(粒子/PVdF)を85/15にした。実施例18-8では質量比(粒子/PVdF)を90/10にした。
実施例18-9~実施例18-15では、フィラー(タルク粒子)とバインダー高分子化合物(PVdF)との質量比を変えたこと以外は、実施例16-2と同様にして、ラミネートフィルム型電池を作製した。具体的には、実施例18-9では質量比(粒子/PVdF)を20/80にした。実施例18-10では質量比(粒子/PVdF)を40/60にした。実施例18-11では、実施例16-2と同様、質量比(粒子/PVdF)を50/50にした。実施例18-12では質量比(粒子/PVdF)を60/40にした。実施例18-13では質量比(粒子/PVdF)を80/20にした。実施例18-14では質量比(粒子/PVdF)を85/15にした。実施例18-15では質量比(粒子/PVdF)を90/10にした。
作製した各実施例および各比較例のラミネートフィルム型電池について、実施例16-1と同様にして、レーザー計測の合否判定を行った。
実施例19-1では、実施例16-1と同様にしてラミネートフィルム型電池を作製した。
実施例19-2~実施例19-3では、ゲル電解質層を構成するバインダー高分子化合物(樹脂)の種類を変えた。実施例19-2では、バインダー高分子化合物としてPAN(ポリアクリロニトリル)を用いた。実施例19-3では、バインダー高分子化合物として、PEG(ポリエチレングリコール)を用いた。以上のこと以外は、実施例19-1と同様にして、ラミネートフィルム型電池を作製した。
実施例19-4では、実施例16-2と同様にしてラミネートフィルム型電池を作製した。
実施例19-5~実施例19-6では、ゲル電解質層を構成するバインダー高分子化合物の種類を変えた。実施例19-5では、バインダー高分子化合物としてPAN(ポリアクリロニトリル)を用いた。実施例19-6では、バインダー高分子化合物として、PEG(ポリエチレングリコール)を用いた。以上のこと以外は、実施例19-4と同様にして、ラミネートフィルム型電池を作製した。
作製した各実施例および各比較例のラミネートフィルム型電池について、実施例16-1と同様にして、レーザー計測の合否判定を行った。
実施例20-1~実施例20-2では、実施例16-1~実施例16-2のそれぞれと同様であるラミネートフィルム型電池を用いた、図10、図11Aおよび図11Bに示す簡易型の電池パック(ソフトパック)を作製した。
実施例20-3~実施例20-4では、塗料を正極の両面のみに塗布したこと以外は、実施例16-1~実施例16-2のそれぞれと同様であるラミネートフィルム型電池を用いた、図10、図11Aおよび図11Bに示す簡易型の電池パック(ソフトパック)を作製した。
実施例20-5~実施例20-6では、塗料を負極の両面のみに塗布したこと以外は、実施例16-1~実施例16-2のそれぞれと同様であるラミネートフィルム型電池を用いた、図10、図11Aおよび図11Bに示す簡易型の電池パック(ソフトパック)を作製した。
塗料にフィラーを含有しないこと以外は、実施例20-1と同様にして、図10、図11Aおよび図11Bに示す簡易型の電池パック(ソフトパック)を作製した。
塗料にフィラーを含有しないこと以外は、実施例20-5と同様にして、図10、図11Aおよび図11Bに示す簡易型の電池パック(ソフトパック)を作製した。
作製した各実施例および各比較例のソフトパックについて、実施例5-1と同様にして、100kg加圧試験、60℃1ヶ月保存試験を行った。
以上、本技術を各実施の形態および実施例によって説明したが、本技術はこれらに限定されるものではなく、本技術の要旨の範囲内で種々の変形が可能である。
[1]
正極と、
負極と、
セパレータと、
電解液と、
粒子および樹脂を含む粒子含有樹脂層と
を備え、
前記粒子の形状は平面を含み、且つ、前記粒子の平面率は40%超100%以下であり、且つ、前記粒子の屈折率は1.3以上2.4未満である電池。
[2]
前記平面は、結晶面、破砕面、および劈開面うちの少なくとも何れかを含む[1]に記載の電池。
[3]
前記粒子は、無機粒子および有機粒子の少なくとも何れかである[1]~[2]の何れかに記載の電池。
[4]
前記無機粒子は、酸化ケイ素、酸化亜鉛、酸化スズ、酸化マグネシウム、酸化アンチモン、酸化アルミニウム、硫酸マグネシウム、硫酸カルシウム、硫酸バリウム、硫酸ストロンチウム、炭酸マグネシウム、炭酸カルシウム、炭酸バリウム、炭酸リチウム、水酸化マグネシウム、水酸化アルミニウム、水酸化亜鉛、ベーマイト、ホワイトカーボン、酸化ジルコニウム水和物、酸化マグネシウム水和物、水酸化マグネシウム8水和物、炭化ホウ素、窒化ケイ素、窒化ホウ素、窒化アルミニウム、窒化チタン、フッ化リチウム、フッ化アルミニウム、フッ化カルシウム、フッ化バリウム、フッ化マグネシウム、リン酸トリリチウム、リン酸マグネシウム、リン酸水素マグネシウム、ポリリン酸アンモニウム、ケイ酸塩鉱物、炭酸塩鉱物、酸化鉱物からなる群から選ばれた少なくとも何れかの粒子であり、
前記有機粒子は、メラミン、メラミンシアヌレート、ポリリン酸メラミン、架橋ポリメタクリル酸メチル、ポリエチレン、ポリプロピレン、ポリスチレン、ポリテトラフルオロエチレン、ポリビニリデンフルオリド、ポリアミド、ポリイミド、メラミン樹脂、フェノール樹脂、エポキシ樹脂からなる群から選ばれた少なくとも何れかの粒子である[3]に記載の電池。
[5]
前記ケイ酸塩鉱物は、タルク、ケイ酸カルシウム、ケイ酸亜鉛、ケイ酸ジルコニウム、ケイ酸アルミニウム、ケイ酸マグネシウム、カオリナイト、セピオライト、イモゴライト、セリサイト、パイロフィライト、雲母、ゼオライト、ムライト、サポナイト、アタパルジャイト、モンモリロナイトからなる群から選ばれた少なくとも1種であり、
前記炭酸塩鉱物は、ハイドロタルサイト、ドロマイトからなる群から選ばれた少なくとも1種であり、
前記酸化鉱物は、スピネルである[4]に記載の電池。
[6]
前記樹脂は、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、フッ化ビニリデン-テトラフルオロエチレン共重合体、エチレン-テトラフルオロエチレン共重合体、フッ化ビニリデン-テトラフルオロエチレン共重合体、エチレン-テトラフルオロエチレン共重合体、スチレン-ブタジエン共重合体およびその水素化物、アクリロニトリル-ブタジエン共重合体およびその水素化物、アクリロニトリル-ブタジエン-スチレン共重合体およびその水素化物、メタクリル酸エステル-アクリル酸エステル共重合体、スチレン-アクリル酸エステル共重合体、アクリロニトリル-アクリル酸エステル共重合体、エチレンプロピレンラバー、ポリビニルアルコール、ポリ酢酸ビニル、エチルセルロース、セルロース誘導体、ポリフェニレンエーテル、ポリスルホン、ポリエーテルスルホン、ポリフェニレンスルフィド、ポリエーテルイミド、ポリイミド、ポリアミド、ポリアミドイミド、ポリアクリロニトリル、ポリビニルアルコール、ポリエーテル、アクリル酸樹脂、ポリエステル、ポリエチレングリコールからなる群から選ばれた少なくとも何れかである[1]~[5]の何れかに記載の電池。
[7]
前記粒子と前記樹脂との質量比(粒子/樹脂)は、15/85以上90/10以下である[1]~[6]の何れかに記載の電池。
[8]
前記粒子含有樹脂層は、前記電解液を前記樹脂により保持する[1]~[7]の何れかに記載の電池。
[9]
前記粒子含有樹脂層は、前記電解液を前記樹脂および前記粒子の少なくとも何れかにより形成される空隙に保持する[1]~[7]の何れかに記載の電池。
[10]
前記粒子含有樹脂層は、前記正極の一方の主面および他方の主面、前記負極の一方の主面および他方の主面、並びに、前記セパレータの一方の主面および他方の主面の中から選ばれた少なくとも一つの主面上に形成されたものである[1]~[9]の何れかに記載の電池。
[11]
セパレータ基材と、
該セパレータ基材の少なくとも一方の主面に設けられ、且つ、粒子および樹脂を含む粒子含有樹脂層と
を備え、
前記粒子の形状は平面を含み、且つ、前記粒子の平面率は40%超100%以下であり、且つ、前記粒子の屈折率は1.3以上2.4未満であるセパレータ。
[12]
電極と、
該電極の少なくとも一方の主面に設けられ、且つ、粒子および樹脂を含む粒子含有樹脂層と
を備え、
前記粒子の形状は平面を含み、且つ、前記粒子の平面率は40%超100%以下であり、且つ、前記粒子の屈折率は1.3以上2.4未満である粒子含有樹脂層付きの電極。
[13]
粒子と、
樹脂と、
溶媒と
を含み、
前記粒子の形状は平面を含み、且つ、前記粒子の平面率は40%超100%以下であり、且つ、前記粒子の屈折率は1.3以上2.4未満である塗料。
[14]
[1]~[10]の何れかに記載の電池と、
前記電池を制御する制御部と、
前記電池を内包する外装と
を有する電池パック。
[15]
[1]~[10]の何れかに記載の電池を有し、前記電池から電力の供給を受ける電子機器。
[16]
[1]~[10]の何れかに記載の電池と、
前記電池から電力の供給を受けて車両の駆動力に変換する変換装置と、
前記電池に関する情報に基づいて車両制御に関する情報処理を行う制御装置と
を有する電動車両。
[17]
[1]~[10]の何れかに記載の電池を有し、前記電池に接続される電子機器に電力を供給する蓄電装置。
[18]
他の機器とネットワークを介して信号を送受信する電力情報制御装置を備え、
前記電力情報制御装置が受信した情報に基づき、前記電池の充放電制御を行う[17]に記載の蓄電装置。
[19]
[1]~[10]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前記電池に電力が供給される電力システム。
Claims (19)
- 正極と、
負極と、
セパレータと、
電解液と、
粒子および樹脂を含む粒子含有樹脂層と
を備え、
前記粒子の形状は平面を含み、且つ、前記粒子の平面率は40%超100%以下であり、且つ、前記粒子の屈折率は1.3以上2.4未満である電池。 - 前記平面は、結晶面、破砕面、および劈開面うちの少なくとも何れかを含む請求項1に記載の電池。
- 前記粒子は、無機粒子および有機粒子の少なくとも何れかである請求項1に記載の電池。
- 前記無機粒子は、酸化ケイ素、酸化亜鉛、酸化スズ、酸化マグネシウム、酸化アンチモン、酸化アルミニウム、硫酸マグネシウム、硫酸カルシウム、硫酸バリウム、硫酸ストロンチウム、炭酸マグネシウム、炭酸カルシウム、炭酸バリウム、炭酸リチウム、水酸化マグネシウム、水酸化アルミニウム、水酸化亜鉛、ベーマイト、ホワイトカーボン、酸化ジルコニウム水和物、酸化マグネシウム水和物、水酸化マグネシウム8水和物、炭化ホウ素、窒化ケイ素、窒化ホウ素、窒化アルミニウム、窒化チタン、フッ化リチウム、フッ化アルミニウム、フッ化カルシウム、フッ化バリウム、フッ化マグネシウム、リン酸トリリチウム、リン酸マグネシウム、リン酸水素マグネシウム、ポリリン酸アンモニウム、ケイ酸塩鉱物、炭酸塩鉱物、酸化鉱物からなる群から選ばれた少なくとも何れかの粒子であり、
前記有機粒子は、メラミン、メラミンシアヌレート、ポリリン酸メラミン、架橋ポリメタクリル酸メチル、ポリエチレン、ポリプロピレン、ポリスチレン、ポリテトラフルオロエチレン、ポリビニリデンフルオリド、ポリアミド、ポリイミド、メラミン樹脂、フェノール樹脂、エポキシ樹脂からなる群から選ばれた少なくとも何れかの粒子である請求項3に記載の電池。 - 前記ケイ酸塩鉱物は、タルク、ケイ酸カルシウム、ケイ酸亜鉛、ケイ酸ジルコニウム、ケイ酸アルミニウム、ケイ酸マグネシウム、カオリナイト、セピオライト、イモゴライト、セリサイト、パイロフィライト、雲母、ゼオライト、ムライト、サポナイト、アタパルジャイト、モンモリロナイトからなる群から選ばれた少なくとも1種であり、
前記炭酸塩鉱物は、ハイドロタルサイト、ドロマイトからなる群から選ばれた少なくとも1種であり、
前記酸化鉱物は、スピネルである請求項4に記載の電池。 - 前記樹脂は、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、フッ化ビニリデン-テトラフルオロエチレン共重合体、エチレン-テトラフルオロエチレン共重合体、フッ化ビニリデン-テトラフルオロエチレン共重合体、エチレン-テトラフルオロエチレン共重合体、スチレン-ブタジエン共重合体およびその水素化物、アクリロニトリル-ブタジエン共重合体およびその水素化物、アクリロニトリル-ブタジエン-スチレン共重合体およびその水素化物、メタクリル酸エステル-アクリル酸エステル共重合体、スチレン-アクリル酸エステル共重合体、アクリロニトリル-アクリル酸エステル共重合体、エチレンプロピレンラバー、ポリビニルアルコール、ポリ酢酸ビニル、エチルセルロース、セルロース誘導体、ポリフェニレンエーテル、ポリスルホン、ポリエーテルスルホン、ポリフェニレンスルフィド、ポリエーテルイミド、ポリイミド、ポリアミド、ポリアミドイミド、ポリアクリロニトリル、ポリビニルアルコール、ポリエーテル、アクリル酸樹脂、ポリエステル、ポリエチレングリコールからなる群から選ばれた少なくとも何れかである請求項1に記載の電池。
- 前記粒子と前記樹脂との質量比(粒子/樹脂)は、15/85以上90/10以下である請求項1に記載の電池。
- 前記粒子含有樹脂層は、前記電解液を前記樹脂により保持する請求項1に記載の電池。
- 前記粒子含有樹脂層は、前記電解液を前記樹脂および前記粒子の少なくとも何れかにより形成される空隙に保持する請求項1に記載の電池。
- 前記粒子含有樹脂層は、前記正極の一方の主面および他方の主面、前記負極の一方の主面および他方の主面、並びに、前記セパレータの一方の主面および他方の主面の中から選ばれた少なくとも一つの主面上に形成されたものである請求項1に記載の電池。
- セパレータ基材と、
該セパレータ基材の少なくとも一方の主面に設けられ、且つ、粒子および樹脂を含む粒子含有樹脂層と
を備え、
前記粒子の形状は平面を含み、且つ、前記粒子の平面率は40%超100%以下であり、且つ、前記粒子の屈折率は1.3以上2.4未満であるセパレータ。 - 電極と、
該電極の少なくとも一方の主面に設けられ、且つ、粒子および樹脂を含む粒子含有樹脂層と
を備え、
前記粒子の形状は平面を含み、且つ、前記粒子の平面率は40%超100%以下であり、且つ、前記粒子の屈折率は1.3以上2.4未満である粒子含有樹脂層付きの電極。 - 粒子と、
樹脂と、
溶媒と
を含み、
前記粒子の形状は平面を含み、且つ、前記粒子の平面率は40%超100%以下であり、且つ、前記粒子の屈折率は1.3以上2.4未満である塗料。 - 請求項1に記載の電池と、
前記電池を制御する制御部と、
前記電池を内包する外装と
を有する電池パック。 - 請求項1に記載の電池を有し、前記電池から電力の供給を受ける電子機器。
- 請求項1に記載の電池と、
前記電池から電力の供給を受けて車両の駆動力に変換する変換装置と、
前記電池に関する情報に基づいて車両制御に関する情報処理を行う制御装置と
を有する電動車両。 - 請求項1に記載の電池を有し、前記電池に接続される電子機器に電力を供給する蓄電装置。
- 他の機器とネットワークを介して信号を送受信する電力情報制御装置を備え、
前記電力情報制御装置が受信した情報に基づき、前記電池の充放電制御を行う請求項17に記載の蓄電装置。 - 請求項1に記載の電池から電力の供給を受け、または、発電装置もしくは電力網から前記電池に電力が供給される電力システム。
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JP2015546278A JP6372491B2 (ja) | 2013-11-05 | 2014-08-28 | 電池、セパレータ、電極、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 |
CN201480059277.XA CN105684207B (zh) | 2013-11-05 | 2014-08-28 | 电池、隔板、电极、涂料、电池组、电子设备、电动车辆、蓄电装置以及电力系统 |
US15/030,839 US10665841B2 (en) | 2013-11-05 | 2014-08-28 | Battery, separator, electrode, coating material, battery pack, electronic apparatus, electrically driven vehicle, electrical storage device, and electric power system |
KR1020167010781A KR102185159B1 (ko) | 2013-11-05 | 2014-08-28 | 전지, 세퍼레이터, 전극, 도료, 전지 팩, 전자 기기, 전동 차량, 축전 장치 및 전력 시스템 |
EP14860019.0A EP3067981B1 (en) | 2013-11-05 | 2014-08-28 | Battery, separator, electrode, paint, battery pack, electronic apparatus, electric vehicle, electricity storage device, and power system |
US16/861,528 US11532853B2 (en) | 2013-11-05 | 2020-04-29 | Transparent particle-containing resin layer, separator, electrode, and battery including the same, and coating material for making the same |
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US16/861,528 Continuation US11532853B2 (en) | 2013-11-05 | 2020-04-29 | Transparent particle-containing resin layer, separator, electrode, and battery including the same, and coating material for making the same |
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JPWO2015068325A1 (ja) | 2017-03-09 |
EP3067981B1 (en) | 2021-07-21 |
US10665841B2 (en) | 2020-05-26 |
KR20160081903A (ko) | 2016-07-08 |
CN105684207B (zh) | 2020-05-15 |
EP3067981A1 (en) | 2016-09-14 |
US20160254511A1 (en) | 2016-09-01 |
EP3067981A4 (en) | 2017-07-05 |
US20200259147A1 (en) | 2020-08-13 |
US11532853B2 (en) | 2022-12-20 |
CN105684207A (zh) | 2016-06-15 |
JP6372491B2 (ja) | 2018-08-15 |
KR102185159B1 (ko) | 2020-12-01 |
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