WO2015097953A1

WO2015097953A1 - Battery, separator, electrode, paint, battery pack, electronic device, electric vehicle, electricity-storage device, and power system

Info

Publication number: WO2015097953A1
Application number: PCT/JP2014/005257
Authority: WO
Inventors: 八田　一人; 慶一鏡; 暢明下坂; 古賀　景三
Original assignee: ソニー株式会社
Priority date: 2013-12-27
Filing date: 2014-10-16
Publication date: 2015-07-02

Abstract

This battery is provided with a positive electrode, a negative electrode, a liquid electrolyte, and a particle-containing resin layer that contains particles and a resin. The size (D50) of said particles is either between 50 and 450 nm, inclusive, or between 750 and 10,000 nm, inclusive. The index of refraction of the particles is at least 1.3 but less than 2.4, and the mass ratio (particles/resin) between the particles and the resin is between 15/85 and 90/10, inclusive.

Description

Batteries, separators, electrodes, paints, battery packs, electronic devices, electric vehicles, power storage devices, and power systems

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. As 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. Among them, a gel electrolyte battery in which the electrolytic solution is held in a polymer compound to form a so-called gel is widely used.

As a technique related to this technique, Patent Document 1 describes a separator provided with a coating film containing a heat-resistant nitrogen-containing aromatic polymer and ceramic powder. Patent Document 2 describes a porous film containing ceramic particles and a binder bonded to the electrode surface.

JP 2010-198757 A Japanese Patent No. 4781263

In a battery provided with a resin layer containing particles, it was difficult to control the thickness of the resin layer containing particles with high accuracy due to the occurrence of white turbidity in the coating material for forming the battery.

Accordingly, 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.

In order to solve the above problems, the present technology includes a positive electrode, a negative electrode, a separator, an electrolytic solution, and a particle-containing resin layer containing particles and a resin, and the particle diameter D50 of the particles is 50 nm or more and 450 nm or less. Alternatively, the refractive index of the particles is from 1.3 to less than 2.4, and the mass ratio of the particles to the resin (particle / resin) is from 15/85 to 90/10. There is a battery.

The present technology includes a separator base and a particle-containing resin layer provided on at least one main surface of the separator base and containing particles and a resin, and the particle diameter D50 of the particles is 50 nm or more and 450 nm or less, or , 750 nm to 10,000 nm, the refractive index of the particles is 1.3 to less than 2.4, and the mass ratio of the particles to the resin (particle / resin) is 15/85 to 90/10 It is.

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, and the particle diameter D50 of the particles is 50 nm to 450 nm, or 750 nm to 10000 nm. With a particle-containing resin layer, the refractive index of the particle is 1.3 or more and less than 2.4, and the mass ratio of the particle to the resin (particle / resin) is 15/85 or more and 90/10 or less Electrode.

Particles, resin, and solvent, the particle diameter D50 of the particles is 50 nm or more and 450 nm or less, or 750 nm or more and 10,000 nm or less, and the refractive index of the particles is 1.3 or more and less than 2.4; The resin is a paint having a mass ratio (particle / resin) of 15/85 to 90/10.

Moreover, the battery pack, electronic device, electric vehicle, power storage device, and power system of the present technology include the above-described battery.

According to the present technology, 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. 2 is a schematic cross-sectional view of an electrode with a particle-containing resin layer according to an embodiment of the present technology. FIG. 3 is an exploded perspective view showing the configuration of a laminated film type nonaqueous electrolyte battery according to an embodiment of the present technology. 4 is a cross-sectional view showing a cross-sectional configuration along the line II of the spirally wound electrode body shown in FIG. 5A to 5C are exploded perspective views showing the configuration of a laminated film type nonaqueous electrolyte battery using a laminated electrode body. FIG. 6 is a cross-sectional view showing a configuration of a cylindrical nonaqueous electrolyte battery according to an embodiment of the present technology. FIG. 7 is an enlarged cross-sectional view showing a part of a wound electrode body housed in a cylindrical nonaqueous electrolyte battery. FIG. 8 is an enlarged cross-sectional view showing a part of a wound electrode body housed in a cylindrical nonaqueous electrolyte battery. FIG. 9 is a perspective view showing a configuration of a prismatic nonaqueous electrolyte battery according to an embodiment of the present technology. 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. FIG. 15 is a schematic diagram for explaining a battery bending test. FIG. 16 is a schematic cross-sectional view for explaining the battery bending test.

(Technical background)
First, in order to facilitate understanding of the present technology, the technical background of the present technology will be described. Along with the recent demand for higher capacity, the outer packaging of laminated film type polymer batteries has also become simpler, and if there is a large deformation due to strong pressure due to misuse, a short circuit will occur inside the battery. It becomes easy and may not function as a battery. On the other hand, it has been proposed to improve the strength of the gel electrolyte by mixing particles such as alumina in the gel electrolyte.

In a battery such as a lithium ion secondary battery, it is required to further increase the volume energy density. As a measure for improving the volumetric energy density of a battery, a technique for improving the energy density by thinning the separator and allocating the separator to the active material has been studied. There is no problem when the exterior is a metal, but as a countermeasure when metal foreign matter is mixed inside, a technology has been devised to supplement the short-circuit resistance by thinly coating the inorganic filler as the separator becomes thinner ( (Patent Document 1: Japanese Patent Application Laid-Open No. 2010-198757).

This coat layer dissolves the filler and the polymer that serves as the binder in a solvent, forms a coating, applies it, and then removes the solvent through a drying process. It has been shown that such a coating film is effective even if provided on the electrode leaf surface regardless of the separator surface (see Patent Document 2: Japanese Patent No. 4781263).

Controlling the thickness is important when applying a matrix polymer solution containing a gel electrolyte or a filler for forming a coating film or a binder polymer compound solution. The finished coating film is typically provided with, for example, about 1 μm to 5 μm per side from the viewpoint of improving the volumetric energy density, and therefore high-precision coating is required.

In the conventional coating method, after applying the conditions once, the coating was applied to the entire length of the separator or electrode reel, and the diluted solvent was dried by passing through a drying furnace to wind up the finished product reel. In later inspections, due to thickness fluctuations during application, if there are thin or thick parts outside the standard value range, the specified function may not be obtained, or the element dimensions may exceed the standard, etc. Therefore, if there is an abnormality, the entire reel becomes a defective product.

As a countermeasure, it is effective to apply correction in real time while in-line inspection is performed in an undried state after application. However, a non-contact measurement method is indispensable for measuring the paint thickness in-line. It is effective to measure using However, most paints containing particles such as inorganic particles are colored or cloudy, and the thickness cannot be measured in a freshly applied state.

Therefore, in the present technology, 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. In addition, the present technology can provide an electrode or separator having a particle-containing resin layer containing particles having a predetermined strength and thickness with no variation in thickness, and can further provide a high short-circuit resistance and volume energy using them. A battery having a high density can be provided.

Hereinafter, embodiments of the present technology will be described with reference to the drawings. The description will be given in the following order.
1. First embodiment (example of separator)
2. Second Embodiment (Example of electrode with particle-containing resin layer)
3. Third embodiment (example of laminated film type battery)
4). Fourth embodiment (example of laminated film type battery)
5. Fifth embodiment (example of cylindrical battery)
6). Sixth embodiment (example of cylindrical battery)
7). Seventh embodiment (an example of a prismatic battery)
8). Eighth embodiment (example of battery pack)
9. Ninth embodiment (example of battery pack)
10. Tenth embodiment (an example of a power storage system)
11. Other Embodiment (Modification)
The embodiments described below are suitable specific examples of the present technology, and the contents of the present technology are not limited to these embodiments. Moreover, the effect described in this specification is an illustration to the last, is not limited, and does not deny that the effect different from the illustrated effect exists.

1. First Embodiment (1-1) Configuration of Separator A separator according to a first embodiment of the present technology will be described. FIG. 1 is a schematic cross-sectional view illustrating a configuration example of a separator according to the first embodiment of the present technology. As shown in FIG. 1, 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.

[Separator substrate]
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.

For example, 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. In particular, 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. Moreover, it is good also as a porous film formed by melt-kneading the structure which laminated | stacked these 2 or more types of porous films, or 2 or more types of resin materials. 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.

[Particle-containing resin layer]
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. By providing the particle-containing resin layer 11b, the separator characteristics such as heat resistance and oxidation resistance can be improved.

Although details will be described later, 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.

In the present technology, from the viewpoint of ensuring the transparency of the particle-containing resin solution layer that is a precursor of the particle-containing resin layer 11b by reducing light scattering, the filler contained in the particle-containing resin layer 11b is within a predetermined range. The particles have a refractive index and a particle diameter within a predetermined range, and the mass ratio (particle / resin) of the particle-containing resin layer 11b to the resin is within the predetermined range.

The reason why the particle-containing resin layer 11b is configured as described above will be described. For example, white inorganic powders such as alumina particles are formed of colorless and transparent particles, but are white due to light scattering. As a result of intensive studies, the inventors of the present application have found that the scattering in the particle-containing resin solution layer is substantially the same as the wavelength of visible light (blue, green, yellow, orange, red visible light) (over 450 nm and less than 750 nm). It was found to occur on the particle surface with a diameter. Then, it has been found that scattering can be avoided by selecting particles having a particle size smaller than the above wavelength range or by selecting particles having a particle size larger than the above wavelength range. Specifically, particles in the range of 50 nm to 450 nm, or particles of 750 nm to 10000 nm are effective. However, if the particle diameter is too small, the viscosity of the coating material is higher than that suitable for application, and thus it is preferably 50 nm or more. In addition, when the particle diameter is larger than 10,000 nm, there are cases where the particle becomes larger than the thickness to be applied, and the thickness of the battery does not work as designed.

The particle diameter of the particles contained in the particle-containing resin layer 11b can be defined by the value of the particle diameter D50. If the particle diameter D50 is in the above range (particles of 50 nm to 450 nm, or 750 nm to 10000 nm), for example, a part of the particle size distribution of D10, D90, etc. Even in the wavelength region (over 450 nm and less than 750 nm), the transparency as a whole is maintained. Even when the particles are aggregated to form secondary particles, the size of the surface irregularities of the secondary particles is equal to the wavelength of light scattering, so the particle diameter of one particle that is the basis of the irregularities is important. It is.

Furthermore, it was found that the transparency increases when the scattering due to the refraction of light coming from the difference between the refractive index of the resin solution and the refractive index of the particles (the solid is high and the liquid is low) is suppressed. Since the particle-containing resin solution layer contains a large amount of solvent components, the refractive index is often 1.3 or more and 1.8 or less, and a material whose refractive index is as close as possible to this range (refractive index is less than 2.4, preferably When 2.1 or less) is selected, the light travels straight when passing through the particles of the particle-containing resin solution layer.

Furthermore, the mass ratio (particle / resin) between the particles and the resin in the particle-containing resin layer 11b is within a predetermined range (15/85 or more and 90/10 or less). Since the refractive index of the resin solution and the refractive index of the particles are not the same, by setting the mass ratio range and lowering the ratio of the particles, the particle-containing resin can be prevented from becoming dark even if white turbidity occurs. The transparency of the solution can be ensured. In addition, from the viewpoint of ensuring the transparency of the particle-containing resin solution, the lower the ratio of the particles, the better. However, if the particle ratio is too low, the strength of the particle-containing resin layer 11b tends to decrease. The lower limit is set.

The particle-containing resin layer 11b may contain an electrolytic solution. For example, 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. In this case, the particle-containing resin layer 11b containing the electrolytic solution has a first content depending on at least one of the absorbability of the electrolyte contained in the particle-containing resin layer 11b, the solubility in the electrolytic solution, and the swelling property. A state or a second state is formed.

In addition, the absorbability of the electrolyte solution of the resin, the solubility in the electrolyte solution, and the swellability can be changed by adjusting the resin type, the degree of polymerization, the molecular weight, and the like. In this specification, 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. Is referred to as a matrix polymer compound.

(First state)
In the first state, 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. In this case, 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.

(Second state)
In the second state, the electrolyte solution is absorbed in the matrix polymer compound and is included in the particle-containing resin layer 11b. That is, the particle-containing resin layer 11b is impregnated with the electrolytic solution, and the matrix polymer compound swells to become a so-called gel. In this state, 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. In this case, 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)
As the resin, a matrix polymer compound and a binder polymer compound having a property compatible with a solvent can be used. Such 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. Polymer and its hydride, acrylonitrile-butadiene copolymer and its hydride, acrylonitrile-butadiene-styrene copolymer and its hydride, methacrylic acid ester-acrylic acid ester copolymer, styrene-acrylic acid ester copolymer , Rubbers such as acrylonitrile-acrylic acid ester copolymer, ethylene propylene rubber, polyvinyl alcohol, polyvinyl acetate, ethyl cellulose, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose Melting point and glass of cellulose derivatives, polyphenylene ether, polysulfone, polyethersulfone, polyphenylene sulfide, polyetherimide, polyimide, polyamide (especially aramid), polyamideimide, polyacrylonitrile, polyvinyl alcohol, polyether, acrylic resin or polyester Examples thereof include a resin having at least one transition temperature of 180 ° C. or higher and polyethylene glycol.

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.

(Filler)
As the filler contained in the particle-containing resin layer 11b, from the viewpoint of reducing light scattering and ensuring the transparency of the particle-containing resin solution layer, which is a precursor of the particle-containing resin layer 11b, a particle diameter within a predetermined range, In addition, particles having a refractive index within a predetermined range are used.

(Particle diameter)
As the particle diameter of the particles, the particle diameter D50 is set to 50 nm to 450 nm or 750 nm to 10000 nm. This is because the transparency of the particle-containing resin solution layer can be secured by using particles having a particle diameter in these ranges. Further, when the particle diameter D50 is less than 50 nm, the particle diameter is too small and becomes higher than the paint viscosity appropriate for application. This is because when the particle diameter D50 is larger than 10000 nm, there are cases where the particles are larger than the thickness to be applied, and the thickness of the battery cannot be as designed.

The lower limit of the particle diameter D50 in the range of 750 nm to 10,000 nm is preferably 800 nm or more, more preferably 2000 nm or more, from the viewpoint of further improving the transparency of the particle-containing resin solution layer. It is. The upper limit of the particle diameter D50 in the range of 50 nm to 450 nm is preferably 400 nm or less, more preferably 300 nm or less, from the viewpoint of further improving the transparency of the particle-containing resin solution layer.

Further, from the viewpoint of further improving the transparency of the particle-containing resin solution layer, the particle diameter of the particles is such that, in addition to the particle diameter D50, the particle diameter D40 and the particle diameter D60 are 50 nm or more and 450 nm or less, or 750 nm or more. More preferably, it is 10,000 nm or less. That is, the particle diameter D50 of the particles is preferably 50 nm to 450 nm, the particle diameter D40 is 50 nm to 450 nm, and the particle diameter D60 is preferably 50 nm to 450 nm. Alternatively, the particle diameter D50 of the particles is preferably 750 nm or more and 10,000 nm or less, the particle diameter D40 is 750 nm or more and 10,000 nm or less, and the particle diameter D60 is preferably 750 nm or more and 10,000 nm or less.

(Measurement of particle diameter)
The particle diameter D50 of the particles is, for example, a particle having a cumulative volume of 50% calculated from the particle side having a small particle diameter in the particle size distribution measured by the laser diffraction method after removing the resin component from the particle-containing resin layer. Is the diameter. Further, from the measured particle size distribution, a particle diameter D40 value of 40% cumulative volume and a particle diameter D60 of 60% cumulative volume can be obtained.

The shape of the particles is typically, for example, a spherical shape, a plate shape such as a scale shape or a flake shape, or a flat shape such as a needle shape (sometimes referred to as a flat shape), but is not limited thereto. Is not to be done. The shape of the particles is preferably a non-spherical shape other than a spherical shape from the viewpoint of reducing light scattering at the grain boundary and improving the transparency, and among the non-spherical shapes, a plate shape such as a scale shape or a flake shape, or a needle shape A flat shape such as is more preferable. Moreover, as a particle | grain, from the viewpoint which can improve transparency more, the particle | grains which consist of a single crystal or a few single crystals are preferable rather than the secondary particle | grains which are the polycrystal which tends to become spherical, and the aggregate of a primary particle. Note that the spherical shape includes not only a true spherical shape but also a shape in which the true spherical shape is slightly flat or distorted, a shape in which irregularities are formed on the true spherical surface, or a shape in which these shapes are combined. The flat shape refers to a particle having a ratio (long side / short side) of the long side of the particle to the short side of the particle of 2/1 or more. The value can be read from, for example, an enlarged photograph of particles taken with a scanning electron microscope (SEM). A plate shape such as a scale shape or a flake shape and a needle shape are a kind of flat shape, and a thin and flat shape is referred to as a plate shape, and an elongated shape like a needle is referred to as a needle shape. Scale-like and flake-like shapes are types of plates.

As a result of intensive studies, the inventors of the present application have selected at least one of the maximum value and the minimum value of the projected dimension from each direction of the particle when the flat shape particle is selected among these shapes. It has been found that transparency can be further maintained by entering 50 nm or more and 450 nm or less, or 750 nm or more and 10,000 nm or less. For example, in the case of a plate shape, the maximum length of the main surface is preferably 750 nm or more and 10,000 nm or less, and the thickness is preferably in the range of 50 nm or more and 450 nm or less. In the case of a needle shape, the length is 50 nm or more and 10,000 nm or less, and the thickness is in the range of 50 nm or more and 450 nm or less, there is little light scattering.

In addition, for example, having spherical particles with a diameter of 350 nm or more and 850 nm or less, which is the visible light wavelength range, is optimal for balancing the reduction in the viscosity of the paint and battery characteristics and the improvement in the strength of the particle-containing resin layer 11b. It is said that. Therefore, if the volume per particle is set to the same range as the spherical particles having the diameter in the above range, selecting a plate-like or needle-like particle in the projected dimension range can obtain transparency without breaking the balance. It is suitable for.

(Refractive index of particles)
From the viewpoint of ensuring the transparency of the particle-containing resin solution layer, 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). In order to make the refractive index of the solid particles close to the refractive index of the resin solution that is a liquid, among the solid particles, 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.

Specifically, for example, at least one of inorganic particles and organic particles can be used as the particles. Examples of 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. As the particles, particles having electrical insulation properties are typically used. However, 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.

Examples of the metal oxide 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.

As the sulfate compound, magnesium sulfate (MgSO ₄ ), calcium sulfate (CaSO ₄ ), barium sulfate (BaSO ₄ ), strontium sulfate (SrSO ₄ ) and the like can be suitably used. As the 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. Examples of metal hydroxides include magnesium hydroxide (Mg (OH) ₂ , brucite), aluminum hydroxide (Al (OH) ₃ (Buyerlite, Gibbsite)), zinc hydroxide (Zn (OH) ₂ ), etc. , Boehmite (Al ₂ O ₃ H ₂ O or AlOOH, diaspore), white carbon (SiO ₂ .nH ₂ O, silica hydrate), zirconium oxide hydrate (ZrO ₂ .nH ₂ O (n = 0.5) To 10)), oxide hydroxides such as magnesium oxide hydrate (MgO _a · mH ₂ O (a = 0.8 to 1.2, m = 0.5 to 10)), hydrated oxides, Hydroxic hydrates such as magnesium hydroxide octahydrate can be suitably used. As the metal carbide, boron carbide (B ₄ C) or the like can be suitably used. As the metal nitride, silicon nitride (Si ₃ N ₄ ), boron nitride (BN), aluminum nitride (AlN), titanium nitride (TiN), or the like can be suitably used.

As the metal fluoride, lithium fluoride (LiF), aluminum fluoride (AlF ₃ ), calcium fluoride (CaF ₂ ), barium fluoride (BaF ₂ ), magnesium fluoride, or the like can be suitably used. As the 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. More specifically, as the nesosilicate mineral, 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 , wilted stone, clinopite, kyanite), zinc silicate (silica zinc mineral, Zn ₂ SiO ₄ ), zirconium silicate ( Zircon, ZrSiO ₄ ), mullite (3Al ₂ O ₃ .2SiO ₂ to 2Al ₂ O ₃ .SiO ₂ ) and the like.

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⁻ ). In addition, 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.

Examples of the oxide mineral 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.

Of these minerals, some are classified as clay minerals. Examples of the clay mineral include a crystalline clay mineral, an amorphous or quasicrystalline clay mineral, and the like. Examples of 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.

Specifically, 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. Examples of the smectite group 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.

As a structure close to a layered silicate, 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. Etc. Examples of 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.

Other 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. Porous aluminosilicate, attapulgite [(Mg, Al) 2 Si ₄ O ₁₀ (OH) · 6H ₂ O], and the like.

The layered carbonate minerals, hydrotalcite _{_{_{(Mg 6 Al 2 (CO 3}}} ) (OH) 16 · 4 (H 2 O)) and the like.

Examples of the amorphous or quasicrystalline clay mineral 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.

(Mixing ratio of particles and resin)
From the viewpoint of ensuring the transparency of the particle-containing resin solution, the mixing ratio of the particles and the resin is in a range of particles / resin = 15/85 to 90/10 in terms of mass ratio (particle / resin). From the viewpoint of further improvement, the range is more preferably 15/85 or more and 80/20 or less, and further preferably 15/85 or more and less than 70/30. In addition, from the viewpoint of ensuring the transparency of the particle-containing resin solution, the lower the ratio of the particles, the better. However, if the particle ratio is too low, the strength of the particle-containing resin layer 11b tends to decrease. The lower limit is set. Further, for example, the refractive index of a resin such as PVdF is about 1.4, the refractive index of a solvent (N-methyl-2-pyrrolidone, dimethyl carbonate, etc.) is 1.2, and the refractive index of the resin. Is higher than the solvent of the resin solution, and therefore, it is preferable that the content ratio of the resin is large because it can approach the refractive index of the solid particles and suppress scattering more.

(Thickness of particle-containing resin layer)
The thickness of the particle-containing resin layer 11b is preferably, for example, 1 μm or more and 15 μm or less. Although it is preferable because transparency can be further improved by reducing the thickness, if it is too thin, the measurement accuracy of the thickness tends to decrease. On the other hand, if it is too thick, the transparency tends to decrease.

(Thickness of separator)
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. Specifically, the thickness of the separator 11 is preferably 4 μm or more and 20 μm or less, for example. In addition, the thickness of the separator 11 is not limited to this range.

(1-2) Separator Manufacturing Method The separator 11 according to the first embodiment described above can be manufactured as follows.

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.

(First example)
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 | coated to at least one surface of the separator base material 11a, and a particle | grain containing resin solution layer is formed.

When forming the particle-containing resin solution layer, typically, 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. The present technology includes particles having a refractive index within a predetermined range and a particle diameter within a predetermined range, and the mass ratio (particle / resin) of the particle-containing resin layer 11b to the resin is within a predetermined range. Therefore, a paint with improved transparency can be obtained. Thereby, 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.

After the coating, 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. In the first example, 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.

(Second example)
As in the first example, 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 | coated to at least one surface of the separator base material 11a, and a particle | grain containing resin solution layer is formed.

Subsequently, 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.

By using such a method, 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. As described above, 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.

2. Second Embodiment An electrode with a particle-containing resin layer according to a second embodiment of the present technology will be described. FIG. 2 is a schematic cross-sectional view illustrating a configuration example of an electrode with a particle-containing resin layer according to the first embodiment of the present technology.

2, 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. 2 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.

[Particle-containing resin layer]
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.

In addition, in the state where the electrode 21 with particle-containing resin layer according to the second embodiment is incorporated in a battery, the particle-containing resin layer 21b is impregnated with an electrolytic solution, and the particle-containing resin layer 21b includes an electrolytic solution. In this case, 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.

(First state)
In the first state, 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. In this case, the particle-containing resin layer 21b has a function as a separator. In other words, 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. .

(Second state)
In the second state, the electrolytic solution is absorbed by the matrix polymer compound and is included in the particle-containing resin layer 21b. That is, the particle-containing resin layer 21b is impregnated with the electrolytic solution, and the matrix polymer compound swells to become a so-called gel. In this state, 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 21b may disappear with the swelling of the matrix polymer compound. In this case, 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.

<3. Third Embodiment>
In the third embodiment of the present technology, a laminated film type nonaqueous electrolyte battery (battery) will be described. 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.

Hereinafter, two configuration examples (a first configuration example and a second configuration example) of the laminated film type nonaqueous electrolyte battery according to the third embodiment will be described.

Note that 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. In the battery according to the third embodiment, the separator 55 corresponds to the separator base material 11a, and the gel electrolyte layer 56 corresponds to the particle-containing resin layer 11b containing the electrolytic solution formed on the separator base material 11a.

(3-1) First Configuration FIG. 3 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. In the laminate film, 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 | positioned so that it may oppose. 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. Between the exterior member 60 and the positive electrode lead 51 and the negative electrode lead 52, there is an adhesive film 61 for improving the adhesion between the inner resin layer of the exterior member 60 and the positive electrode lead 51 and the negative electrode lead 52 made of a metal material. Has been placed. 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. 4 shows a cross-sectional structure taken along line II of the spirally wound electrode body 50 shown in FIG.

As shown in FIG. 4, 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.

[Positive electrode]
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. As the 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.

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. Examples of 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. Especially, what contains at least 1 sort (s) of 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.

As the positive electrode material, for example, a lithium-containing compound represented by Li _x M1O ₂ or Li _y M2PO ₄ can be used. In the formula, 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). _1-z Co _z O ₂ (0 <z <1)), 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)), or lithium manganese composite oxide (LiMn ₂ O ₄ ) or lithium manganese nickel composite oxide (LiMn _2−t N _t O ₄ (0 <t <2)) having a spinel structure. . Among these, 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.

Specific examples of such a lithium composite oxide include lithium cobaltate (LiCoO ₂ ), lithium nickelate (LiNiO ₂ ), and lithium manganate (LiMn ₂ O ₄ ). A solid solution in which a part of the transition metal element is substituted with another element can also be used. Examples thereof include nickel cobalt composite lithium oxide (LiNi _0.5 Co _0.5 O ₂ , LiNi _0.8 Co _0.2 O _2, etc.). These lithium composite oxides can generate a high voltage and have an excellent energy density.

Furthermore, from the viewpoint that higher electrode filling properties and cycle characteristics can be obtained, 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.

In addition, examples of 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. Of course, 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.

As the conductive agent, for example, a carbon material such as carbon black or graphite is used. Examples of 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).

[Negative electrode]
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.

Although not shown, 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.

In the nonaqueous electrolyte battery 62, 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. In particular, when a material that becomes a lithium alloy or absorbs lithium at a voltage close to 0 V with respect to Li / Li ^{+ is} used as the negative electrode active material, 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. When 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. Of these, 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. Some are classified as: 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. In particular, graphite is preferable because it has a high electrochemical equivalent and can provide a high energy density. Further, non-graphitizable carbon is preferable because excellent cycle characteristics can be obtained. Furthermore, 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.

As another 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. Also included are materials containing as a constituent element. 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. In the present technology, 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. Moreover, 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. Specifically, magnesium (Mg), boron (B), aluminum (Al), titanium (Ti), gallium (Ga), indium (In), silicon (Si), germanium (Ge), tin (Sn), Lead (Pb), bismuth (Bi), cadmium (Cd), silver (Ag), zinc (Zn), hafnium (Hf), zirconium (Zr), yttrium (Y), palladium (Pd) or platinum (Pt) Can be mentioned. These may be crystalline or amorphous.

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.

As an alloy of silicon, for example, as a second constituent element other than silicon, tin (Sn), nickel (Ni), copper (Cu), iron (Fe), cobalt (Co), manganese (Mn), zinc ( One containing at least one of the group consisting of Zn), indium (In), silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb) and chromium (Cr) Can be mentioned. Examples of tin alloys include silicon (Si), nickel (Ni), copper (Cu), iron (Fe), cobalt (Co), and manganese (Mn) as second constituent elements other than tin (Sn). , Zinc (Zn), indium (In), silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb) and chromium (Cr). Including.

Examples of the tin (Sn) compound or silicon (Si) compound include those containing oxygen (O) or carbon (C). In addition to tin (Sn) or silicon (Si), the above-described compounds are used. Two constituent elements may be included.

Among these, as the negative electrode material, 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. And the 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. Examples of other constituent elements include silicon (Si), iron (Fe), nickel (Ni), chromium (Cr), indium (In), niobium (Nb), germanium (Ge), titanium (Ti), and molybdenum. (Mo), aluminum (Al), phosphorus (P), gallium (Ga) or bismuth (Bi) are preferable and may contain two or more. This is because the capacity or cycle characteristics can be further improved.

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. In 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. However, the combination of carbon (C) with other elements suppresses such aggregation or crystallization. Because it can.

As a measuring method for examining the bonding state of elements, for example, X-ray photoelectron spectroscopy (XPS) can be mentioned. In XPS, 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. . Moreover, if it is surface contamination carbon, it will appear at 284.8 eV. On the other hand, when 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. That is, when 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.

In XPS measurement, for example, the C1s peak is used to correct the energy axis of the spectrum. Usually, since surface-contaminated carbon exists on the surface, the C1s peak of the surface-contaminated carbon is set to 284.8 eV, which is used as an energy standard. In the XPS measurement, 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.

[Separator]
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.

[Gel electrolyte layer]
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.

(Electrolyte salt)
The electrolyte salt contains, for example, one or more light metal compounds such as lithium salts. Examples of 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). Among these, 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 of the non-aqueous solvent include lactone solvents such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, and ε-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.

In addition, it is preferable to use 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. preferable. 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. This is because even when 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. Of these, difluoroethylene carbonate is preferably used as the non-aqueous solvent. This is because the cycle characteristic improvement effect is excellent.

(3-2) Manufacturing Method of Nonaqueous Electrolyte Battery 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.

[Positive electrode manufacturing process]
A positive electrode active material, a conductive agent, and a binder are mixed to prepare a positive electrode mixture, and the positive electrode mixture is dispersed in a solvent such as N-methyl-2-pyrrolidone to form a paste-like positive electrode mixture slurry Is made. Next, the positive electrode mixture slurry is applied to the positive electrode current collector 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.

[Negative electrode fabrication process]
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. Next, 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.

[Particle-containing resin layer formation step (separator preparation step)]
First, a separator similar to that of the first embodiment in which the particle-containing resin layer is formed on one main surface or both main surfaces of the separator 55 is manufactured. The details of the particle-containing resin layer forming step are the same as in the first embodiment. The configuration of the separator 55 corresponds to the configuration of the separator base material 11a and has the same configuration. The separator 55 and the particle-containing resin layer formed on at least one main surface of the separator 55 are formed on the separator 11 according to the first embodiment (at least one main surface of the separator base material 11a and the separator base material 11a). Corresponding to the separator 11) including the particle-containing resin layer 11b.

[Winding process]
Next, 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.

[Battery assembly process]
Next, 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). At that time, an adhesion film 61 is inserted between the positive electrode lead 51 and the negative electrode lead 52 and the exterior member 60.

Subsequently, after preparing a non-aqueous electrolyte and injecting it from the unwelded portion of the exterior member 60, the unwelded portion of the exterior member 60 is sealed by heat fusion or the like. At this time, by vacuum sealing, 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. Thereby, the nonaqueous electrolyte battery 62 shown in FIGS. 3 and 4 is completed.

(3-3) Second configuration (laminated type)
In the first configuration described above, the nonaqueous electrolyte battery 62 in which the spirally wound electrode body 50 is sheathed with the exterior member 60 has been described. However, as shown in FIGS. The electrode body 70 may be used. FIG. 5A is an external view of a nonaqueous electrolyte battery 62 that houses the laminated electrode body 70. FIG. 5B is an exploded perspective view showing a state in which the laminated electrode body 70 is accommodated in the exterior member 60. FIG. 5C is an external view showing the external appearance of the nonaqueous electrolyte battery 62 shown in FIG. 5A from the bottom surface side.

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. Although not shown, the gel electrolyte layer is provided in contact with the positive electrode 73 and the negative electrode 74. For example, 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.

In addition, 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.

<4. Fourth Embodiment>
In the fourth embodiment of the present technology, a laminated film type nonaqueous electrolyte battery (battery) will be described. 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.

Hereinafter, two configuration examples (a first configuration example and a second configuration example) of the laminate film type nonaqueous electrolyte battery according to the fourth embodiment will be described.

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. In the battery according to the fourth embodiment, 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.

(4-1) First Configuration 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. 3 and 4 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. And the gel electrolyte layer 56 is formed because the particle | grain containing resin layer formed in the surface of an electrode contains electrolyte solution. Except for the above, this embodiment is the same as the third embodiment. In the following, overlapping description of the same configuration as that of the third embodiment will be omitted as appropriate, and differences from the third embodiment will be described in detail.

[Gel electrolyte layer]
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. In this case, 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.

(4-2) Method for Producing Nonaqueous Electrolyte Battery Typically, 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. Manufactured by sequentially performing a resin layer forming step (electrode manufacturing step with particle-containing resin layer), a winding step, and a battery assembly step.

[Particle-containing resin layer forming step]
First, 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.

[Winding process]
Next, the positive electrode 53 with a particle-containing resin layer and the negative electrode 54 with a particle-containing resin layer are stacked and wound with a separator 55 interposed therebetween, so that a wound electrode body 50 having a wound structure is produced.

Subsequently, after preparing a non-aqueous electrolyte and injecting it from the unwelded portion of the exterior member 60, the unwelded portion of the exterior member 60 is sealed by heat fusion or the like. At this time, by vacuum sealing, 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. . Thereby, the nonaqueous electrolyte battery 62 shown in FIGS. 3 and 4 is completed.

(4-3) Second Configuration In the first configuration example described above, the nonaqueous electrolyte battery 62 in which the wound electrode body 50 is sheathed with the exterior member 60 has been described. The electrode body 70 may be used. A second configuration example of the nonaqueous electrolyte battery 62 according to the fourth embodiment is the same as the configuration shown in FIGS. 5A to 5C.

5. Fifth Embodiment In the fifth embodiment, a cylindrical nonaqueous electrolyte battery will be described. 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.

(5-1) Configuration of Nonaqueous Electrolyte Battery FIG. 6 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. In the safety valve mechanism, 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. . By connecting the safety valve 84 and the positive electrode lead 95 via the sub disk 89, the positive electrode lead 95 is prevented from being drawn from the hole 86a when the safety valve 84 is reversed. Further, the safety valve mechanism is electrically connected to the battery lid 83 via the heat sensitive resistance element 87.

In 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.

In addition, when further gas is generated inside the battery and the internal pressure of the battery further increases, a part of the safety valve 84 is broken and the gas can be discharged to the battery lid 83 side.

In addition, for example, a plurality of gas vent holes (not shown) are provided around the hole 86a of the shut-off disk 86. When gas is generated from the wound electrode body 90, the gas is effectively removed from the battery lid. It is set as the structure which can discharge | emit to 83 side.

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. To prevent. 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. As described above, 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. 7 shows an enlarged part of the spirally wound electrode body 90 shown in FIG. Hereinafter, the positive electrode 91, the negative electrode 92, and the separator 93 will be described in detail.

[Positive electrode]
In the positive electrode 91, 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. As the positive electrode current collector 91A, 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 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).

[Negative electrode]
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.

[Separator]
The separator 93 is the same as the separator 11 according to the first embodiment. That is, as shown in FIG. 7, 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.

(5-2) Manufacturing method of non-aqueous electrolyte battery [positive electrode manufacturing method, negative electrode manufacturing method]
The positive electrode 91 and the negative electrode 92 are produced in the same manner as in the third embodiment.

[Manufacturing method of separator]
In the same manner as in the first 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.

[Preparation of non-aqueous electrolyte]
The nonaqueous electrolytic solution is prepared by dissolving an electrolyte salt in a nonaqueous solvent.

[Assembly of non-aqueous electrolyte battery]
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 a and 82 b and housed in the battery can 81. After the wound electrode body 90 is accommodated in the battery can 81, a non-aqueous electrolyte is injected into the battery can 81 and impregnated in the separator 93. After that, 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. Thereby, the nonaqueous electrolyte battery 80 of this technique shown in FIG. 6 is formed.

In 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.

6). Sixth Embodiment In a sixth embodiment, 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.

(6-1) Configuration of Nonaqueous Electrolyte Battery As shown in FIG. 8, each of the particle-containing resin layer 91C and the particle-containing resin layer 92C, for example, is interposed between the positive electrode 91 and the negative electrode 92 together with the separator 93. In addition to preventing contact between the bipolar active materials, like 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. In addition, as 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.

A configuration in which only the electrode (positive electrode) with a particle-containing resin layer in which the particle-containing resin layer 91C is provided on both or one main surface of the positive electrode 91 without forming the particle-containing resin layer 92C with respect to the negative electrode 92 is incorporated. It is good. Even if only the electrode (negative electrode) with the particle containing resin layer which provided the particle containing resin layer 92C in both or one main surface of the negative electrode 92 without forming the particle containing resin layer 91C with respect to the positive electrode 91 is incorporated. Good. Further, 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.

(6-2) Nonaqueous electrolyte battery manufacturing method [Positive electrode 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.

[Production method of negative electrode]
Similarly to the second embodiment, 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.

[Separator]
The separator 93 has the same configuration as that of the separator base material 93a.

[Assembly of non-aqueous electrolyte battery]
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.

Thereafter, the wound surface of the wound electrode body 90 is sandwiched between the pair of insulating plates 82 a and 82 b and stored in the battery can 81. After the wound electrode body 90 is housed 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. After that, 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. Thereby, the nonaqueous electrolyte battery 80 of this technique shown in FIG. 6 is formed.

In 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 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.

7). Seventh Embodiment In the seventh embodiment, a rectangular nonaqueous electrolyte battery will be described. The battery according to the seventh 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.

(7-1) Configuration of Nonaqueous Electrolyte Battery FIG. 9 shows the configuration of a nonaqueous electrolyte battery 100 according to the seventh embodiment. This non-aqueous electrolyte battery is a so-called square battery, in which the wound electrode body 120 is accommodated in a square outer can 111.

The nonaqueous electrolyte battery 100 includes a rectangular tube-shaped outer can 111, a wound electrode body 120 that is a power generation element housed in the outer can 111, a battery lid 112 that closes an opening of the outer can 111, a battery The electrode pin 113 and the like provided in the approximate center of the lid 112 are configured.

The outer can 111 is formed, for example, as a hollow, bottomed rectangular tube with a conductive metal such as iron (Fe). The inner surface of the outer can 111 is preferably configured to increase the conductivity of the outer can 111 by, for example, applying nickel plating or applying a conductive paint. Further, the outer peripheral surface of the outer can 111 may be covered with an outer label formed of, for example, a plastic sheet or paper, or may be protected by applying an insulating paint. The battery lid 112 is formed of a conductive metal such as iron (Fe), for example, like the outer can 111.

The wound electrode body 120 is obtained by laminating a positive electrode and a negative electrode with a separator interposed between them and winding them in an oval shape. Since the positive electrode, the negative electrode, the separator, and the nonaqueous electrolytic solution are the same as those in the fifth embodiment, detailed description thereof is omitted.

The wound electrode body 120 having such a configuration is provided with a number of positive terminals 121 connected to the positive current collector and a number of negative terminals connected to the negative current collector. All the positive terminals 121 and the negative terminals are led to one end of the spirally wound electrode body 120 in the axial direction. The positive terminal 121 is connected to the lower end of the electrode pin 113 by fixing means such as welding. The negative electrode terminal is connected to the inner surface of the outer can 111 by fixing means such as welding.

The electrode pin 113 is made of a conductive shaft member, and is held by an insulator 114 with its head protruding to the upper end. The electrode pin 113 is fixed to a substantially central portion of the battery lid 112 through the insulator 114. The insulator 114 is made of a highly insulating material and is fitted into a through hole 115 provided on the surface side of the battery lid 112. Further, the electrode pin 113 is penetrated through the through hole 115, and the tip end portion of the positive electrode terminal 121 is fixed to the lower end surface thereof.

The battery lid 112 provided with such electrode pins 113 and the like is fitted in the opening of the outer can 111, and the contact surface between the outer can 111 and the battery lid 112 is joined by a fixing means such as welding. Yes. Thereby, the opening part of the armored can 111 is sealed by the battery cover 112, and is comprised airtight and liquid-tight. The battery lid 112 is provided with an internal pressure release mechanism 116 that breaks a part of the battery lid 112 to release (release) the internal pressure to the outside when the pressure in the outer can 111 rises to a predetermined value or more. ing.

The internal pressure release mechanism 116 has two first opening grooves 116a (one first opening groove 116a not shown) linearly extending in the longitudinal direction on the inner surface of the battery lid 112, and the same as the battery. The inner surface of the lid 32 includes a second opening groove 116b extending in the width direction orthogonal to the longitudinal direction and having both ends communicating with the two first opening grooves 116a. The two first opening grooves 116a are provided in parallel to each other so as to be along the outer edge of the battery lid 112 in the vicinity of the inner side of the two long sides positioned so as to face the width direction of the battery lid 32. ing. Further, the second opening groove 116 b is provided so as to be positioned at a substantially central portion between one short side outer edge and the electrode pin 113 on one side in the longitudinal direction of the electrode pin 113.

The first opening groove 116a and the second opening groove 116b are, for example, both V-shaped with a cross-sectional shape opened to the lower surface side. Note that the shapes of the first opening groove 116a and the second opening groove 116b are not limited to the V-shape shown in this embodiment. For example, the shapes of the first opening groove 116a and the second opening groove 116b may be U-shaped or semicircular.

The electrolyte injection port 117 is provided so as to penetrate the battery lid 112. The electrolyte injection port 117 is used to inject the non-aqueous electrolyte after the battery lid 112 and the outer can 111 are caulked, and is sealed by the sealing member 118 after the non-aqueous electrolyte is injected. The For this reason, when forming a wound electrode body by previously forming a gel electrolyte between the positive electrode, the negative electrode, and the separator, the electrolyte solution inlet 117 and the sealing member 118 may not be provided.

[Separator]
The separator is the same separator as in the first embodiment, and uses a binder polymer compound as the resin of the particle-containing resin layer.

(7-2) Method for Manufacturing Nonaqueous Electrolyte Battery This nonaqueous electrolyte battery can be manufactured, for example, as follows.

[Method for producing positive electrode and negative electrode]
The positive electrode and the negative electrode can be produced by the same method as in the fifth embodiment.

[Assembly of non-aqueous electrolyte battery]
A positive electrode, a negative electrode, and a separator (having a particle-containing resin layer formed on at least one surface of a base material) are sequentially laminated and wound to produce a wound electrode body 120 that is wound in an oblong shape. Subsequently, the wound electrode body 120 is accommodated in the outer can 111.

Then, the electrode pin 113 provided on the battery lid 112 and the positive electrode terminal 121 led out from the wound electrode body 120 are connected. Although not shown, the negative electrode terminal led out from the wound electrode body 120 and the battery can are connected. Thereafter, the outer can 111 and the battery lid 112 are fitted, and for example, a non-aqueous electrolyte is injected from the electrolyte injection port 117 under reduced pressure, and the sealing member 118 is sealed. As described above, the nonaqueous electrolyte battery 100 can be obtained.

8). Eighth Embodiment In an eighth embodiment, a rectangular nonaqueous electrolyte battery will be described. The battery according to the eighth embodiment is an electrode with a particle-containing resin layer similar to that of the second embodiment, and a battery using a binder polymer compound is incorporated as the resin of the particle-containing resin layer. The separator may have a configuration similar to that of the separator substrate 11a on which the particle-containing resin layer is not formed. Except for the above, this embodiment is the same as the seventh embodiment.

9. Ninth Embodiment In the ninth embodiment, a battery pack of a laminate film type battery (nonaqueous electrolyte battery) provided with the same gel electrolyte layer as in the third embodiment or the fourth embodiment. Explain the example

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.

An example of the configuration of a simple battery pack will be described. 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.

As shown in FIGS. 10 and 11A to 11B, the simplified battery pack includes a battery cell 131, leads 132a and 132b led out from the battery cell 131, insulating tapes 133a to 133c, an insulating plate 134, A circuit board 135 on which a protection circuit (PCM (Protection Circuit Module)) is formed and a connector 136 are provided. The battery cell 131 is the same as the nonaqueous electrolyte secondary battery according to the third or fourth embodiment, for example.

The insulating plate 134 and the circuit board 135 are disposed on the terrace portion 131 a at the front end of the battery cell 131, and the leads 132 a and the leads 132 b led out from the battery cell 131 are connected to the circuit board 135.

A connector 136 for output is connected to the circuit board 135. Members such as the battery cell 131, the insulating plate 134, and the circuit board 135 are fixed by sticking insulating tapes 133a to 133c at predetermined positions.

<10. Tenth Embodiment>
FIG. 12 is a block diagram showing a circuit configuration example when the batteries according to the third to eighth 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.

Further, 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. In addition, in FIG. 12, although the case where the six secondary batteries 301a are connected to 2 parallel 3 series (2P3S) is shown as an example, it is like 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. In the example, 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.

Here, for example, when the secondary battery is a lithium ion secondary battery, 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. .

As the charge / discharge switch, for example, a semiconductor switch such as a MOSFET can be used. In this case, the parasitic diode of the MOSFET functions as the

diodes

302b and 303b. When a P-channel FET is used as the charge / discharge switch, 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. When 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.

For example, in the case of overcharge or overdischarge, the 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. In the memory 317, 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.

<11. Eleventh embodiment>
The batteries according to the third to eighth embodiments and the battery packs according to the ninth to tenth 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.

Also, 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.

Hereinafter, a specific example of a power storage system using a power storage device to which the above-described battery of the present technology is applied will be described among the application examples described above.

This power storage system has the following configuration, for example. 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. These power storage systems are implemented as a system for efficiently supplying power in cooperation with an external power supply network.

Furthermore, 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. Hereinafter, the power storage system will be described.

(11-1) Residential Power Storage System as an Application Example An example in which a power storage device using a battery of the present technology is applied to a residential power storage system will be described with reference to FIG. For example, in 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. Supplied to the device 403. At the same time, 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. Furthermore, 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. There is a method of using a sensor network according to the standard. The 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.

As described above, not only the centralized power system 402 such as the thermal power generation 402a, the nuclear power generation 402b, and the hydroelectric power generation 402c but also 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.

In this example, the example in which the control device 410 is stored in the power storage device 403 has been described. However, the control device 410 may be stored in the smart meter 407 or may be configured independently. Furthermore, 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.

(11-2) Power Storage System in Vehicle as Application Example An example in which the present technology is applied to a power storage system for a vehicle will be described with reference to FIG. 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. In addition, by using DC-AC (DC-AC) or reverse conversion (AC-DC conversion) at a required place, 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.

When the hybrid vehicle 500 decelerates by a braking mechanism (not shown), 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.

Although not shown, an information processing device that performs information processing related to vehicle control based on information related to the secondary battery may be provided. As such 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.

In the above description, the series hybrid vehicle that runs on the motor using the power generated by the generator driven by the engine or the power stored once in the battery has been described as an example. However, 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.

Hereinafter, the present technology will be described in detail by way of examples. In addition, this technique is not limited to the structure of the following Example.

<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. 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 μm so that a part of the positive electrode current collector was exposed. Thereafter, 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. Finally, the positive electrode terminal was attached to the exposed portion of the positive electrode current collector to form the positive electrode.

[Production of negative electrode]
96% by mass of granular graphite powder having an average particle diameter of 20 μm as a negative electrode active material, 1.5% by mass of acrylic acid-modified styrene-butadiene copolymer as a binder, and 1.5% by mass of carboxymethylcellulose as a thickener % Was mixed to make a negative electrode mixture, and an appropriate amount of water was further added and stirred to prepare a negative electrode mixture slurry. This negative electrode mixture slurry was applied to both sides of a negative electrode current collector made of a strip-shaped copper foil having a thickness of 15 μm so that a part of the negative electrode current collector was exposed. Then, the dispersion medium of the apply | 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.

[Preparation of separator]
A 9 μm-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.

First, boehmite particles as a filler (particle diameter D50: 1000 nm, refractive index 1.7, flat particles (plate-like particles)) and matrix polymer compound (resin) vinylidene fluoride and hexafluoropropylene The polymer (PVdF-HFP, refractive index 1.4) was dispersed in N-methyl-2-pyrrolidone (NMP, refractive index 1.2) to prepare a paint (particle-containing resin solution). At this time, the amount of each material was adjusted so that the solid content (boehmite particles and PVdF-HFP) was 20% by mass with respect to the total amount of the coating material. That is, the content of boehmite particles is 10% by mass with respect to the total amount of paint, the content of PVdF-HFP is 10% by mass with respect to the total amount of paint, and the content of NMP is with respect to the total amount of paint. 80% by mass. The mass ratio (particle / resin) between boehmite particles and PVdF-HFP is 50/50.

Next, this paint was uniformly applied to each of both surfaces of the base material with a predetermined paint thickness (5.0 μm in Example 1-1). At this time, during coating, 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. In addition, the coating thickness measurement immediately after application | coating is measured by the triangulation of a laser beam. It is obtained from the difference in the distance of the reflection point between the reflected light on the paint surface and the reflected light on the coating object (electrode or separator). Based on this information, the opening degree of the coating head gap or the amount of paint discharged is automatically adjusted via a program.

Thereafter, the NMP is removed from the particle-containing resin solution layer by passing the substrate coated with the paint in a dryer, and the substrate is composed of PVdF-HFP and boehmite particles formed on both sides of the substrate. A separator having a particle-containing resin layer was produced.

[Assembly of laminated film type battery]
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.

Next, 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.

After that, an electrolytic solution was poured into this, and the remaining one side was heat-sealed under reduced pressure and sealed. At this time, the electrolyte solution was impregnated into the particle-containing resin layer, and the matrix polymer compound was swollen to form a gel electrolyte (gel electrolyte layer). In addition, what was prepared as follows was used as electrolyte solution. An 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. In this case, the mass ratio of the constituents of the electrolyte _{(EC / DMC / LiPF 6)} (EC / DMC / LiPF 6) was adjusted to the amount of each component such that the 35/50/15. Thus, a laminated film type battery shown in FIG. 3 having a thickness of 4.5 mm, a width of 30 mm, and a height of 50 mm was produced.

<Example 1-2 to Example 1-55>
In Examples 1-2 to 1-55, laminate film type batteries were produced in the same manner as in Example 1-1 except that the particles used were changed as shown in Table 1 below.

<Comparative Example 1-1>
A laminated film type battery was produced in the same manner as in Example 1-1 except that the particles were not mixed in the paint.

<Comparative Example 1-2 to Comparative Example 1-10>
In Comparative Examples 1-2 to 1-10, as shown in Table 1 below, the material type of the particles used was changed to one having a different refractive index or colored particles, and the shape of the particles was also changed to spherical or polyhedral. Except for this, a laminated film type battery was produced in the same manner as in Example 1-1.

<Comparative Example 1-11>
Example 1 except that the material type of the particles used was changed to one having a different refractive index, the shape of the particles was changed to a polyhedron, and the mass ratio (particle / resin) was changed as shown in Table 1 below. In the same manner as in Example 1, a laminate film type battery was produced.

<Comparative Example 1-12>
A laminated film type battery was produced in the same manner as in Example 1-1 except that the mass ratio (particle / resin) was changed as shown in Table 1 below.

<Comparative Example 1-13 to Comparative Example 1-15>
A laminated film type battery was produced in the same manner as in Example 1-1 except that the particle diameter of the particles was changed as shown in Table 1 below.

<Comparative Example 1-16>
A laminated film type battery was produced in the same manner as Comparative Example 1-12 except that the material type and particle diameter of the particles were changed as shown in Table 1 below, and the shape of the particles was changed to a polyhedron.

(Evaluation: Particle size, paint appearance)
In the above-mentioned Examples and Comparative Examples, the particle diameter of the particles and the appearance of the paint are measured or evaluated as follows. (The same applies to Examples and Comparative Examples described later)

(Measurement of particle diameter)
In the particle size distribution measured by laser diffractometry, the particles after removing the gel electrolyte component etc. from the gel electrolyte layer (particle-containing resin layer containing the electrolyte solution) have a cumulative volume of 50% calculated from the particle side with a small particle diameter. The particle diameter was defined as the particle diameter D50 of the particles. In addition, the value of the particle diameter D40 of the volume cumulative 40% and the value of the particle diameter D60 of the volume cumulative 60% were obtained from the measured particle size distribution as needed.

(Appearance evaluation)
The appearance of the paint film was observed by visual observation. The degree of transparency was further evaluated stepwise as transparent, transparent, generally transparent, and translucent. In each of the cases of transparent, almost transparent, and almost transparent, the outline of the application target (electrode or separator) was completely visible through the paint film. Moreover, when it was opaque, the outline of the application target (electrode or separator) could not be visually recognized through the paint film.

(Battery evaluation: Pass / fail judgment of laser measurement)
The measured value of the laser thickness meter during coating was recorded. Then, after drying and removing the solvent, the thickness of the measurement site where the measurement value of the laser thickness gauge was recorded was measured with a contact-type thickness gauge. In the measurement using a contact-type thickness meter, measurement was performed by applying a load of 50 g to a flat contact terminal having a diameter of 5 mm, and the value obtained by subtracting the thickness of the application target (electrode or separator) from the measured value was defined as the application thickness. And when the difference of the measured value of a laser thickness meter and application | coating thickness was less than +/- 10% in the percentage with respect to predetermined | prescribed coating material thickness, it was set as the rejection in other than that.

In the paint film production process in the battery manufacturing process described above, the solvent (NMP) dilution ratio and the drying were adjusted so that the coating thickness of the paint was the same as the completed thickness after removal of the solvent (NMP) by drying. Temperature is used as a manufacturing condition. That is, the thickness of the coating immediately after application whose solid content was known was determined by calculation from the area density of the coating film in advance, the solvent of the coating film was removed, and the thickness after drying was measured with a contact-type thickness meter. The NMP dilution rate and the drying temperature adjusted so that the difference between the calculated value and the measured value was within ± 10% as a percentage of the measured value were used as the production conditions.

(Battery evaluation: Battery bending test)
The produced battery was charged at a constant current of 1 C at a constant current of 1 C until the battery voltage reached 4.2 V, and then the total charging time was 2.5 hours at a constant voltage of 4.2 V. Until constant voltage charging. Next, as shown in FIGS. 15 and 16, the charged battery CELL is arranged on the two round bars S juxtaposed at an interval of 30 mm, and one battery from the upper side with respect to the center position of the battery CELL. Was pressed until 300N or the pressed portion was deflected by 3 mm (down to 3 mm downward). At that time, the voltage of the battery CELL was confirmed with a voltmeter (tester) 600, and if a voltage drop of 1% or more was confirmed, the short circuit determination was rejected. Moreover, when it short-circuited, it was set as the measurement impossible, and other than that was set as the pass.

Evaluation results are shown in Table 1.

As shown in Table 1, in Examples 1-1 to 1-55, the paint includes particles having a particle diameter and a refractive index within a predetermined range, and the mass ratio (particle / resin) is a predetermined value. It is within the range. Thereby, since the paint was transparent, the pass / fail judgment of the laser measurement was acceptable. Moreover, since the thickness control of the gel electrolyte was successful, the battery bending test was acceptable. In Comparative Example 1-1, the gel electrolyte did not contain particles, so the strength was insufficient, and the battery bending test failed. In Comparative Examples 1-2 to 1-10, since the refractive index of the particles contained in the coating material is not within the predetermined range, the coating material is not transparent. Moreover, since the paint was not transparent, the thickness control was not successful, and the thickness of the gel electrolyte was insufficient, so the battery bending test was rejected. In Comparative Example 1-11, since the particle concentration was lowered, the paint became almost transparent, and the pass / fail judgment of the laser measurement was acceptable. On the other hand, the battery bending test failed because the concentration of the particles was too low. In Comparative Example 1-12, the paint was translucent, and the laser measurement pass / fail judgment was unacceptable. Moreover, since the thickness of the gel electrolyte was insufficient, the battery bending test was rejected. In Comparative Example 1-13, since the particle diameter of the particles was not within the predetermined range, the paint was not transparent, and the laser measurement pass / fail judgment was unacceptable. Moreover, since the thickness of the gel electrolyte was insufficient, the battery bending test was rejected. In Comparative Example 1-14, since the particle diameter of the particles was too small, the viscosity of the coating material was too high to be applied. In Comparative Example 1-15, since the particle diameter of the particles was too large, it could not be applied with a thickness of 5 μm. In Comparative Example 1-16, since the refractive index, particle diameter, and mass ratio (particle / resin) of the particles were not within the predetermined ranges, the paint was not transparent and the laser measurement pass / fail judgment was unacceptable. . Moreover, since the paint was not transparent, the thickness control was not successful, and the thickness of the gel electrolyte was insufficient, so the battery bending test was rejected. If the transparency is poor, laser measurement results in data that is thicker than the actual paint film thickness, and the amount of paint applied is automatically adjusted based on this data. Thus, a paint film having a thickness smaller than a predetermined thickness is obtained. Therefore, when the transparency is poor, the value measured by the contact-type thickness meter becomes small. As the transparency increases, the measurement accuracy of the coating film thickness of laser measurement increases, so it becomes difficult to create a thinly coated part, and it is not necessary to apply a thick margin, so the coating film can be made thinner and the volume of the battery Energy density can be improved.

<Example 2-1 to Example 2-8>
Example 1-1 and Example 1-1 except that the amounts of each component of boehmite particles, resin (PVdF-HFP), LiPF ₆ and solvent (NMP), which are constituents of the paint, were changed as shown in Table 2 below. Similarly, a laminate film type battery was produced. In Table 2, the amount of each component of particles, resin (PVdF-HFP), LiPF ₆ , and solvent is expressed as a mass percentage with respect to the total amount of paint (total amount of constituent components).

<Example 2-9 to Example 2-16>
Except for changing the amounts of talc particles, resin (PVdF-HFP), LiPF ₆ and solvent (NMP) as constituent components of the paint as shown in Table 2 below, Example 1-2 and Similarly, a laminate film type battery was produced. In Table 2, the amount of each component of particles, resin (PVdF-HFP), LiPF ₆ , and solvent is expressed as a mass percentage with respect to the total amount of paint (total amount of constituent components).

<Example 2-17 to Example 2-24>
Example 1-8, except that the amount of each component of aluminum oxide particles, resin (PVdF-HFP), LiPF ₆ and solvent (NMP), which are constituents of the paint, was changed as shown in Table 2 below. In the same manner, a laminate film type battery was produced. In Table 2, the amount of each component of particles, resin (PVdF-HFP), LiPF ₆ , and solvent is expressed as a mass percentage with respect to the total amount of paint quality (total amount of constituent components).

(Battery evaluation: Pass / fail judgment of laser measurement)
Regarding the produced laminated film type batteries of each Example and each Comparative Example, the pass / fail judgment of laser measurement was performed in the same manner as in Example 1-1.

Table 2 shows the evaluation results.

As shown in Table 2, in Examples 2-1 to 2-24, the paint includes particles having a particle diameter and a refractive index within a predetermined range, and the mass ratio (particle / resin) is a predetermined value. It is within the range. Thereby, since the paint was transparent, the pass / fail judgment of the laser measurement was acceptable.

<Example 3-1 to Example 3-13>
In Example 3-1 to Example 3-13, the same procedure as in Example 1-1 was performed, except that the particle diameter D50 of boehmite particles, which are constituents of the paint, was changed as shown in Table 3 below. A laminated film type battery was produced.

<Example 3-14 to Example 3-26>
In Examples 3-14 to 3-26, the particle diameter D50 of talc particles, which are constituents of the paint, was changed as shown in Table 3 below. A battery was produced as follows. Except for the above, a laminated film type battery was produced in the same manner as in Example 1-2.

[Preparation of positive electrode, formation of particle-containing resin layer]
A positive electrode was produced in the same manner as in Example 1-2. Moreover, the particle | grain containing resin layer was formed as follows on both surfaces of a positive electrode.

Next, the same paint as in Example 1-2 was uniformly applied to each of both surfaces of the positive electrode with a predetermined paint thickness (5.0 μm). At this time, during coating, 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.

Then, 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.

[Production of negative electrode, formation of particle-containing resin layer]
A negative electrode was produced in the same manner as in Example 1-2. In addition, a particle-containing resin layer was formed on both sides of the negative electrode in the same manner as the positive electrode.

[Preparation of separator]
A 9 μm-thick polyethylene (PE) microporous film was used as the substrate.

[Assembly of laminated film type battery]
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.

After that, an electrolytic solution was poured into this, and the remaining one side was heat-sealed under reduced pressure and sealed. In addition, what was prepared as follows was used as electrolyte solution. An 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. In this case, 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. Thus, a laminated film type battery having a battery shape of thickness 4.5 mm, 30 mm, and height 50 mm was produced.

<Example 3-27 to Example 3-39>
In Examples 3-27 to 3-39, the particle diameter D50 of the aluminum oxide particles, which are constituents of the paint, was changed as shown in Table 3 below. A battery was produced in the same manner as in Example 3-14. Except for the above, a laminated film type battery was produced in the same manner as in Example 1-8.

Table 3 shows the evaluation results.

As shown in Table 3, in Examples 3-1 to 3-39, the paint includes particles having a particle diameter and a refractive index within a predetermined range, and the mass ratio (particle / resin) is a predetermined value. It is within the range. Thereby, since the paint was transparent, the pass / fail judgment of the laser measurement was acceptable.

<Example 4-1 to Example 4-8>
In Examples 4-1 to 4-8, the material type of the paint was changed to boehmite. The particle size D40, particle size D50, and particle size D60 of boehmite particles, which are constituents of the paint, were changed as shown in Table 4 below. The predetermined paint thickness when applying the paint was set to 12.0 μm. Except for the above, a laminated film type battery was produced in the same manner as in Example 1-14.

Table 4 shows the evaluation results.

As shown in Table 4, in Examples 4-1 to 4-8, the paint includes particles having a particle diameter and a refractive index within a predetermined range, and the mass ratio (particle / resin) is a predetermined value. It is within the range. Thereby, since the paint was transparent, the pass / fail judgment of the laser measurement was acceptable. In Example 4-3, there was some coating unevenness due to the large particles. In Example 4-7, since the particles were small, the viscosity was high and there was some coating unevenness.

<Example 5-1 to Example 5-3>
In Example 5-1 to Example 5-3, a laminated film type battery was prepared in the same manner as in Example 3-14, except that the plate-like talc particles shown in Table 5 below were used as the filler. Produced.

<Example 5-4 to Example 5-6>
In Example 5-4 to Example 5-6, a laminated film type battery was obtained in the same manner as in Example 3-27 except that acicular aluminum oxide particles shown in Table 5 below were used as the filler. Was made.

Table 5 shows the evaluation results.

As shown in Table 5, in Examples 5-1 to 5-6, the paint includes particles having a particle diameter and a refractive index within a predetermined range, and the mass ratio (particle / resin) is a predetermined value. It is within the range. Thereby, since the paint was transparent, the pass / fail judgment of the laser measurement was acceptable.

<Example 6-1 to Example 6-29>
In Examples 6-1 to 6-29, as shown in Table 6 below, a laminate film type was obtained in the same manner as in Example 1-1 except that the type of resin constituting the paint was changed. A battery was produced.

Table 6 shows the evaluation results

As shown in Table 6, in Examples 6-1 to 6-29, the paint includes particles having a particle diameter and a refractive index within a predetermined range, and the mass ratio (particle / resin) is a predetermined value. It is within the range. Thereby, since the paint was transparent, the pass / fail judgment of the laser measurement was acceptable.

<Example 7-1 to Example 7-6>
In Examples 7-1 to 7-6, laminating was performed in the same manner as in Example 1-1 except that the predetermined paint thickness when applying the paint was changed as shown in Table 7 below. A film type battery was produced.

(Battery evaluation: Pass / fail judgment of laser measurement)
Regarding the manufactured laminated film type batteries of each Example, the pass / fail judgment of laser measurement was performed in the same manner as in Example 1-1.

Table 7 shows the evaluation results.

As shown in Table 7, in Examples 7-1 to 7-6, the paint includes particles having a particle diameter and a refractive index within a predetermined range, and the mass ratio (particle / resin) is a predetermined value. It is within the range. Thereby, since the paint was transparent, the pass / fail judgment of the laser measurement was acceptable. In Example 7-6, the particle diameter was the same as the coating thickness, and slight coating unevenness occurred. When the thickness of the coating was 1 μm or less, uneven coating was likely to occur and the transparency was liable to be slightly reduced.

<Example 8-1>
In Example 8-1, a laminated film type battery was produced in the same manner as in Example 1-1.

<Example 8-2>
[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.

[Preparation of separator]
A 9 μm-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.

First, boehmite particles (particle diameter D50: 1000 nm, refractive index 1.7, flat particles (plate-like particles)) as a filler and vinylidene fluoride (PVdF, refractive index 1.4) as a binder polymer compound (resin). ) Was dispersed in N-methyl-2-pyrrolidone (NMP, refractive index 1.2) to prepare a paint (particle-containing resin solution). Under the present circumstances, the quantity of each material was adjusted so that solid content (boehmite particle | grains and PVdF) might be 20 mass% with respect to the whole quantity of a coating material. That is, the content of boehmite particles is 10% by mass with respect to the total amount of paint, the content of PVdF is 10% by mass with respect to the total amount of paint, and the content of NMP is 80% with respect to the total amount of paint. It was set as mass%. In addition, the mass ratio (particle / resin) of boehmite particles and PVdF is 50/50.

Next, this paint was uniformly applied to each of both surfaces of the base material with a predetermined paint thickness shown in Table 8. At this time, during coating, 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.

Then, 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.

After that, an electrolytic solution was poured into this, and the remaining one side was heat-sealed under reduced pressure and sealed. In addition, what was prepared as follows was used as electrolyte solution. An 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. In this case, 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. Thus, a laminated film type battery shown in FIG. 3 having a thickness of 4.5 mm, a width of 30 mm, and a height of 50 mm was produced.

<Example 8-3>
In Example 8-3, the configuration of each of the positive electrode, the negative electrode, the separator, and the particle-containing resin layer and the application target of the particle-containing resin layer were the same as in Example 8-2, and the laminated electrode body was covered with a laminate film. A laminate film type battery was produced.

[Assembly of laminated film type battery]
The same paint as in Example 8-2 was uniformly applied to each of both surfaces of the base material with a predetermined paint thickness shown in Table 8. At this time, during coating, 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.

Next, a rectangular positive electrode and a rectangular negative electrode, and a rectangular separator were laminated in the order of the positive electrode, the separator, the negative electrode, and the separator to form a laminated electrode body.

Next, the laminated electrode body was covered with a laminate film having a soft aluminum layer, and the three sides around the laminated electrode body were heat-sealed and sealed and sealed. After that, an electrolytic solution was poured into this, and the remaining one side was heat-sealed under reduced pressure and sealed. Thus, a laminated film type battery shown in FIGS. 5A to 5C having a battery shape of 4.5 mm in thickness, 30 mm in width, and 50 mm in height was produced.

<Example 8-4>
In the same manner as in Example 8-1, a positive electrode and a negative electrode were produced. In addition, a separator having a particle-containing resin layer formed on both sides was obtained using the same paint as in Example 8-2.

[Assembly of square battery]
A positive electrode, a negative electrode, and a separator having a particle-containing resin layer formed on both sides are laminated in the order of the positive electrode, the separator, the negative electrode, and the separator, wound many times in the longitudinal direction in a flat shape, A wound electrode body was formed by fixing with an adhesive tape. Next, as shown in FIG. 9, the wound electrode body was accommodated in a rectangular battery can. Subsequently, after connecting the electrode pin provided on the battery lid and the positive electrode terminal derived from the wound electrode body, the battery can is sealed with the battery lid, and the nonaqueous electrolyte is injected from the electrolyte inlet. And sealed with a sealing member. Thus, a prismatic battery shown in FIG. 9 having a battery shape of 5.2 mm thickness, 34 mm width, and 36 mm height (523436 size) was produced.

In the same manner as in Example 8-1, a positive electrode and a negative electrode were produced. In addition, a separator having a particle-containing resin layer formed on both sides was obtained using the same paint as in Example 8-2.

[Assembly of cylindrical battery]
A positive electrode, a negative electrode, and a separator with a particle-containing resin layer formed on both sides are laminated in the order of the positive electrode, separator, negative electrode, and separator, wound many times in the longitudinal direction, and then the winding end is fixed with an adhesive tape. Thus, a wound electrode body was formed. Next, the positive electrode terminal was bonded to the safety valve bonded to the battery lid, and the negative electrode lead was connected to the negative electrode can. After the wound electrode body was sandwiched between a pair of insulating plates and housed inside the battery can, a center pin was inserted into the center of the wound electrode body.

Subsequently, a non-aqueous electrolyte was injected into the inside of the cylindrical battery can from above the insulating plate. Finally, a safety valve mechanism including a safety valve, a disk holder, and a shut-off disk, a PTC element, and a battery lid were sealed in the open portion of the battery can by caulking through an insulating sealing gasket. Thereby, the battery shape was 18 mm in diameter and 65 mm in height (ICR18650 size), and the cylindrical battery shown in FIG. 6 was produced.

<Example 8-6>
In Example 8-6, a simple battery pack (soft pack) shown in FIGS. 10, 11A, and 11B was manufactured using the same laminate film type battery as in Example 8-1.

<Example 8-7>
In Example 8-7, a laminated film type battery was produced in the same manner as in Example 8-1, except that the coating material was applied only to one surface on the negative electrode side of the separator.

<Example 8-8>
In Example 8-8, a laminate film type battery was produced in the same manner as in Example 8-1, except that the coating material was applied only to one side of the separator on the positive electrode side.

<Example 8-9>
[Preparation of positive electrode, formation of particle-containing resin layer]
A positive electrode was produced in the same manner as in Example 8-1. Moreover, the particle | grain containing resin layer was formed as follows on both surfaces of a positive electrode.

Next, the same paint as in Example 8-2 was uniformly applied to each of both surfaces of the positive electrode with a predetermined paint thickness (5.0 μm). At this time, during coating, 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.

[Production of negative electrode, formation of particle-containing resin layer]
A negative electrode was produced in the same manner as in Example 8-1. In addition, a particle-containing resin layer was formed on both sides of the negative electrode in the same manner as the positive electrode.

<Example 8-10>
[Preparation of positive electrode, formation of particle-containing resin layer]
A positive electrode was produced in the same manner as in Example 8-1. Moreover, the particle | grain containing resin layer was formed as follows on both surfaces of a positive electrode.

(Formation of particle-containing resin layer)
The same paint as in Example 8-1 was uniformly applied at a predetermined paint thickness (5.0 μm) shown on each of both surfaces of the positive electrode. At this time, during coating, 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.

Thereafter, the NMP is removed from the particle-containing resin solution layer by passing the positive electrode on which the paint is applied in a dryer, thereby forming a particle-containing resin layer composed of PVdF-HFP and boehmite particles on both sides of the positive electrode. did.

[Production of negative electrode, formation of particle-containing resin layer]
A negative electrode was produced in the same manner as in Example 1-1. In addition, a particle-containing resin layer was formed on both sides of the negative electrode in the same manner as the positive electrode.

Thereafter, the same electrolytic solution as in Example 8-1 was poured into this, and the remaining one side was heat-sealed under reduced pressure and sealed. At this time, the electrolyte solution was impregnated into the particle-containing resin layer, and the matrix polymer compound was swollen to form a gel electrolyte (gel electrolyte layer). Thus, a laminated film type battery shown in FIG. 3 having a thickness of 4.5 mm, a width of 30 mm, and a height of 50 mm was produced.

<Example 8-11>
In Example 8-11, the configuration of each of the positive electrode, the negative electrode, the separator, and the particle-containing resin layer and the application target of the particle-containing resin layer were the same as in Example 8-9, and the laminated electrode body was packaged with a laminate film. A laminate film type battery was produced.

[Assembly of laminated film type battery]
The same coating material as in Example 8-9 was uniformly applied to both the positive electrode surface and the negative electrode surface with a predetermined coating thickness (5.0 μm). At this time, during coating, 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.

Thereafter, each electrode to which the paint was applied was passed through a dryer to remove NMP from the particle-containing resin solution layer to obtain a positive electrode with a particle-containing resin layer and a negative electrode with a particle-containing resin layer.

Next, the laminated electrode body was covered with a laminate film having a soft aluminum layer, and the three sides around the laminated electrode body were heat-sealed and sealed and sealed. After that, the same electrolytic solution as in Example 8-9 was poured into this, and the remaining one side was heat-sealed under reduced pressure and sealed. Thus, a laminated film type battery shown in FIGS. 5A to 5C having a battery shape of 4.5 mm in thickness, 30 mm in width, and 50 mm in height was produced.

<Example 8-12>
In the same manner as in Example 8-9, a positive electrode with a particle-containing resin layer, a negative electrode with a particle-containing resin layer having a particle-containing resin layer formed on both surfaces, and a separator were obtained.

[Assembly of square battery]
A positive electrode with a particle-containing resin layer and a negative electrode with a particle-containing resin layer, and a separator are laminated in the order of positive electrode, separator, negative electrode and separator, wound many times in the longitudinal direction into a flat shape, A wound electrode body was formed by fixing with an adhesive tape. Next, as shown in FIG. 9, the wound electrode body was accommodated in a rectangular battery can. Subsequently, after connecting the electrode pin provided on the battery lid and the positive electrode terminal derived from the wound electrode body, the battery can is sealed with the battery lid, and the nonaqueous electrolyte is injected from the electrolyte inlet. And sealed with a sealing member. Thus, a prismatic battery shown in FIG. 9 having a battery shape of 5.2 mm thickness, 34 mm width, and 36 mm height (523436 size) was produced.

<Example 8-13>
In the same manner as in Example 8-9, a positive electrode with a particle-containing resin layer having a particle-containing resin layer formed on both sides, a negative electrode with a particle-containing resin layer having a particle-containing resin layer formed on both sides, and a separator were obtained.

[Assembly of cylindrical battery]
A positive electrode with a particle-containing resin layer, a negative electrode with a particle-containing resin layer, and a separator are laminated in the order of positive electrode, separator, negative electrode, and separator, wound many times in the longitudinal direction, and then the winding end is fixed with an adhesive tape Thus, a wound electrode body was formed. Next, the positive electrode terminal was bonded to the safety valve bonded to the battery lid, and the negative electrode lead was connected to the negative electrode can. After the wound electrode body was sandwiched between a pair of insulating plates and housed inside the battery can, a center pin was inserted into the center of the wound electrode body.

<Example 8-14>
In Example 8-14, a simple battery pack (soft pack) shown in FIGS. 10, 11A, and 11B using the same laminate film type battery as in Example 8-9 was produced.

<Example 8-15>
In Example 8-15, a laminated film type battery was produced in the same manner as in Example 8-9, except that the paint was applied only on both sides of the negative electrode.

<Example 8-16>
In Example 8-16, a laminated film type battery was produced in the same manner as in Example 8-1, except that the paint was applied only on both sides of the positive electrode.

(Battery evaluation: pass / fail judgment of laser measurement, battery bending test)
Regarding the produced laminated film type batteries of each Example, a laser measurement pass / fail judgment and a battery bending test were performed in the same manner as in Example 1-1.

Table 8 shows the evaluation results.

As shown in Table 8, in Examples 8-1 to 8-16, the paint includes particles having a particle diameter and a refractive index within a predetermined range, and the mass ratio (particle / resin) is a predetermined value. It is within the range. Thereby, since the paint was transparent, the pass / fail judgment of the laser measurement was acceptable. Moreover, since the thickness control of the particle-containing resin layer was successful, the battery bending test was acceptable.

<Evaluation of other examples and other comparative examples>
At least one of the particles and the mass ratio (particle / resin) of the paint was applied to Example 3-14 to Example 3-39, Example 4-1 to Example 4-8, and Example 5-1 to The same laser measurement pass judgment was performed for the wound laminate film battery as in Example 8-1 except that it was changed to the same as in Example 5-6. As a result, the same evaluation results as those shown in Table 3, Table 4, and Table 5 were obtained.

At least one of the particles and the mass ratio (particle / resin) of the coating material was changed to the same as in Example 1-2 to Example 1-55 and Comparative Example 1-1 to Comparative Example 1-16 Except for the above, a winding type laminate film battery similar to that in Example 8-2 was also subjected to the same laser measurement pass / fail judgment and battery bending test. As a result, the same evaluation results as those shown in Table 1 were obtained. At least one of the particles and the mass ratio (particle / resin) of the paint was applied to Example 2-1 to Example 2-24, Example 3-1 to Example 3-39, and Example 4-1 to The same laser measurement was performed for the wound laminate film battery as in Example 8-2 except that it was changed to the same as in Example 4-8 and Example 5-1 to Example 5-6. A pass judgment was made. As a result, evaluation results similar to those shown in Tables 2 to 5 were obtained. The same laser is applied to the wound laminate film battery similar to that in Example 8-2 except that the material type of the resin is changed to the same as in Example 6-1 to Example 6-29. Measurement acceptance / rejection and battery bending test were performed. As a result, the same evaluation results as those shown in Table 6 were obtained. The same laser measurement pass / fail was also obtained for the wound laminate film battery as in Example 8-2, except that the coating thickness was changed to the same as in Examples 7-1 to 7-6. Judgment and battery bending test were performed. As a result, the same evaluation results as those shown in Table 7 were obtained.

In the same manner as described above, at least one of paint particles, mass ratio (particle / resin), resin material type, and paint thickness was measured according to Examples and Comparative Examples shown in Tables 1 to 7 (Example 1). The same evaluation was made for the batteries similar to those in Examples 8-3 to 8-9 and Examples 8-11 to 8-16 except that the battery was changed to the same as that in Example 8-3. went. As a result, the same evaluation results as those shown in Tables 1 to 7 were obtained.

In the same manner as described above, at least one of paint particles, mass ratio (particle / resin), resin material type, and paint thickness was measured according to Examples and Comparative Examples shown in Tables 1 to 7 (Example 1). 1, except for Example 3-14 to Example 3-39, Example 4-1 to Example 4-8, and Example 5-1 to Example 5-6) The same evaluation was performed on the same batteries as in Examples 8-10. As a result, the same evaluation results as those shown in Tables 1 to 3 and Tables 6 to 7 were obtained.

10. Other Embodiments The present technology has been described above with reference to the embodiments and examples. However, the present technology is not limited thereto, and various modifications can be made within the scope of the gist of the present technology.

For example, the numerical values, structures, shapes, materials, raw materials, manufacturing processes and the like given in the above-described embodiments and examples are merely examples, and different numerical values, structures, shapes, materials, raw materials, and the like as necessary. A manufacturing process or the like may be used.

Further, the configurations, methods, processes, shapes, materials, numerical values, and the like of the above-described embodiments and examples can be combined with each other without departing from the gist of the present technology. For example, the nonaqueous electrolyte battery may be a primary battery.

In addition, the present technology can be similarly applied to a case of having another battery structure such as a coin type or a button type.

In the third to fourth embodiments, 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. In this case, the gel electrolyte layer 56 may have a configuration in which the filler is omitted. In the third embodiment, the electrode may be an electrode with a particle-containing resin layer using a binder polymer compound. In this case, the gel electrolyte layer 56 may have a configuration in which the filler is omitted.

In addition, this technique can also take the following structures.
[1]
A positive electrode;
A negative electrode,
A separator;
An electrolyte,
A particle-containing resin layer containing particles and resin,
The particle diameter D50 of the particles is 50 nm or more and 450 nm or less, or 750 nm or more and 10,000 nm or less,
The particle has a refractive index of 1.3 or more and less than 2.4,
The battery has a mass ratio (particle / resin) between the particles and the resin of 15/85 or more and 90/10 or less.
[2]
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 [1], which is formed on at least one selected main surface.
[3]
The resin is a binder polymer compound,
The battery according to [2], wherein the particle-containing resin layer holds the electrolytic solution in a void formed by at least one of the resin and the particles.
[4]
The resin is a matrix polymer compound,
The particle-containing resin layer includes the particles and the matrix polymer compound, and the particle-containing resin solution layer, which is a precursor of the particle-containing resin layer, has both surfaces of at least one of the positive electrode and the negative electrode, Or formed on at least one surface of both surfaces of the separator,
The battery according to [2], wherein the particle-containing resin solution layer is impregnated with the electrolytic solution, and the matrix polymer compound swells and gels.
[5]
The battery according to any one of [1] to [4], wherein the particle-containing resin layer has a thickness of 1 μm to 15 μm.
[6]
The battery according to any one of [1] to [5], wherein the particles are at least one of inorganic particles and organic particles.
[7]
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. , Aluminum hydroxide, zinc hydroxide, boehmite, white carbon, zirconium oxide hydrate, magnesium oxide hydrate, magnesium hydroxide octahydrate, boron carbide, silicon nitride, boron nitride, aluminum nitride, titanium nitride, fluorine Lithium fluoride, aluminum fluoride, calcium fluoride, barium fluoride, magnesium fluoride, trilithium phosphate, magnesium phosphate, magnesium hydrogen phosphate, ammonium polyphosphate, silicate mineral, carbonate mineral, oxide mineral At least one of particles selected from Ranaru group,
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 battery according to [6], which is at least one particle selected from the group consisting of:
[8]
The silicate mineral is talc, calcium silicate, zinc silicate, zirconium silicate, aluminum silicate, magnesium silicate, kaolinite, sepiolite, imogolite, sericite, pyrophyllite, mica, zeolite, mullite, saponite. At least one selected from the group consisting of attapulgite and montmorillonite,
The carbonate mineral is at least one selected from the group consisting of hydrotalcite and dolomite,
The battery according to [7], wherein the oxide mineral is spinel.
[9]
The resin is polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride-tetrafluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer. 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] to [8].
[10]
The battery according to any one of [1] to [9], wherein the particles are plate-like particles having a thickness of 50 nm to 450 nm or needle-like particles having a thickness of 50 nm to 450 nm.
[11]
A separator substrate;
A particle-containing resin layer provided on at least one main surface of the separator substrate and containing particles and a resin;
The particle diameter D50 of the particles is 50 nm or more and 450 nm or less, or 750 nm or more and 10,000 nm or less,
The particle has a refractive index of 1.3 or more and less than 2.4,
The mass ratio (particle / resin) between the particles and the resin is a separator of 15/85 or more and 90/10 or less.
[12]
Electrodes,
A particle-containing resin layer provided on at least one main surface of the electrode and containing particles and a resin;
The particle diameter D50 of the particles is 50 nm or more and 450 nm or less, or 750 nm or more and 10,000 nm or less,
The particle has a refractive index of 1.3 or more and less than 2.4,
The electrode with the particle | grain containing resin layer whose mass ratio (particle / resin) of the said particle | grain and the said resin is 15/85 or more and 90/10 or less.
[13]
Particles,
Resin,
A solvent,
The particle diameter D50 of the particles is 50 nm or more and 450 nm or less, or 750 nm or more and 10,000 nm or less,
The particle has a refractive index of 1.3 or more and less than 2.4,
The coating material whose mass ratio (particle / resin) of said particle | grain and said resin is 15/85 or more and 90/10 or less.
[14]
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.
[15]
[1] An electronic apparatus comprising the battery according to any one of [10] and receiving power supply from the battery.
[16]
The battery according to any one of [1] to [10];
A conversion device that receives supply of electric power from the battery and converts it into driving force of a vehicle;
An electric vehicle comprising: a control device that performs information processing related to vehicle control based on information related to the battery.
[17]
[1] 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.
[18]
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.
[19]
[1] 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.

DESCRIPTION OF SYMBOLS 11 ... Separator, 11a ... Separator base material, 11b ... Particle-containing resin layer, 21 ... Electrode with particle-containing resin layer, 21a ... Electrode, 21b ... Particle-containing resin layer, 50・・・ Wound electrode body, 51 ・・・ Positive electrode lead, 52 ・・・ Negative electrode lead, 53 ・・・ Positive electrode, 53A ・・・ Positive electrode current collector, 53B ・・・ Positive electrode active material layer, 54 ・・・Negative electrode, 54A ... negative electrode current collector, 54B ... negative electrode active material layer, 55 ... separator, 56 ... gel electrolyte layer, 57 ... 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 ... Fixed 80, nonaqueous electrolyte battery, 81 ... battery can, 82a, 82 ... Insulating plate, 83 ... Battery cover, 84 ... Safety valve, 84a ... Projection, 85 ... Disc holder, 86 ... Shut-off disc, 86a ... Hole, 87 ... Heat-sensitive resistance element, 88 ... gasket, 89 ... sub-disc, 90 ... wound electrode body, 91 ... positive electrode, 91A ... positive electrode current collector, 91B ... positive electrode active material Layer, 91C ... particle-containing resin layer, 92 ... negative electrode, 92A ... negative electrode current collector, 92B ... negative electrode active material layer, 92C ... particle-containing resin layer, 93 ... separator, 93a ... Separator base material, 93b ... Particle-containing resin layer, 94 ... Center pin, 95 ... Positive electrode lead, 96 ... Negative electrode lead, 100 ... Nonaqueous electrolyte battery, 111 ... -Exterior can, 112 ... Battery cover, 113 ... Electrode pin, 114 ... Edge body 115... Through-hole 116... Internal pressure release mechanism 116 a... First opening groove 116 b ... Second opening groove 117 117 Electrolyte injection port 118. -Sealing member, 120 ... Winding electrode body, 121 ... Positive electrode terminal, 131 ... Battery cell, 131a ... Terrace part, 132a, 132b ... Lead, 133a, 133b, 133c ... Insulating tape 134 ... Insulating plate 135 ... Circuit board 136 ... Connector 301 ... Battery pack 301a ... Secondary battery 302a ... Charge control switch 302b -Diode, 303a ... Discharge control switch, 303b ... Diode, 304 ... Switch part, 307 ... Current detection resistor, 308 ... Temperature detection element, 310 ... Control part, 311 ...・ Electric Pressure detection unit, 313 ... Current measurement unit, 314 ... Switch control unit, 317 ... Memory, 318 ... Temperature detection unit, 321 ... Positive terminal, 322 ... Negative terminal, 400 ··· Power storage system, 401 ··· Housing, 402 ··· Centralized power system, 402a · · · Thermal power generation, 402b · · · Nuclear power generation, 402c · · · Hydroelectric power generation, 403 · · · Power storage device, ..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, DESCRIPTION OF SYMBOLS 11 ... Sensor, 412 ... Information network, 413 ... Server, 500 ... Hybrid vehicle, 501 ... Engine, 502 ... Generator, 503 ... Electric power driving force converter, 504a ... Drive wheel, 504b ... Drive wheel, 505a ... Wheel, 505b ... Wheel, 508 ... Battery, 509 ... Vehicle control device, 510 ... Sensor, 511 ... Charge mouth

Claims

A positive electrode;
A negative electrode,
A separator;
An electrolyte,
A particle-containing resin layer containing particles and resin,
The particle diameter D50 of the particles is 50 nm or more and 450 nm or less, or 750 nm or more and 10,000 nm or less,
The particle has a refractive index of 1.3 or more and less than 2.4,
The battery has a mass ratio (particle / resin) between the particles and the resin of 15/85 or more and 90/10 or less.
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 claim 1, wherein the battery is formed on at least one selected main surface.
The resin is a binder polymer compound,
The battery according to claim 2, wherein the particle-containing resin layer holds the electrolytic solution in a gap formed by at least one of the resin and the particles.
The resin is a matrix polymer compound,
The particle-containing resin layer includes the particles and the matrix polymer compound, and the particle-containing resin solution layer, which is a precursor of the particle-containing resin layer, has both surfaces of at least one of the positive electrode and the negative electrode, Or formed on at least one surface of both surfaces of the separator,
The battery according to claim 2, wherein the particle-containing resin solution layer is impregnated with the electrolytic solution, and the matrix polymer compound swells and gels.
The battery according to claim 1, wherein the particle-containing resin layer has a thickness of 1 μm or more and 15 μm or less.
The battery according to claim 1, wherein the particles are at least one of inorganic particles and organic particles.
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. , Aluminum hydroxide, zinc hydroxide, boehmite, white carbon, zirconium oxide hydrate, magnesium oxide hydrate, magnesium hydroxide octahydrate, boron carbide, silicon nitride, boron nitride, aluminum nitride, titanium nitride, fluorine Lithium fluoride, aluminum fluoride, calcium fluoride, barium fluoride, magnesium fluoride, trilithium phosphate, magnesium phosphate, magnesium hydrogen phosphate, ammonium polyphosphate, silicate mineral, carbonate mineral, oxide mineral At least one of particles selected from Ranaru group,
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 battery according to claim 6, wherein the battery is at least one particle selected from the group consisting of:
The silicate mineral is talc, calcium silicate, zinc silicate, zirconium silicate, aluminum silicate, magnesium silicate, kaolinite, sepiolite, imogolite, sericite, pyrophyllite, mica, zeolite, mullite, saponite. At least one selected from the group consisting of attapulgite and montmorillonite,
The carbonate mineral is at least one selected from the group consisting of hydrotalcite and dolomite,
The battery according to claim 7, wherein the oxide mineral is spinel.
The resin is polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride-tetrafluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer. 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 At least one selected from the group consisting of ether, polysulfone, polyethersulfone, polyphenylene sulfide, polyetherimide, polyimide, polyamide, polyamideimide, polyacrylonitrile, polyvinyl alcohol, polyether, acrylic resin, polyester, polyethylene glycol The battery according to claim 1.
2. The battery according to claim 1, wherein the particles are plate-like particles having a thickness of 50 nm to 450 nm or needle-like particles having a thickness of 50 nm to 450 nm.
A separator substrate;
A particle-containing resin layer provided on at least one main surface of the separator substrate and containing particles and a resin;
The particle diameter D50 of the particles is 50 nm or more and 450 nm or less, or 750 nm or more and 10,000 nm or less,
The particle has a refractive index of 1.3 or more and less than 2.4,
The mass ratio (particle / resin) between the particles and the resin is a separator of 15/85 or more and 90/10 or less.
Electrodes,
A particle-containing resin layer provided on at least one main surface of the electrode and containing particles and a resin;
The particle diameter D50 of the particles is 50 nm or more and 450 nm or less, or 750 nm or more and 10,000 nm or less,
The particle has a refractive index of 1.3 or more and less than 2.4,
The electrode with the particle | grain containing resin layer whose mass ratio (particle / resin) of the said particle | grain and the said resin is 15/85 or more and 90/10 or less.
Particles,
Resin,
A solvent,
The particle diameter D50 of the particles is 50 nm or more and 450 nm or less, or 750 nm or more and 10,000 nm or less,
The particle has a refractive index of 1.3 or more and less than 2.4,
The coating material whose mass ratio (particle / resin) of said particle | grain and said resin is 15/85 or more and 90/10 or less.
A battery according to claim 1;
A control unit for controlling the battery;
A battery pack having an exterior housing the battery.
An electronic device having the battery according to claim 1 and receiving supply of electric power from the battery.
A battery according to claim 1;
A conversion device that receives supply of electric power from the battery and converts it into driving force of a vehicle;
An electric vehicle comprising: a control device that performs information processing related to vehicle control based on information related to the battery.
A power storage device that has the battery according to claim 1 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 claim 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 claim 1 or that supplies power to the battery from a power generation device or a power network.