Separator and secondary battery

Abstract

Provided is a secondary cell with low deterioration. Provided is a very safe secondary cell. Provided is a separator having superior characteristics. Provided is a separator for realizing the very safe secondary cell. Provided is a novel separator. The present invention provides a separator in which a polymer porous film, and a layer having a ceramic material including metal oxide microparticles, are layered, wherein the film thickness of the layer having the ceramic material is 1-100 µm (inclusive), and the film thickness of the polymer porous film is 4-50 µm (inclusive).

Description

[Technical Field]

[0001] The present invention relates to a secondary battery using a separator and a method for manufacturing the same, or to a mobile information terminal, a vehicle, etc. that has a secondary battery.

[0002] One embodiment of the present invention relates to an object, a method, or a manufacturing method. Alternatively, the present invention relates to a process, a machine, a manufacture, or a composition of matter. One embodiment of the present invention relates to a semiconductor device, a display device, a light-emitting device, a power storage device, a lighting device, an electronic device, or a manufacturing method thereof.

[0003] In this specification, the term "electronic device" refers to any device having a power storage device, and includes electro-optical devices having a power storage device, information terminal devices having a power storage device, and the like.

[0004] In this specification, the term "power storage device" refers to elements and devices in general that have a power storage function, including, for example, power storage devices such as lithium ion secondary batteries (also called secondary batteries), lithium ion capacitors, and electric double layer capacitors. [Background technology]

[0005] In recent years, there has been active development of various types of electricity storage devices, such as lithium-ion secondary batteries, lithium-ion capacitors, and air batteries. Demand for high-power, high-energy-density lithium-ion secondary batteries, in particular, has rapidly expanded alongside the development of the semiconductor industry, as they are used in portable information terminals such as mobile phones, smartphones, and notebook computers, portable music players, digital cameras, medical devices, and next-generation clean-energy vehicles such as hybrid vehicles (HVs), electric vehicles (EVs), and plug-in hybrid vehicles (PHVs), making them indispensable in today's information society as a rechargeable energy source.

[0006] In order to simultaneously improve the thermal and electrochemical safety and performance of lithium ion secondary batteries, improvements to the separator have been investigated.

[0007] For example, Patent Document 1 discloses a method for producing an organic-inorganic composite porous separator membrane containing an organic material and an inorganic material. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Special Publication No. 2008-524824 Summary of the Invention [Problem to be solved by the invention]

[0009] An object of one embodiment of the present invention is to provide a secondary battery with little deterioration. Alternatively, an object of one embodiment of the present invention is to provide a highly safe secondary battery. Alternatively, an object of one embodiment of the present invention is to provide a separator with excellent characteristics. Alternatively, an object of one embodiment of the present invention is to provide a separator that realizes a highly safe secondary battery. Alternatively, an object of one embodiment of the present invention is to provide a novel separator. Alternatively, an object of one embodiment of the present invention is to provide a method for manufacturing a separator that realizes a highly safe secondary battery. Alternatively, an object of one embodiment of the present invention is to provide a method for manufacturing a novel separator.

[0010] Note that the description of these problems does not preclude the existence of other problems. Note that one embodiment of the present invention does not necessarily solve all of these problems. Note that problems other than these can be extracted from the description in the specification, drawings, and claims. [Means for solving the problem]

[0011] One aspect of the present invention is a separator comprising a porous polymer membrane and a layer having a ceramic material containing metal oxide fine particles laminated together, wherein the layer having the ceramic material has a thickness of 1 μm or more and 100 μm or less, and the porous polymer membrane has a thickness of 4 μm or more and 50 μm or less.

[0012] Alternatively, in one embodiment of the present invention, the density of the layer having the ceramic material is 0.1 g / cm 3 More than 2g / cm 3 Below is the separator:

[0013] Another aspect of the present invention is a separator, wherein the porosity of the porous polymer film is 20% by volume or more and 90% by volume or less.

[0014] Alternatively, in one aspect of the present invention, the weight per unit area of ​​the porous polymer membrane is 4 g / m 2 More than 20g / m 2 Preferably, 5 g / m or less 2 More than 12g / m 2 Below is the separator:

[0015] Another embodiment of the present invention is a separator in which the metal oxide fine particles contain one or more of magnesium oxide, aluminum oxide, titanium oxide, silicon oxide, magnesium hydroxide, aluminum hydroxide, and titanium hydroxide.

[0016] Another embodiment of the present invention is a separator in which the metal oxide fine particles contain magnesium hydroxide.

[0017] Another embodiment of the present invention is a separator in which the metal oxide fine particles have an average particle size of 0.01 μm or more and 50 μm or less.

[0018] Another aspect of the present invention is a separator in which a layer containing a ceramic material is in contact with one surface of a porous polymer membrane.

[0019] Alternatively, one aspect of the present invention is a separator comprising a porous polymer membrane and layers each having a plurality of ceramic materials including metal oxide microparticles, the layers each having a plurality of ceramic materials being positioned so as to sandwich the porous polymer membrane, the thickness of the layer each having a ceramic material being 1 μm or more and 100 μm or less, and the thickness of the porous polymer membrane being 4 μm or more and 50 μm or less.

[0020] Alternatively, in one aspect of the present invention, the density of the layer having the ceramic material is 0.1 g / cm 3 More than 2g / cm 3 Below is the separator:

[0021] Another aspect of the present invention is a separator, wherein the porosity of the porous polymer film is 20% by volume or more and 90% by volume or less.

[0022] Alternatively, in one aspect of the present invention, the weight per unit area of ​​the porous polymer membrane is 4 g / m 2 More than 20g / m 2 Preferably, it is 5 g / m or less. 2 More than 12g / m 2 Below is the separator:

[0023] Another embodiment of the present invention is a separator in which the metal oxide fine particles contain one or more of magnesium oxide, aluminum oxide, titanium oxide, silicon oxide, magnesium hydroxide, aluminum hydroxide, and titanium hydroxide.

[0024] Another embodiment of the present invention is a separator in which the metal oxide fine particles contain magnesium hydroxide.

[0025] Another embodiment of the present invention is a separator in which the metal oxide fine particles have an average particle size of 0.01 μm or more and 50 μm or less.

[0026] Another aspect of the present invention is a separator in which a layer containing a ceramic material is in contact with one surface of a porous polymer membrane.

[0027] Another embodiment of the present invention is a secondary battery including a positive electrode, a negative electrode, and the above-described separator and an electrolyte sandwiched between the positive electrode and the negative electrode.

[0028] In the above configuration, it is preferable that the electrolyte is disposed inside the pores of the porous polymer membrane.

[0029] Alternatively, one aspect of the present invention is a method for producing a separator, comprising: a first step of mixing a ceramic material containing metal oxide fine particles with a first solvent to prepare a first mixture; a second step of mixing the first mixture, a first binder, and a second solvent to prepare a second mixture; a third step of mixing the second mixture, a second binder, and a third solvent to prepare a third mixture; a fourth step of applying the third mixture to a porous polymer membrane; and a fifth step of heating the porous polymer membrane coated with the third mixture at a temperature of 60°C to 300°C to dry it.

[0030] In the fifth step, the porous polymer membrane coated with the third mixture is more preferably heated at a temperature of 60° C. or higher and 200° C. or lower to dry it.

[0031] The porosity of a porous polymer membrane refers to the ratio of the volume of pores in the porous polymer membrane. The porosity of a layer containing a ceramic material refers to the ratio of the volume of pores in the layer containing a ceramic material. The density can be calculated from the thickness, weight, and area.

[0032] The porosity of the layer containing the ceramic material is, for example, 50% by volume or more. [Effects of the Invention]

[0033] According to one embodiment of the present invention, a secondary battery with little deterioration can be provided. According to another embodiment of the present invention, a highly safe secondary battery can be provided. According to another embodiment of the present invention, a separator with excellent characteristics can be provided. According to another embodiment of the present invention, a separator that realizes a highly safe secondary battery can be provided. According to another embodiment of the present invention, a novel separator can be provided. According to another embodiment of the present invention, a method for manufacturing a separator that realizes a highly safe secondary battery can be provided. According to another embodiment of the present invention, a method for manufacturing a novel separator can be provided.

[0034] Note that the description of these effects does not preclude the existence of other effects. Note that one embodiment of the present invention does not necessarily have all of these effects. Note that effects other than these will become apparent from the description in the specification, drawings, claims, etc., and it is possible to extract other effects from the description in the specification, drawings, claims, etc. [Brief explanation of the drawings]

[0035] 1A to 1D are cross-sectional views of an example of a secondary battery. 2A to 2D are cross-sectional views of an example of a secondary battery. FIG. 3 is a flow diagram showing an example of a method for producing a separator coated with a ceramic material. FIG. 4 shows a method for preparing the material. FIG. 5 is an example of a cross-sectional view showing a process of one embodiment of the present invention. FIG. 6 is a diagram illustrating the crystal structure of the positive electrode active material. FIG. 7 is a diagram illustrating the crystal structure of the positive electrode active material. 8A and 8B are diagrams showing an example of the external appearance of a secondary battery. 9A and 9B are diagrams illustrating a method for producing a secondary battery. 10A and 10B are diagrams illustrating a method for manufacturing a secondary battery. FIG. 11 is a diagram showing an example of the appearance of a secondary battery. FIG. 12 is a top view showing an example of a secondary battery manufacturing apparatus. FIG. 13 is a cross-sectional view showing an example of a method for producing a secondary battery. 14A to 14C are perspective views showing an example of a method for manufacturing a secondary battery, and Fig. 14D is a cross-sectional view corresponding to Fig. 14C. 15A to 15F are perspective views showing an example of a method for manufacturing a secondary battery. FIG. 16 is a cross-sectional view showing an example of a secondary battery. Fig. 17A is a diagram showing an example of a secondary battery, and Fig. 17B and Fig. 17C are diagrams showing an example of a method for producing a laminate. 18A to 18C are diagrams showing an example of a method for manufacturing a secondary battery. 19A and 19B are cross-sectional views showing an example of a laminate, and Fig. 19C is a cross-sectional view showing an example of a secondary battery. 20A and 20B are diagrams showing an example of a secondary battery, and Fig. 20C is a diagram showing the inside of the secondary battery. 21A to 21C are diagrams showing an example of a secondary battery. Fig. 22A is a perspective view showing an example of a battery pack, Fig. 22B is a block diagram showing an example of a battery pack, and Fig. 22C is a block diagram showing an example of a vehicle having a motor. 23A to 23E are diagrams showing an example of a transportation vehicle. FIG. 24A is a diagram showing an electric bicycle, FIG. 24B is a diagram showing a secondary battery of the electric bicycle, and FIG. 24C is a diagram explaining an electric motorcycle. 25A and 25B are diagrams illustrating an example of a power storage device. 26A to 26E are diagrams showing an example of an electronic device. 27A to 27H are diagrams illustrating an example of an electronic device. 28A to 28C are diagrams illustrating an example of an electronic device. FIG. 29 is a diagram illustrating an example of an electronic device. 30A to 30C are diagrams illustrating an example of an electronic device. 31A to 31C are diagrams showing an example of an electronic device. FIG. 32 is a diagram showing the results of measuring the concentration of cobalt solution by atomic absorption spectrometry. DETAILED DESCRIPTION OF THE INVENTION

[0036] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following description, and it will be readily understood by those skilled in the art that various modifications can be made to the embodiments and details. Furthermore, the present invention should not be interpreted as being limited to the description of the embodiments shown below.

[0037] Furthermore, in this specification and the like, crystal planes and directions are indicated by Miller indices. In crystallography, crystal planes and directions are indicated by a superscript bar after the number, but in this specification and the like, due to restrictions on application notation, numbers may be expressed by a minus sign (-) before them instead of a bar above them. Furthermore, individual directions indicating directions within a crystal are expressed with [ ], collective directions indicating all equivalent directions are expressed with < >, individual planes indicating crystal planes are expressed with ( ), and collective planes with equivalent symmetry are expressed with {}.

[0038] In this specification, the surface layer of particles of active material or the like is preferably, for example, a region within 50 nm from the surface, more preferably within 35 nm, and even more preferably within 20 nm. Surfaces formed by cracks or fissures may also be referred to as the surface. The region deeper than the surface layer is referred to as the interior.

[0039] In this specification, the layered rock-salt type crystal structure of a composite oxide containing lithium and a transition metal refers to a crystal structure having a rock-salt type ion arrangement in which cations and anions are alternately arranged, and in which the transition metal and lithium are regularly arranged to form a two-dimensional plane, allowing two-dimensional diffusion of lithium. Defects such as cation or anion deficiencies may also be present. Furthermore, strictly speaking, the layered rock-salt type crystal structure may have a distorted rock-salt type crystal lattice structure.

[0040] In this specification and the like, the rock salt type crystal structure refers to a structure in which cations and anions are arranged alternately, and it is also possible for there to be a deficiency of cations or anions.

[0041] In this specification and the like, the O3'-type crystal structure of a composite oxide containing lithium and a transition metal refers to a crystal structure in the space group R-3m that is not a spinel-type crystal structure, but in which ions of cobalt, magnesium, etc. occupy hexacoordinated oxygen positions and the arrangement of cations has a symmetry similar to that of the spinel-type. Note that in the O3'-type crystal structure, a light element such as lithium may occupy a tetracoordinated oxygen position, and in this case, the arrangement of ions also has a symmetry similar to that of the spinel-type.

[0042] The O3' type crystal structure can also be said to be similar to the CdCl2 type crystal structure, although it has random Li between the layers. This CdCl2 type-like crystal structure is similar to the CdCl2 type crystal structure, but the O3' type crystal structure has random Li between the layers. 0.06 Although this is close to the crystal structure when charged to NiO2, it is known that simply pure lithium cobalt oxide or layered rock salt-type positive electrode active materials containing a large amount of cobalt do not normally adopt this crystal structure.

[0043] The anions in layered rock salt crystals and rock salt crystals have a cubic close-packed structure (face-centered cubic lattice structure). It is estimated that the anions in O3'-type crystals also have a cubic close-packed structure. When these crystals contact, there is a crystal plane where the cubic close-packed structures formed by the anions are aligned. However, the space group of layered rock salt crystals and O3'-type crystals is R-3m, which is different from the space groups of rock salt crystals, Fm-3m (the space group of general rock salt crystals) and Fd-3m (the space group of rock salt crystals with the simplest symmetry). Therefore, the Miller indices of the crystal planes that satisfy the above conditions are different between layered rock salt crystals and O3'-type crystals and rock salt crystals. In this specification, when the cubic close-packed structures formed by the anions are aligned in layered rock salt crystals, O3'-type crystals, and rock salt crystals, the crystal orientations may be said to be approximately aligned.

[0044] The general alignment of the crystal orientations of the two regions can be determined from TEM (transmission electron microscope), STEM (scanning transmission electron microscope), HAADF-STEM (high-angle annular dark-field scanning transmission electron microscope), and ABF-STEM (annular bright-field scanning transmission electron microscope) images. X-ray diffraction (XRD), electron diffraction, and neutron diffraction can also be used. In STEM images, the arrangement of cations and anions can be observed as repeated bright and dark lines. When the orientation of the cubic close-packed structure of the layered rock salt crystal and the rock salt crystal is aligned, the angle between the repeated bright and dark lines between the crystals can be observed to be within ±5°, more preferably ±2.5°. Light elements such as oxygen and fluorine may not be clearly visible in TEM images, but in such cases, the alignment of the orientations can be determined from the arrangement of metal elements.

[0045] In this specification, the theoretical capacity of a positive electrode active material refers to the amount of electricity when all of the intercalable lithium contained in the positive electrode active material is deintercalated. For example, the theoretical capacity of LiCoO2 is 274 mAh / g, the theoretical capacity of LiNiO2 is 274 mAh / g, and the theoretical capacity of LiMn2O4 is 148 mAh / g.

[0046] The amount of lithium remaining in the positive electrode active material that can be inserted or removed can be determined by the x in the composition formula, for example, Li x x in CoO2, or Li x This is represented by x in MO2 (M is a transition metal). x can also be considered the occupancy rate of Li on the lithium site. When lithium cobalt oxide satisfies the stoichiometric ratio, it is LiCoO2, and the occupancy rate of Li on the lithium site is x = 1. A secondary battery that has completed discharge is also LiCoO2, and x can be said to be approximately 1. End of discharge here refers to a state where, for example, the voltage drops below 2.5 V (vs. Li at the counter electrode) at a current of 100 mA / g. In lithium-ion secondary batteries, when the occupancy rate of lithium on the lithium site reaches x = 1 and no more lithium can enter, the voltage drops rapidly. This is when discharge is considered to have completed. Generally, in lithium-ion secondary batteries using LiCoO2, the discharge voltage drops rapidly before reaching 2.5 V, so discharge is considered to have completed under the above conditions.

[0047] In this specification, a non-equilibrium phase change refers to a phenomenon that causes a non-linear change in a physical quantity. For example, a non-equilibrium phase change occurs around the peak in the dQ / dV curve obtained by differentiating capacitance (Q) with voltage (V), and it is believed that the crystal structure changes significantly.

[0048] A secondary battery has, for example, a positive electrode and a negative electrode. A material constituting the positive electrode is a positive electrode active material. The positive electrode active material is, for example, a substance that undergoes a reaction that contributes to the charge / discharge capacity. Note that the positive electrode active material may partially contain a substance that does not contribute to the charge / discharge capacity.

[0049] In this specification and the like, the positive electrode active material of one embodiment of the present invention may be referred to as a positive electrode material, a positive electrode material for a secondary battery, or the like. Also, in this specification and the like, the positive electrode active material of one embodiment of the present invention preferably includes a compound. Also, in this specification and the like, the positive electrode active material of one embodiment of the present invention preferably includes a composition. Also, in this specification and the like, the positive electrode active material of one embodiment of the present invention preferably includes a composite.

[0050] Discharge rate is the relative ratio of the current during discharge to the battery capacity, and is expressed in units of C. For a battery with a rated capacity of X (Ah), the current equivalent to 1C is X (A). When discharging at a current of 2X (A), it is said to have been discharged at 2C, and when discharging at a current of X / 5 (A), it is said to have been discharged at 0.2C. The same is true for charge rate; when charging at a current of 2X (A), it is said to have been charged at 2C, and when charging at a current of X / 5 (A), it is said to have been charged at 0.2C.

[0051] Constant current charging, for example, refers to a method of charging at a constant charge rate. Constant voltage charging, for example, refers to a method of charging at a constant voltage once the upper voltage limit is reached. Constant current discharging, for example, refers to a method of discharging at a constant discharge rate.

[0052] (Embodiment 1) In this embodiment, an example of a secondary battery of one embodiment of the present invention will be described with reference to Fig. 1. The secondary battery includes an outer casing (not shown), a positive electrode 503, a negative electrode 506, a separator 507, and an electrolyte 508 in which a lithium salt or the like is dissolved. The separator 507 is provided between the positive electrode 503 and the negative electrode 506.

[0053] 1A, a positive electrode 503 includes a positive electrode active material layer 502 and a positive electrode current collector 501. The positive electrode active material layer 502 includes a positive electrode active material 561, a conductive additive, and a binder. FIG. 1B is an enlarged view of a region 502a of the positive electrode active material layer 502, showing an example in which acetylene black 553 and graphene 554 are used as conductive additives. The positive electrode will be described in detail later.

[0054] The negative electrode 506 includes a negative electrode active material layer 505 and a negative electrode current collector 504. The negative electrode active material layer 505 includes a negative electrode active material 563, a conductive additive, and a binder (not shown). FIG. 1D is an enlarged view of a region 505a of the negative electrode active material layer 505, showing an example in which acetylene black 556 and graphene 557 are used as conductive additives. The negative electrode will be described in detail later.

[0055] As the binder, it is preferable to use a rubber material such as styrene-butadiene rubber (SBR), styrene-isoprene-styrene rubber, acrylonitrile-butadiene rubber, butadiene rubber, ethylene-propylene-diene copolymer, etc. Also, fluororubber can be used as the binder.

[0056] Furthermore, it is preferable to use, for example, a water-soluble polymer as the binder. Examples of water-soluble polymers that can be used include polysaccharides. Examples of polysaccharides that can be used include cellulose derivatives such as carboxymethyl cellulose (CMC), methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, and regenerated cellulose, as well as starch. It is even more preferable to use these water-soluble polymers in combination with the aforementioned rubber material.

[0057] Alternatively, it is preferable to use materials such as polystyrene, polymethyl acrylate, polymethyl methacrylate (polymethyl methacrylate, PMMA), sodium polyacrylate, polyvinyl alcohol (PVA), polyethylene oxide (PEO), polypropylene oxide, polyimide, polyvinyl chloride, polytetrafluoroethylene, polyethylene, polypropylene, polyisobutylene, polyethylene terephthalate, nylon, polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), ethylene propylene diene polymer, polyvinyl acetate, and nitrocellulose as the binder.

[0058] The binder may be used in combination with two or more of the above.

[0059] For example, a material with particularly excellent viscosity adjusting effect may be used in combination with other materials. For example, while rubber materials have excellent adhesive strength and elasticity, it may be difficult to adjust the viscosity when mixed with a solvent. In such cases, it is preferable to mix a material with particularly excellent viscosity adjusting effect with a rubber material. As a material with particularly excellent viscosity adjusting effect, for example, a water-soluble polymer may be used. Furthermore, as water-soluble polymers with particularly excellent viscosity adjusting effect, the above-mentioned polysaccharides, for example, carboxymethyl cellulose (CMC), methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, cellulose derivatives such as regenerated cellulose, and starch may be used.

[0060] In addition, the solubility of cellulose derivatives such as carboxymethyl cellulose can be increased by converting them into salts such as sodium or ammonium salts of carboxymethyl cellulose, making them more effective as viscosity adjusters. Higher solubility can also improve dispersibility with the active material and other components when preparing electrode slurry. In this specification, the cellulose and cellulose derivatives used as electrode binders also include their salts.

[0061] Because water-soluble polymers have functional groups, they tend to be stably adsorbed onto the surface of active materials, etc. When water-soluble polymers are adsorbed onto the surface of active materials, etc., particles of the active materials repel each other electrostatically, allowing the active materials, etc. to be stably dispersed. Furthermore, many cellulose derivatives, such as carboxymethyl cellulose, have functional groups, such as hydroxyl groups and carboxyl groups, and because of the functional groups, the polymers may interact with each other and widely cover the surface of the active material, which is expected to suppress excessive electrolyte decomposition.

[0062] When the binder covers the surface of the active material or contacts the surface, it is expected to form a film, which acts as a passivation film and suppresses decomposition of the electrolyte. Here, for example, when a passivation film is formed on the surface of the active material, it can suppress decomposition of the electrolyte at the battery reaction potential. Furthermore, it is more desirable that the passivation film suppresses electrical conductivity while still allowing lithium ions to conduct.

[0063] The active material layer can be produced by mixing an active material, a binder, a conductive additive and a solvent to prepare a slurry, forming the slurry on a current collector, and volatilizing the solvent.

[0064] The solvent used for the slurry is preferably a polar solvent, such as water, methanol, ethanol, acetone, tetrahydrofuran (THF), dimethylformamide (DMF), N-methylpyrrolidone (NMP), and dimethyl sulfoxide (DMSO), or a mixture of two or more of these.

[0065] The positive electrode current collector 501 and the negative electrode current collector 504 can be made of a highly conductive material that does not alloy with carrier ions such as lithium, such as metals such as stainless steel, gold, platinum, zinc, iron, copper, aluminum, and titanium, or alloys thereof. Aluminum alloys containing elements that improve heat resistance, such as silicon, titanium, neodymium, scandium, and molybdenum, can also be used. They may also be made of a metal element that reacts with silicon to form a silicide. Examples of metal elements that react with silicon to form a silicide include zirconium, titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, and nickel. The current collectors can be in various shapes, such as sheet, mesh, punched metal, and expanded metal. The current collectors preferably have a thickness of 10 μm to 30 μm.

[0066] It is preferable that the negative electrode current collector 504 is made of a material that does not alloy with carrier ions such as lithium.

[0067] As a current collector, a titanium compound may be provided by laminating it on the above-described metal element. As the titanium compound, for example, titanium nitride, titanium oxide, titanium nitride in which part of nitrogen is substituted with oxygen, titanium oxide in which part of oxygen is substituted with nitrogen, and titanium oxynitride (TiO x N y , 0 < x < 2, 0 < y < 1), one selected therefrom, or two or more may be mixed or laminated and used. Among them, titanium nitride is particularly preferable because it has high conductivity and a high function of suppressing oxidation. By providing the titanium compound on the surface of the current collector, for example, the reaction between the material of the active material layer formed on the current collector and the metal can be suppressed. When the active material layer contains a compound having oxygen, the oxidation reaction between the metal element and oxygen can be suppressed. For example, when aluminum is used as the current collector and the active material layer is formed using graphene oxide described later, there may be a concern about the oxidation reaction between the oxygen of graphene oxide and aluminum. In such a case, by providing a titanium compound on aluminum, the oxidation reaction between the current collector and graphene oxide can be suppressed.

[0068] Also, as graphene 554 and graphene 557, graphene or a graphene compound can be used.

[0069] In this specification and the like, the graphene compound includes multilayer graphene, multi-graphene, graphene oxide, multilayer graphene oxide, multi-graphene oxide, reduced graphene oxide, reduced multilayer graphene oxide, reduced multi-graphene oxide, graphene quantum dots, and the like. The graphene compound refers to a compound having carbon, having a flat or sheet-like shape, and having a two-dimensional structure formed by carbon six-membered rings. The two-dimensional structure formed by the carbon six-membered rings may also be referred to as a carbon sheet. The graphene compound may have a functional group. Also, the graphene compound preferably has a bent shape. Also, the graphene compound may be rounded like a carbon nanofiber.

[0070] In a positive electrode or a negative electrode according to one embodiment of the present invention, graphene or a graphene compound can function as a conductive agent. Multiple graphenes or graphene compounds can form three-dimensional conductive paths within the positive electrode or negative electrode, thereby enhancing the conductivity of the positive electrode or negative electrode. Furthermore, graphene or a graphene compound can cling to particles in the positive electrode or negative electrode, thereby suppressing particle collapse in the positive electrode or negative electrode and enhancing the strength of the positive electrode or negative electrode. Graphene or a graphene compound has a thin sheet shape and can form an excellent conductive path even when its volume within the positive electrode or negative electrode is small. This allows the volume of the active material in the positive electrode or negative electrode to be increased, thereby enhancing the capacity of the secondary battery.

[0071] [Separator] Separator 507 can be made of, for example, paper, nonwoven fabric, glass fiber, ceramics, etc. Alternatively, it can be made of nylon (polyamide), vinylon (polyvinyl alcohol fiber), polyester, acrylic, polyolefin, polyurethane, polypropylene, polyethylene, etc. The separator is preferably processed into an envelope shape and disposed so as to encase either the positive electrode or the negative electrode.

[0072] Separator 507 may be made of a polymer film containing, for example, polypropylene, polyethylene, or the like.

[0073] Polymer films containing polypropylene, polyethylene, etc. can be produced by either the dry method or the wet method. The dry method involves heating and stretching a polymer film containing polypropylene, polyethylene, etc., to create gaps between the crystals and create fine holes. The wet method involves mixing a solvent into the resin beforehand, forming it into a film, and then extracting the solvent to create holes.

[0074] 1C1 shows an enlarged view of region 507a as an example of separator 507 (produced by a wet method). In this example, a structure in which a plurality of holes 582 are formed in polymer film 581 is shown. FIG. 1C2 shows an enlarged view of region 507b as another example of separator 507 (produced by a dry method). In this example, a structure in which a plurality of holes 585 are formed in polymer film 584 is shown.

[0075] The pore diameter of the separator may differ between the surface layer portion on the positive electrode side and the surface layer portion on the negative electrode side. In this specification, the surface layer portion of the separator is preferably, for example, a region within 5 μm, more preferably within 3 μm, from the surface.

[0076] The separator may have a multi-layer structure, for example, a structure in which two types of polymer materials are laminated.

[0077] Also, a structure in which a polymer film containing, for example, polypropylene or polyethylene is coated with a ceramic material, a fluorine material, a polyamide material, or a mixture of these may be used.

[0078] As the ceramic material, a metal-containing oxide or hydroxide can be used. Examples of the metal-containing oxide or hydroxide that can be used include magnesium oxide, titanium oxide, aluminum oxide, silicon oxide, magnesium hydroxide, aluminum hydroxide, and titanium hydroxide. As the titanium oxide, either a material with a rutile structure or a material with an anatase structure can be used, but in some cases, a material with an anatase structure is more preferable. The metal oxide that can be used as the ceramic material may be in the form of fine particles.

[0079] The ceramic material may be coated onto the polymer film by, for example, particle coating or thin film coating.

[0080] As the fluorine-based material, for example, PVdF, polytetrafluoroethylene, etc. can be used.

[0081] Examples of polyamide-based materials that can be used include nylon and aramid (meta-aramid, para-aramid).

[0082] Coating the polymer membrane with a ceramic material improves oxidation resistance, suppressing separator degradation during high-voltage charging and discharging and improving the reliability of the secondary battery. Coating the polymer membrane with a fluorine-based material also improves adhesion between the separator and electrodes, improving output characteristics. Coating the polymer membrane with a polyamide material, especially aramid, improves heat resistance, improving the safety of the secondary battery.

[0083] In addition, increasing the surface area of ​​the ceramic material is effective in increasing the amount of cobalt adsorbed. Materials with a layered crystal structure, such as Mg(OH)2, tend to form flat, thin particles. By using such particles to form a layer containing the ceramic material, the amount of cobalt adsorbed can be increased. The specific surface area of ​​the ceramic material is, for example, 10 m 2 The specific surface area can be measured by a gas adsorption method or the like.

[0084] For example, both sides of a polypropylene-containing film may be coated with a mixture of one or more ceramic materials selected from magnesium hydroxide and titanium oxide and a binder such as PVdF. Alternatively, the surface of the polypropylene-containing film that comes into contact with the positive electrode may be coated with a mixture of one or more ceramic materials selected from magnesium hydroxide and titanium oxide and a binder such as PVdF, and the surface that comes into contact with the negative electrode may be coated with a fluorine-containing material.

[0085] FIG. 2A shows a separator 507 having a porous polymer membrane 521 and a layer 522 having a ceramic material coated on the porous polymer membrane 521. The porous polymer membrane 521 is a membrane similar to the perforated polymer membrane 581 shown in FIG. 1C1. FIG. 2C1 shows an enlarged view of a region 521a as an example of the porous polymer membrane 521 of the separator 507. In this example, a structure similar to the region 507a of the separator 507 shown in FIG. 1C1 is shown. FIG. 2C2 shows an enlarged view of a region 521b as another example of the porous polymer membrane 521 of the separator 507. In this example, a structure similar to the region 507b of the separator 507 shown in FIG. 1C2 is shown.

[0086] When a separator with a multilayer structure is used, the safety of the secondary battery can be maintained even if the overall thickness of the separator is thin, and therefore the capacity per volume of the secondary battery can be increased.

[0087] In addition, ionic liquids are flame-retardant. When an ionic liquid is used as the electrolyte and the separator is impregnated with the ionic liquid, a flame-retardant secondary battery can be realized.

[0088] A method for producing a separator coated with a ceramic material will be described below with reference to FIG.

[0089] First, a slurry of the ceramic material to be coated on the separator is prepared. The slurry can be prepared, for example, by mixing the ceramic material with a solvent and a binder. At this time, the mixing may be performed in a high viscosity state. Mixing the materials in a high viscosity state by kneading them is sometimes called kneading. The binder described in the preparation of the active material layer can be used as the binder.

[0090] In step S21, a ceramic material and a solvent are prepared. A combination of ceramic materials may be used. The solvent may be, for example, one or a mixture of two or more of N-methylpyrrolidone (NMP), water, methanol, ethanol, acetone, tetrahydrofuran (THF), dimethylformamide (DMF), and dimethyl sulfoxide (DMSO).

[0091] The mixing may be carried out using a kneader, such as a planetary mixer.

[0092] In step S22, the ceramic material prepared in step S21 and the solvent are kneaded together, and a mixture is obtained in step S23. In order to disperse the ceramic material, it is preferable to first knead the ceramic material and the solvent together.

[0093] In step S24, a binder and a solvent are added to the mixture obtained in step S23, and then they are kneaded in step S25 to obtain a mixture in step S26. The binder is preferably added little by little to prevent aggregation. In step S25, for example, the mixture obtained in step S23, the binder, and the solvent are kneaded as a mixture with a solid content ratio of 50% to 80%, which is preferable because it allows for high viscosity mixing. The solid content ratio refers to the proportion of solids (here, ceramic material and binder) in the mixture. Next, in step S27, a binder and a solvent are added to the mixture obtained in step S26, and then they are kneaded in step S28 to obtain a slurry in step S29. The solid content ratio of the prepared slurry is preferably 30%.

[0094] In step S30, the prepared slurry is applied onto a polymer material. The application may be performed using a blade method, a printing method, or the like. Alternatively, a continuous coater may be used for application. In step S31, a polymer material coated with the slurry can be obtained.

[0095] In step S32, the solvent is evaporated from the slurry applied on the polymer material using a method such as ventilation drying or vacuum drying. The solvent may be evaporated, for example, using warm air or hot air at a temperature of 30°C or higher and 160°C or lower. The atmosphere is not particularly limited.

[0096] Through the above steps, in step S33, a separator coated with a ceramic-based material can be produced.

[0097] 〔Positive Electrode〕 Next, the positive electrode will be described.

[0098] <Positive Electrode Active Material> Examples of the positive electrode active material include composite oxides having an olivine-type crystal structure, a layered rock salt-type crystal structure, or a spinel-type crystal structure. For example, compounds such as LiFePO4, LiFeO2, LiNiO2, LiMn2O4, V2O5, Cr2O5, and MnO2 can be mentioned.

[0099] In addition, it is preferable to mix lithium nickelate (LiNiO2 or LiNi 1-x M x O2 (0 < x < 1) (M = Co, Al, etc.)) with a lithium-containing material having a spinel-type crystal structure containing manganese such as LiMn2O4 as the positive electrode active material. By adopting such a configuration, the characteristics of the secondary battery can be improved.

[0100] Also, as the positive electrode active material, a composition formula Li a Mn b M c O dA lithium-manganese composite oxide that can be expressed by the formula (b + c) can be used. Here, the metal M is preferably a metal element selected from among lithium and manganese, or silicon or phosphorus, and more preferably nickel. When measuring the entire lithium-manganese composite oxide particle, <a / (b+c)<2、かつc>it is preferable that the composition be 0 0 during discharge and satisfy 0.26≦(b+c) / d<0.5. The composition of metals, silicon, phosphorus, etc. in the entire lithium-manganese composite oxide particle can be measured using, for example, an inductively coupled plasma mass spectrometer (ICP-MS). The oxygen composition in the entire lithium-manganese composite oxide particle can be measured using, for example, EDX. It can also be determined by valence evaluation using fused gas analysis and XAFS (X-ray absorption fine structure) analysis in combination with ICPMS analysis. The lithium-manganese composite oxide refers to an oxide containing at least lithium and manganese, and may contain at least one element selected from the group consisting of chromium, cobalt, aluminum, nickel, iron, magnesium, molybdenum, zinc, indium, gallium, copper, titanium, niobium, silicon, and phosphorus.

[0101] Generally, as the positive electrode active material is repeatedly charged and discharged, a side reaction occurs in which transition metals such as cobalt dissolve into the electrolyte. Furthermore, cobalt ions dissolved from the positive electrode active material adhere to the negative electrode surface, causing cobalt to precipitate and thicken the coating on the negative electrode surface. However, because the separator of one embodiment of the present invention is believed to be capable of adsorbing cobalt, it is expected to be able to reduce the concentration of cobalt dissolved into the electrolyte. This prevents the coating on the negative electrode surface from thickening, thereby suppressing deterioration of the secondary battery.

[0102] <Example of a method for producing a cobalt-containing material> ​Next, an example of a method for producing LiMO2, which is one embodiment of a material that can be used as a positive electrode active material, will be described with reference to FIG. 4. For example, at least one of manganese, cobalt, and nickel can be used as the metal M. Furthermore, the metal M can further contain a metal X in addition to the metals listed above. Furthermore, there are no particular limitations on the substitution position of the metal M. Below, a cobalt-containing material in which the metal X is Mg will be used as an example. Note that the positive electrode active material of one embodiment of the present invention has a crystalline structure of a lithium composite oxide represented by LiMO2, but its composition is not limited to Li:M:O=1:1:2.

[0103] First, in step S11, a composite oxide containing lithium, a transition metal, and oxygen is used as the composite oxide 801. Here, it is preferable to use one or more transition metals containing cobalt.

[0104] A composite oxide containing lithium, a transition metal, and oxygen can be synthesized by heating a lithium source and a transition metal source in an oxygen atmosphere. The transition metal source is preferably a metal capable of forming a layered rock-salt composite oxide belonging to the space group R-3m with lithium. For example, at least one of manganese, cobalt, and nickel can be used. Aluminum may also be used in addition to these transition metals. That is, the transition metal source may be a cobalt source alone, a nickel source alone, a combination of a cobalt source and a manganese source, a combination of a cobalt source and a nickel source, or a combination of a cobalt source, a manganese source, and a nickel source. Furthermore, an aluminum source may also be used in addition to these metal sources. The heating temperature in this step is preferably higher than that in step S17, which will be described later. For example, the heating step may be performed at 1000°C. This heating step is sometimes referred to as calcination.

[0105] When using a pre-synthesized composite oxide containing lithium, transition metals, and oxygen, it is preferable to use one with few impurities. In this specification, the main components of the composite oxide containing lithium, transition metals, and oxygen, the cobalt-containing material, and the positive electrode active material are lithium, cobalt, nickel, manganese, aluminum, and oxygen, and elements other than the main components are considered impurities. For example, when analyzed by glow discharge mass spectrometry (GD-MS), the total impurity concentration is preferably 10,000 ppmw (parts per million weight) or less, more preferably 5000 ppmw or less. In particular, the total impurity concentration of transition metals such as titanium and arsenic is preferably 3000 ppmw or less, more preferably 1500 ppmw or less.

[0106] For example, lithium cobalt oxide particles (product name: Cellseed C-10N) manufactured by Nippon Chemical Industry Co., Ltd. can be used as pre-synthesized lithium cobalt oxide. This lithium cobalt oxide has an average particle size (D50) of approximately 12 μm, and impurity analysis by glow discharge mass spectrometry reveals that the magnesium and fluorine concentrations are 50 ppmw or less, the calcium, aluminum, and silicon concentrations are 100 ppmw or less, the nickel concentration is 150 ppmw or less, the sulfur concentration is 500 ppmw or less, the arsenic concentration is 1100 ppmw or less, and the concentrations of other elements other than lithium, cobalt, and oxygen are 150 ppmw or less.

[0107] The composite oxide 801 in step S11 preferably has a layered rock-salt crystal structure with few defects and strain. Therefore, it is preferable that the composite oxide has few impurities. If a composite oxide containing lithium, a transition metal, and oxygen contains a large amount of impurities, it is likely to have a crystal structure with many defects or strains.

[0108] In step S12, fluoride 802 is prepared. Examples of fluorides that can be used include lithium fluoride (LiF), magnesium fluoride (MgF), aluminum fluoride (AlF), titanium fluoride (TiF), cobalt fluoride (CoF, CoF), nickel fluoride (NiF), zirconium fluoride (ZrF), vanadium fluoride (VF), manganese fluoride, iron fluoride, chromium fluoride, niobium fluoride, zinc fluoride (ZnF), calcium fluoride (CaF), sodium fluoride (NaF), potassium fluoride (KF), barium fluoride (BaF), cerium fluoride (CeF), lanthanum fluoride (LaF), and sodium aluminum hexafluoride (NaAlF). Fluoride 802 may be any fluoride that functions as a fluorine source. Therefore, instead of or as a part of the fluoride 802, for example, fluorine (F2), carbon fluoride, sulfur fluoride, oxygen fluoride (OF2, O2F2, O3F2, O4F2, O2F), etc. may be used and mixed into the atmosphere in the heating step described below.

[0109] When the fluoride 802 is a compound having a metal X, it can also serve as the compound 803 (a compound having a metal X) described later.

[0110] In this embodiment, lithium fluoride (LiF) is prepared as the fluoride 802. LiF is preferable because it has a cation common to LiCoO2. LiF is also preferable because it has a relatively low melting point of 848°C and is easily melted in the annealing step described below.

[0111] Furthermore, when LiF is used as the fluoride 802, it is preferable to prepare a compound 803 (a compound having a metal X) in addition to the fluoride 802 in step S13. The compound 803 is a compound having a metal X.

[0112] In step S13, a compound 803 is prepared. As the compound 803, a fluoride, oxide, hydroxide, or the like of a metal X can be used, and it is particularly preferable to use a fluoride.

[0113] When magnesium is used as the metal X, MgF2 or the like can be used as the compound 803. Magnesium can be distributed in high concentration near the surface of the cobalt-containing material.

[0114] In addition to the fluoride 802 and the compound 803, a material containing a metal other than cobalt and other than the metal X may be mixed. Examples of materials containing a metal other than cobalt and other than the metal X include a nickel source, a manganese source, an aluminum source, an iron source, a vanadium source, a chromium source, a niobium source, and a titanium source. For example, it is preferable to mix the hydroxide, fluoride, oxide, etc. of each metal in a finely pulverized form. The finely pulverized form can be obtained, for example, by a wet method.

[0115] Furthermore, the order of steps S11, S12 and S13 may be freely changed.

[0116] Next, in step S14, the materials prepared in steps S11, S12, and S13 are mixed and pulverized. Mixing can be performed dry or wet, but wet mixing is preferred because it allows for finer pulverization. If wet mixing is used, a solvent is prepared. Examples of solvents that can be used include ketones such as acetone, alcohols such as ethanol and isopropanol, ether, dioxane, acetonitrile, and N-methyl-2-pyrrolidone (NMP). It is more preferable to use an aprotic solvent that is less likely to react with lithium. In this embodiment, acetone is used.

[0117] For example, a ball mill, a bead mill, etc. can be used for mixing. When using a ball mill, it is preferable to use zirconia balls as the media. It is preferable to thoroughly perform this mixing and pulverizing process to finely pulverize the mixture 804.

[0118] Next, in step S15, the mixed and crushed materials are collected, and in step S16, a mixture 804 is obtained.

[0119] The mixture 804 preferably has a D50 of, for example, 600 nm or more and 20 μm or less, and more preferably 1 μm or more and 10 μm or less.

[0120] In step S17, a heat treatment (also called annealing) is performed on the mixture 804. The heating temperature in step S17 is preferably equal to or higher than the temperature at which the mixture 804 melts. In addition, the heating temperature is preferably lower than the decomposition temperature (1130°C) of LiCoO2.

[0121] By using LiF as the fluoride 802 and annealing S17 with a lid, a cobalt-containing material 808 with excellent cycle characteristics can be produced. Furthermore, when LiF and MgF2 are used as the fluoride 802, the eutectic point of LiF and MgF2 is around 742°C. Therefore, setting the annealing temperature of S17 at 742°C or higher is thought to promote the reaction with LiCoO2, resulting in the production of LiMO2. Furthermore, a mixture of LiF, MgF2, and LiCoO2 exhibits an endothermic peak around 820°C in differential scanning calorimetry (DSC). Therefore, the annealing temperature is preferably 742°C or higher, and more preferably 820°C or higher.

[0122] Therefore, the annealing temperature is preferably 742° C. or higher and 1130° C. or lower, and more preferably 742° C. or higher and 1000° C. or lower. Also, the annealing temperature is preferably 820° C. or higher and 1130° C. or lower, and more preferably 820° C. or higher and 1000° C. or lower.

[0123] In addition, in this embodiment, it is believed that LiF, a fluoride, functions as a flux. Therefore, since the volume inside the heating furnace is larger than the volume of the container and is lighter than oxygen, it is expected that LiF will volatilize and the amount of LiF in the mixture 804 will decrease, suppressing the generation of LiMO2. Therefore, it is necessary to heat the mixture while suppressing the volatilization of LiF.

[0124] Therefore, by heating the mixture 804 in an atmosphere containing LiF, i.e., by heating the mixture 804 in a furnace under a high LiF partial pressure, the volatilization of LiF in the mixture 804 is suppressed. By annealing with a lid using a fluoride (LiF or MgF) that forms a eutectic mixture, the annealing temperature can be lowered to below the decomposition temperature of LiCoO2 (1130°C), specifically to between 742°C and 1000°C, allowing the formation of LiMO2 to proceed efficiently. As a result, a cobalt-containing material with good properties can be produced, and the annealing time can also be shortened.

[0125] An example of the annealing method in S17 is shown in FIG.

[0126] The heating furnace 120 shown in FIG. 5 includes a furnace space 102, a hot plate 104, a heater 106, and an insulating material 108. Annealing is preferably performed with a lid 118 attached to the container 116. This configuration allows the space 119 defined by the container 116 and lid 118 to be filled with a fluoride-containing atmosphere. By maintaining the lid during annealing to maintain a constant or non-decreasing concentration of gasified fluoride in the space 119, fluorine and magnesium can be incorporated near the particle surfaces. Because the space 119 has a smaller volume than the furnace space 102, a small amount of fluoride volatilizes, creating a fluoride-containing atmosphere. In other words, the reaction system can be converted to a fluoride-containing atmosphere without significantly reducing the amount of fluoride contained in the mixture 804. Therefore, LiMO2 can be efficiently produced. Furthermore, using the lid 118 allows the mixture 804 to be annealed in a fluoride-containing atmosphere simply and inexpensively.

[0127] Here, the valence of Co (cobalt) in LiCoO2 produced according to one embodiment of the present invention is preferably approximately trivalent. Cobalt can be divalent or trivalent. Therefore, to suppress the reduction of cobalt, the atmosphere in the heating furnace space 102 preferably contains oxygen, more preferably the ratio of oxygen to nitrogen in the atmosphere in the heating furnace space 102 is equal to or greater than that of the air atmosphere, and even more preferably the oxygen concentration in the atmosphere in the heating furnace space 102 is equal to or greater than that of the air atmosphere. Therefore, it is necessary to introduce an oxygen-containing atmosphere into the heating furnace space. However, since cobalt atoms with nearby magnesium atoms may be more stable in a divalent state, not all cobalt atoms need to be trivalent.

[0128] Therefore, in one embodiment of the present invention, before heating, a step of creating an oxygen-containing atmosphere in the heating furnace space 102 and a step of placing the container 116 containing the mixture 804 in the heating furnace space 102 are performed. By performing these steps in this order, the mixture 804 can be annealed in an atmosphere containing oxygen and fluoride. Furthermore, it is preferable to seal the heating furnace space 102 during annealing to prevent gas from being transported to the outside. For example, it is preferable to perform annealing without flowing gas.

[0129] There are no particular limitations on the method for creating an oxygen-containing atmosphere in the heating furnace space 102, but examples include a method of evacuating the heating furnace space 102 and then introducing an oxygen-containing gas such as oxygen gas or dry air, and a method of infusing an oxygen-containing gas such as oxygen gas or dry air for a certain period of time. Among these, it is preferable to evacuate the heating furnace space 102 and then introduce oxygen gas (oxygen substitution). Note that the air in the heating furnace space 102 may be considered to be an oxygen-containing atmosphere.

[0130] When the lid 118 is placed on the container 116, an oxygen-containing atmosphere is created, and the container 116 is heated, an appropriate amount of oxygen enters the container 116 through the gap in the lid 118 placed on the container 116, and an appropriate amount of fluoride can be retained in the container 116.

[0131] Furthermore, there is a possibility that fluoride and the like adhering to the inner walls of the container 116 and the lid 118 may fly again due to heating and adhere to the mixture 804 .

[0132] The annealing in step S17 is preferably carried out at an appropriate temperature for an appropriate time. The appropriate temperature and time vary depending on conditions such as the size and composition of the particles of the composite oxide 801 in step S11. If the particles are small, a lower temperature or shorter time may be more preferable than if the particles are large. After the annealing in step S17, a step of removing the lid is included.

[0133] For example, when the average particle size (D50) of the particles in step S11 is about 12 μm, the annealing time is preferably, for example, 3 hours or more, and more preferably 10 hours or more.

[0134] On the other hand, when the average particle size (D50) of the particles in step S11 is about 5 μm, the annealing time is preferably, for example, from 1 hour to 10 hours, and more preferably about 2 hours.

[0135] The temperature drop time after annealing is preferably, for example, 10 hours or more and 50 hours or less.

[0136] Next, in step S18, the annealed material is recovered, and in step S19, a cobalt-containing material 808 is obtained.

[0137] [Positive electrode active material structure] Materials with a layered rock-salt crystal structure, such as lithium cobalt oxide (LiCoO2), are known to have high discharge capacity and are excellent as positive electrode active materials for secondary batteries. An example of a material with a layered rock-salt crystal structure is a composite oxide represented by LiMO2. Metal M includes the metals listed above. Furthermore, metal M can include metal X listed above in addition to the metals listed above.

[0138] It is known that the strength of the Jahn-Teller effect in transition metal compounds varies depending on the number of electrons in the d orbital of the transition metal.

[0139] In compounds containing nickel, distortion may occur due to the Jahn-Teller effect. Therefore, when LiNiO2 is charged and discharged at high voltages, there is a concern that the crystal structure may collapse due to distortion. In LiCoO2, the influence of the Jahn-Teller effect is suggested to be small, and LiCoO2 may have better durability against charge and discharge at high voltages, which is preferable.

[0140] The positive electrode active material will be described with reference to FIGS.

[0141] The positive electrode active material prepared according to one embodiment of the present invention can reduce the displacement of the CoO2 layer during repeated high-voltage charge and discharge. Furthermore, the volume change can be reduced. Therefore, the compound can achieve excellent cycle characteristics. Furthermore, the compound can have a stable crystal structure in a high-voltage charged state. Therefore, the compound may be less likely to cause a short circuit when maintained in a high-voltage charged state. In such cases, safety is further improved, which is preferable.

[0142] In this compound, the change in crystal structure and the difference in volume between a fully discharged state and a high-voltage charged state are small when compared per the same number of transition metal atoms.

[0143] The positive electrode active material of one embodiment of the present invention contains lithium, the metal M described above, oxygen, and titanium. The positive electrode active material of one embodiment of the present invention preferably contains a halogen such as fluorine or chlorine.

[0144] In addition, in each region, such as the surface layer portion, the interior, and the first region in the surface layer portion, the concentration of elements such as metal M has, for example, a gradient. That is, for example, at the boundary between each region, the concentration of each element does not change abruptly, but changes with a gradient. Here, in addition to cobalt and magnesium, for example, aluminum, nickel, etc. can be used as metal M. In such a case, aluminum and nickel each have, for example, a concentration gradient in each region, such as the surface layer portion, the interior, and the first region in the surface layer portion.

[0145] A cathode active material according to one embodiment of the present invention has a first region. When the cathode active material according to one embodiment of the present invention has a particulate form, the first region preferably includes a region located inside the particle surface. At least a portion of the surface layer may be included in the first region. The first region preferably has a layered rock-salt structure and is represented by the space group R-3m. The first region is a region containing lithium and a metal M. FIG. 6 shows an example of the crystal structure of the first region before and after charge and discharge. Furthermore, the surface layer of the cathode active material according to one embodiment of the present invention may have a crystal containing magnesium and oxygen and having a structure different from the layered rock-salt structure, in addition to or instead of the region having a layered rock-salt structure described below in FIG. 6 and the like.

[0146] Li in Figure 6 xThe crystal structure when the occupancy rate in CoO2 is x = 1 is the same as in Figure 7, R-3m(O3). On the other hand, when x = approximately 0.2, the first region has a crystal structure different from the H1-3 type crystal structure. This structure is in the space group R-3m and is not a spinel type crystal structure. However, ions such as cobalt and magnesium occupy the oxygen hexacoordination sites, and the cation arrangement has a symmetry similar to that of the spinel type. Furthermore, the symmetry of the CoO2 layers in this structure is the same as that of the O3 type. Therefore, this structure is referred to as the O3' type crystal structure in this specification. Note that in the diagram of the O3' type crystal structure shown in Figure 6, lithium can be present at any lithium site with a probability of approximately 20%, but this is not limited to this. Lithium may be present only at a specific portion of the lithium sites. Furthermore, in both the O3 type crystal structure and the O3' type crystal structure, magnesium is preferably present in a dilute form between the CoO2 layers, i.e., at the lithium sites. Furthermore, halogens such as fluorine may be present randomly and dilutely at the oxygen sites.

[0147] In the O3'-type crystal structure, light elements such as lithium may occupy the oxygen tetracoordination site, and in this case too, the arrangement of ions has a symmetry similar to that of the spinel type.

[0148] The O3' type crystal structure can also be said to be a crystal structure similar to the CdCl2 type crystal structure, although it has random Li between the layers. This CdCl2 type-like crystal structure is similar to the CdCl2 type crystal structure, but the O3' type crystal structure has random Li between the layers. 0.06 This is similar to the crystal structure when charged to NiO2, but it is known that pure lithium cobalt oxide or layered rock salt-type positive electrode active materials that contain a large amount of cobalt do not usually have this crystal structure.

[0149] In the first region, the change in the crystal structure when a large amount of lithium is released during high-voltage charging is suppressed more than in the comparative example described below. For example, as shown by the dotted line in Figure 6, there is almost no displacement of the CoO2 layers in these crystal structures.

[0150] More specifically, the first region exhibits high structural stability even at high charge voltages. For example, in FIG. 7, the H1-3 crystal structure is formed at a voltage of approximately 4.6 V relative to the potential of lithium metal. However, the cathode active material of one embodiment of the present invention can maintain the R-3m(O3) crystal structure even at a charge voltage of approximately 4.6 V. Even at higher charge voltages, for example, at voltages of approximately 4.65 V to 4.7 V relative to the potential of lithium metal, the cathode active material of one embodiment of the present invention can adopt the O3' crystal structure. When the charge voltage is further increased above 4.7 V, the H1-3 crystal structure may finally be observed in the cathode active material of one embodiment of the present invention. Furthermore, at lower charge voltages (for example, even when the charge voltage is 4.5 V or higher but less than 4.6 V relative to the potential of lithium metal), the cathode active material of one embodiment of the present invention may adopt the O3' crystal structure.

[0151] Note that when graphite is used as the negative electrode active material in a secondary battery, the voltage of the secondary battery is lower than the above-mentioned value by the potential of the graphite. The potential of graphite is approximately 0.05 V to 0.2 V relative to the potential of lithium metal. Therefore, even when the voltage of a secondary battery using graphite as the negative electrode active material is 4.3 V or higher and 4.5 V or lower, the positive electrode active material of one embodiment of the present invention can maintain the R-3m(O3) crystal structure. Furthermore, even when the charge voltage is higher, for example, when the voltage of the secondary battery is higher than 4.5 V and lower than 4.6 V, there is a region in which the O3'-type crystal structure can be formed. Furthermore, even when the charge voltage is lower, for example, when the voltage of the secondary battery is 4.2 V or higher but lower than 4.3 V, the positive electrode active material of one embodiment of the present invention can sometimes form the O3'-type crystal structure.

[0152] Therefore, in the first region, the crystal structure is less likely to collapse even when charging and discharging are repeated at a high voltage.

[0153] In addition, in the positive electrode active material of one embodiment of the present invention, the difference in volume per the same number of cobalt atoms between the O3-type crystal structure and the O3'-type crystal structure in a discharged state is 2.5% or less, more specifically 2.2% or less.

[0154] In addition, the O3' type crystal structure can be expressed by the coordinates of cobalt and oxygen in the unit cell being Co(0,0,0.5), O(0,0,x), 0.20≦x≦0.25.

[0155] Magnesium, which exists randomly and dilutely between the CoO2 layers, i.e., at the lithium sites, has the effect of suppressing the displacement of the CoO2 layers when charged at high voltage. Therefore, when magnesium exists between the CoO2 layers, the O3'-type crystal structure is easily formed.

[0156] However, if the heat treatment temperature is too high, cation mixing occurs, increasing the possibility that magnesium will enter the cobalt site. Magnesium present in the cobalt site may not be effective in maintaining the R-3m structure during high-voltage charging. Furthermore, if the heat treatment temperature is too high, there are concerns that adverse effects such as cobalt being reduced to a divalent state and lithium evaporating may occur.

[0157] Therefore, it is preferable to add a halogen compound such as a fluorine compound to the lithium cobalt oxide before the heat treatment to distribute magnesium throughout the particles. The addition of the halogen compound lowers the melting point of the lithium cobalt oxide. Lowering the melting point makes it easier to distribute magnesium throughout the particles at a temperature where cation mixing is unlikely to occur. Furthermore, the presence of a fluorine compound is expected to improve corrosion resistance to hydrofluoric acid produced by decomposition of the electrolyte.

[0158] Note that increasing the magnesium concentration above a desired value may reduce the effect on stabilizing the crystal structure. This is thought to be because magnesium occupies not only the lithium site but also the cobalt site. The number of magnesium atoms in the positive electrode active material prepared according to one embodiment of the present invention is preferably 0.001 to 0.1 times the number of cobalt atoms, more preferably greater than 0.01 and less than 0.04, and even more preferably approximately 0.02. The magnesium concentration shown here may be, for example, a value obtained by performing elemental analysis of the entire particles of the positive electrode active material using ICP-MS or the like, or may be based on the value of the raw material composition during the preparation of the positive electrode active material.

[0159] The number of nickel atoms in the positive electrode active material of one embodiment of the present invention is preferably 7.5% or less of the number of cobalt atoms, preferably 0.05% to 4%, and more preferably 0.1% to 2%. The nickel concentration shown here may be a value obtained by performing elemental analysis of the entire particles of the positive electrode active material using, for example, ICP-MS, or may be based on the value of the blending ratio of raw materials in the process of producing the positive electrode active material.

[0160] <Particle size> If the particle size of the positive electrode active material of one embodiment of the present invention is too large, problems such as difficulty in diffusing lithium and excessive roughness of the surface of the active material layer when applied to a current collector arise. On the other hand, if the particle size is too small, problems such as difficulty in supporting the active material layer when applied to a current collector and excessive reaction with the electrolyte occur. Therefore, the average particle size (D50: also referred to as median diameter) is preferably 1 μm or more and 100 μm or less, more preferably 2 μm or more and 40 μm or less, and even more preferably 5 μm or more and 30 μm or less.

[0161] <Analysis method> Whether a certain positive electrode active material exhibits the O3'-type crystal structure when charged at a high voltage can be determined by analyzing the positive electrode charged at a high voltage using XRD, electron diffraction, neutron diffraction, electron spin resonance (ESR), nuclear magnetic resonance (NMR), etc. XRD is particularly preferred because it can analyze the symmetry of transition metals such as cobalt contained in the positive electrode active material with high resolution, it can compare the level of crystallinity and the orientation of the crystals, it can analyze the periodic distortion of the lattice and the crystallite size, and it can obtain sufficient accuracy even when measuring the positive electrode obtained by disassembling the secondary battery.

[0162] As described above, the positive electrode active material of one embodiment of the present invention is characterized by minimal change in crystal structure between the high-voltage charged state and the discharged state. Materials in which 50 wt% or more of a crystal structure exhibiting a significant change from the discharged state during high-voltage charging are undesirable because they cannot withstand high-voltage charging and discharging. It should be noted that the desired crystal structure may not be achieved simply by adding impurity elements. For example, even if both materials share the common feature of being lithium cobalt oxide containing magnesium and fluorine, there are cases in which the O3'-type crystal structure accounts for 60 wt% or more during high-voltage charging, and cases in which the H1-3-type crystal structure accounts for 50 wt% or more. Furthermore, at a certain voltage, the O3'-type crystal structure may be nearly 100 wt%, and further increasing the voltage may result in the H1-3-type crystal structure. Therefore, it is preferable to analyze the crystal structure of the positive electrode active material of one embodiment of the present invention using XRD or other methods. A more detailed analysis can be performed by combining measurements such as XRD with other analytical methods.

[0163] However, when positive electrode active materials are charged or discharged at high voltage, their crystal structure may change when exposed to air. For example, they may change from an O3'-type crystal structure to an H1-3-type crystal structure. Therefore, it is recommended that all samples be handled in an inert atmosphere, such as an argon-containing atmosphere.

[0164] The positive electrode active material shown in FIG. 7 is lithium cobalt oxide (LiCoO2) to which no metal X is added. The lithium cobalt oxide shown in FIG. xThe crystal structure changes with the change in the occupancy rate x in CoO2.

[0165] As shown in Figure 7, Li x Lithium cobalt oxide, with an occupancy rate of x=1 in CoO2, has a region with a crystal structure of space group R-3m, with three CoO2 layers in the unit cell. For this reason, this crystal structure is sometimes called an O3-type crystal structure. Note that a CoO2 layer is an octahedral structure in which cobalt is six-coordinated with oxygen, and the layers are connected in a plane with edge sharing.

[0166] When x = 0, lithium cobalt oxide has a trigonal space group P-3m1 crystal structure with one CoO2 layer in the unit cell, which is why this crystal structure is sometimes called the O1-type crystal structure.

[0167] Furthermore, conventional lithium cobalt oxides with x = 0.24 or so have a crystal structure of the space group R-3m. This structure can be described as a structure in which CoO structures such as P-3m1(O1) and LiCoO structures such as R-3m(O3) are alternately stacked. Therefore, this crystal structure is sometimes referred to as the H1-3 crystal structure. Because actual lithium insertion and extraction can be uneven, the H1-3 crystal structure is experimentally observed from x = 0.25 or so. Furthermore, the H1-3 crystal structure actually has twice the number of cobalt atoms per unit cell compared to other structures. However, in Figure 7 and other parts of this specification, the c-axis of the H1-3 crystal structure is shown as half the unit cell to facilitate comparison with other structures.

[0168] As an example, the coordinates of cobalt and oxygen in the unit cell of the H1-3 crystal structure can be expressed as Co(0,0,0.42150±0.00016), O1(0,0,0.27671±0.00045), and O2(0,0,0.11535±0.00045). O1 and O2 are each an oxygen atom. Thus, the H1-3 crystal structure is expressed by a unit cell using one cobalt and two oxygen atoms. On the other hand, the O3' crystal structure of one embodiment of the present invention is preferably expressed by a unit cell using one cobalt and one oxygen atom. This indicates that the symmetry between cobalt and oxygen differs between the O3' crystal structure and the H1-3 structure, and that the O3' crystal structure exhibits smaller changes from the O3 structure than the H1-3 structure. The unit cell that is more preferably used to represent the crystal structure of the positive electrode active material may be selected, for example, so that the GOF (goodness of fit) value is smaller in Rietveld analysis of XRD.

[0169] Li x When conventional lithium cobalt oxide is repeatedly charged and discharged so that the occupancy rate x in CoO2 becomes 0.24 or less, the crystal structure changes repeatedly (i.e., a non-equilibrium phase change) between the H1-3 type crystal structure and the R-3m(O3) structure in the discharged state.

[0170] However, these two crystal structures have a large deviation in the CoO2 layers. As shown by the dotted lines and arrows in Figure 7, in the H1-3 crystal structure, the CoO2 layers are significantly deviated from the R-3m(O3) structure. Such dynamic structural changes can adversely affect the stability of the crystal structure.

[0171] Furthermore, the difference in volume is large: when compared per the same number of cobalt atoms, the difference in volume between the H1-3 crystal structure and the O3 crystal structure in the discharged state is more than 3.0%.

[0172] In addition, the H1-3 type crystal structure, which has continuous CoO2 layers such as P-3m1(O1), is likely to be unstable.

[0173] Therefore, repeated high-voltage charging and discharging causes the crystalline structure of lithium cobalt oxide to collapse, which leads to a deterioration in cycle characteristics. This is thought to be because the collapse of the crystalline structure reduces the number of sites where lithium can exist stably and makes it difficult for lithium to be inserted and extracted.

[0174] [Negative electrode] Next, the negative electrode will be described.

[0175] <Negative electrode active material> As the negative electrode active material, for example, an alloy-based material or a carbon-based material can be used.

[0176] The negative electrode active material can be an element capable of undergoing charge-discharge reactions through alloying and dealloying reactions with lithium. For example, materials containing at least one of silicon, tin, gallium, aluminum, germanium, lead, antimony, bismuth, silver, zinc, cadmium, and indium can be used. These elements have a larger capacity than carbon, and silicon, in particular, has a high theoretical capacity of 4200 mAh / g. For this reason, silicon is preferred as the negative electrode active material. Compounds containing these elements can also be used. Examples include SiO, Mg2Si, Mg2Ge, SnO, SnO2, Mg2Sn, SnS2, V2Sn3, FeSn2, CoSn2, Ni3Sn2, Cu6Sn5, Ag3Sn, Ag3Sb, Ni2MnSb, CeSb3, LaSn3, La3Co2Sn7, CoSb3, InSb, and SbSn. Here, elements that can undergo charge-discharge reactions by alloying / dealloying reactions with lithium, and compounds containing such elements, are sometimes called alloy-based materials.

[0177] In this specification and the like, SiO refers to, for example, silicon monoxide. Alternatively, SiO refers to SiO x Here, x preferably has a value of 1 or close to 1. For example, x is preferably 0.2 or more and 1.5 or less, and more preferably 0.3 or more and 1.2 or less.

[0178] Examples of carbonaceous materials that can be used include graphite, easily graphitizable carbon (soft carbon), non-graphitizable carbon (hard carbon), carbon nanotubes, graphene, and carbon black.

[0179] Examples of graphite include artificial graphite and natural graphite. Examples of artificial graphite include mesocarbon microbeads (MCMB), coke-based artificial graphite, and pitch-based artificial graphite. Here, spherical graphite having a spherical shape can be used as the artificial graphite. For example, MCMB may have a spherical shape and is preferred. Furthermore, it is relatively easy to reduce the surface area of ​​MCMB, and this may be preferred. Examples of natural graphite include flake graphite and spherical natural graphite.

[0180] When lithium ions are inserted into graphite (when lithium-graphite intercalation compounds are formed), graphite exhibits a low potential similar to that of metallic lithium (0.05 V to 0.3 V vs. Li / Li + ) This allows lithium-ion secondary batteries using graphite to exhibit high operating voltages. Furthermore, graphite is preferred because it has advantages such as a relatively high capacity per unit volume, relatively small volume expansion, low cost, and higher safety compared to lithium metal.

[0181] In addition, titanium dioxide (TiO2), lithium titanium oxide (Li4Ti5O 12 ), lithium-graphite intercalation compound (Li x C6), niobium pentoxide (Nb2O5), tungsten oxide (WO2), molybdenum oxide (MoO2), and other oxides can be used.

[0182] In addition, the negative electrode active material is a composite nitride of lithium and transition metals, Li3N-type 3-x M x N (M=Co, Ni, Cu) can be used. For example, Li 2.6 Co 0.4 N3 has a large charge / discharge capacity (900mAh / g, 1890mAh / cm 3 ) and is preferred.

[0183] When a composite nitride of lithium and a transition metal is used, lithium ions are contained in the negative electrode active material, and therefore it can be preferably combined with a material that does not contain lithium ions, such as V2O5 or Cr3O8, as the positive electrode active material. Even when a material containing lithium ions is used as the positive electrode active material, the composite nitride of lithium and a transition metal can be used as the negative electrode active material by first desorbing the lithium ions contained in the positive electrode active material.

[0184] In addition, materials that undergo a conversion reaction can also be used as the negative electrode active material. For example, transition metal oxides that do not form alloys with lithium, such as cobalt oxide (CoO), nickel oxide (NiO), and iron oxide (FeO), can be used as the negative electrode active material. Materials that undergo a conversion reaction include oxides such as Fe2O3, CuO, Cu2O, RuO2, and Cr2O3, and CoS 0.89 It also occurs with sulfides such as NiS and CuS, nitrides such as Zn3N2, Cu3N and Ge3N4, phosphides such as NiP2, FeP2 and CoP3, and fluorides such as FeF3 and BiF3.

[0185] As the conductive additive and binder that can be contained in the negative electrode active material layer, the same materials as the conductive additive and binder that can be contained in the positive electrode active material layer can be used.

[0186] <Negative electrode current collector> The negative electrode current collector may be made of the same material as the positive electrode current collector, or may be made of copper, etc. It is preferable that the negative electrode current collector be made of a material that does not alloy with carrier ions such as lithium.

[0187] [Electrolyte] Examples of the electrolyte include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, chloroethylene carbonate, vinylene carbonate, γ-butyrolactone, γ-valerolactone, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, 1,3-dioxane, 1,4-dioxane, dimethoxyethane (DME), dimethyl sulfoxide, diethyl ether, methyl diglyme, acetonitrile, benzonitrile, tetrahydrofuran, sulfolane, and sultone, and any combination and ratio of two or more of these can be used.

[0188] The electrolyte preferably contains fluorine. For example, an electrolyte containing one or more fluorinated cyclic carbonates and lithium ions can be used as the fluorine-containing electrolyte. The fluorinated cyclic carbonate improves non-flammability and can enhance the safety of the lithium ion secondary battery.

[0189] Fluorinated cyclic carbonates include fluorinated ethylene carbonates, such as monofluoroethylene carbonate (fluoroethylene carbonate, FEC, F1EC), difluoroethylene carbonate (DFEC, F2EC), trifluoroethylene carbonate (F3EC), and tetrafluoroethylene carbonate (F4EC). DFEC includes isomers such as cis-4,5 and trans-4,5. For low-temperature operation, it is important to use one or more fluorinated cyclic carbonates as an electrolyte to solvate lithium ions and transport them within the electrolyte contained in the electrodes during charging and discharging. Using a fluorinated cyclic carbonate not as a small additive but to contribute to the transport of lithium ions during charging and discharging enables low-temperature operation.

[0190] The use of a fluorinated cyclic carbonate in the electrolyte reduces the desolvation energy required for lithium ions solvated in the electrolyte contained in the electrode to enter active material particles. Reducing this desolvation energy facilitates insertion and desorption of lithium ions into active material particles, even at low temperatures. While lithium ions may migrate in a solvated state, they may also undergo a hopping phenomenon, in which the coordinated solvent molecules are swapped. Easier desolvation from lithium ions facilitates migration via the hopping phenomenon, which may facilitate lithium ion migration.

[0191] A plurality of solvated lithium ions may form clusters in the electrolyte and move within the negative electrode, between the positive electrode and the negative electrode, within the positive electrode, etc.

[0192] Examples of fluorinated cyclic carbonates are shown below.

[0193] Monofluoroethylene carbonate (FEC) is represented by the following formula (1).

[0194] [ka]

[0195] Tetrafluoroethylene carbonate (F4EC) is represented by the following formula (2).

[0196] [ka]

[0197] Difluoroethylene carbonate (DFEC) is represented by the following formula (3).

[0198] [ka]

[0199] Furthermore, by using one or more flame-retardant and non-volatile ionic liquids (room-temperature molten salts) as the electrolyte solvent, it is possible to prevent the secondary battery from exploding or catching fire even if the internal temperature rises due to an internal short circuit or overcharging. Impregnating the separator with an ionic liquid can realize a non-flammable secondary battery. Ionic liquids consist of cations and anions, including organic cations and anions. Examples of organic cations include aliphatic onium cations such as quaternary ammonium cations, tertiary sulfonium cations, and quaternary phosphonium cations, as well as aromatic cations such as imidazolium cations and pyridinium cations. Examples of anions include monovalent amide anions, monovalent methide anions, fluorosulfonate anions, perfluoroalkylsulfonate anions, tetrafluoroborate anions, perfluoroalkylborate anions, hexafluorophosphate anions, and perfluoroalkylphosphate anions.

[0200] As an ionic liquid having an imidazolium cation, for example, an ionic liquid represented by the following general formula (G1) can be used. In general formula (G1), R 1 represents an alkyl group having 1 to 4 carbon atoms, and R 2 ~R 4 R5 represents an alkyl group or a main chain composed of two or more atoms selected from C, O, Si, N, S, and P. 5 A substituent may be introduced into the main chain of the polymer. Examples of the substituent to be introduced include an alkyl group and an alkoxy group.

[0201] [ka]

[0202] Examples of the cation represented by general formula (G1) include 1-ethyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-methyl-3-(propoxyethyl)imidazolium cation, and 1-hexyl-3-methylimidazolium cation.

[0203] As the ionic liquid having a pyridinium cation, for example, an ionic liquid represented by the following general formula (G2) may be used. In general formula (G2), R 6 represents an alkyl group or a main chain composed of two or more atoms selected from C, O, Si, N, S, and P, and R 7 ~R 11 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 6 A substituent may be introduced into the main chain of the polymer. Examples of the substituent to be introduced include an alkyl group and an alkoxy group.

[0204] [ka]

[0205] As the ionic liquid having a quaternary ammonium cation, for example, ionic liquids represented by the following general formulae (G3), (G4), (G5) and (G6) can be used.

[0206] [ka]

[0207] In general formula (G3), R 28 ~R 31 each independently represents an alkyl group having 1 to 20 carbon atoms, a methoxy group, a methoxymethyl group, a methoxyethyl group, or a hydrogen atom.

[0208] [ka]

[0209] In general formula (G4), R 12 ~R 17 each independently represents an alkyl group having 1 to 20 carbon atoms, a methoxy group, a methoxymethyl group, a methoxyethyl group, or a hydrogen atom. An example of a cation represented by general formula (G4) is a 1-methyl-1-propylpyrrolidinium cation.

[0210] [ka]

[0211] In general formula (G5), R 18 ~R 24 each independently represents an alkyl group having 1 to 20 carbon atoms, a methoxy group, a methoxymethyl group, a methoxyethyl group, or a hydrogen atom. Examples of the cation represented by general formula (G5) include an N-methyl-N-propylpiperidinium cation and a 1,3-dimethyl-1-propylpiperidinium cation.

[0212] [ka]

[0213] In general formula (G6), n and m are 1 or more and 3 or less. α is 0 or more and 6 or less; when n is 1, α is 0 or more and 4 or less; when n is 2, α is 0 or more and 5 or less; and when n is 3, α is 0 or more and 6 or less. β is 0 or more and 6 or less; when m is 1, β is 0 or more and 4 or less; when m is 2, β is 0 or more and 5 or less; and when m is 3, β is 0 or more and 6 or less. When α or β is 0, this indicates unsubstituted. This does not include cases where both α and β are 0. X or Y represents, as a substituent, a linear or side-chain alkyl group having 1 to 4 carbon atoms, a linear or side-chain alkoxy group having 1 to 4 carbon atoms, or a linear or side-chain alkoxyalkyl group having 1 to 4 carbon atoms.

[0214] As an ionic liquid having a tertiary sulfonium cation, for example, an ionic liquid represented by the following general formula (G7) can be used. In general formula (G7), R 25 ~R 27 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. 25 ~R 27 A main chain composed of two or more atoms selected from C, O, Si, N, S and P atoms may be used as the main chain.

[0215] [ka]

[0216] As an ionic liquid having a quaternary phosphonium cation, for example, an ionic liquid represented by the following general formula (G8) can be used. In general formula (G8), R 32 ~R 35 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. 32 ~R 35 A main chain composed of two or more atoms selected from C, O, Si, N, S and P atoms may be used as the main chain.

[0217] [ka]

[0218] A represented by general formulas (G1) to (G8) - As the anion, one or more of a monovalent amide anion, a monovalent methide anion, a fluorosulfonate anion, a perfluoroalkylsulfonate anion, a tetrafluoroborate anion, a perfluoroalkylborate anion, a hexafluorophosphate anion, and a perfluoroalkylphosphate anion can be used.

[0219] Monovalent amide anions include (C n F 2n+1 SO2)2N- (n = 0 to 3), and the monovalent cyclic amide anion is (CF2SO2)2N - The monovalent methide anions include (C n F 2n+1 SO2)3C - (n = 0 to 3), monovalent cyclic methide anions include (CF2SO2)2C - (CF3SO2) and the like can be used. As the fluoroalkylsulfonate anion, (C m F 2m+1 SO3) - (m=0 or more and 4 or less). Fluoroalkylborate anions include {BF n (C m H k F 2m+1-k ) 4-n} - (n = 0 or more and 3 or less, m = 1 or more and 4 or less, k = 0 or more and 2m or less). Fluoroalkyl phosphate anions include {PF n (C m H k F 2m+1-k ) 6-n} - (n = 0 to 5, m = 1 to 4, k = 0 to 2m)

[0220] Furthermore, as the monovalent amide anion, for example, one or more of a bis(fluorosulfonyl)amide anion and a bis(trifluoromethanesulfonyl)amide anion can be used.

[0221] The ionic liquid may also have one or more of a hexafluorophosphate anion and a tetrafluoroborate anion.

[0222] Hereafter, (FSO2)2N - The anion represented by the formula is the FSA anion, (CF3SO2)2N - The anion represented by the formula is sometimes referred to as the TFSA anion.

[0223] The secondary battery of one embodiment of the present invention has, as carrier ions, one or more of alkali metal ions such as sodium ions and potassium ions, and alkaline earth metal ions such as calcium ions, strontium ions, barium ions, beryllium ions, and magnesium ions.

[0224] When lithium ions are used as carrier ions, the electrolyte contains a lithium salt, such as LiPF, LiClO, LiAsF, LiBF, LiAlCl, LiSCN, LiBr, LiI, LiSO, and LiB. 10 Cl 10 , Li2B 12 Cl 12 , LiCF3SO3, LiC4F9SO3, LiC(CF3SO2)3, LiC(C2F5SO2)3, LiN(CF3SO2)2, LiN(C4F9SO2)(CF3SO2), LiN(C2F5SO2)2, etc. can be used.

[0225] In this specification, the term "electrolyte" is a general term that includes solid, liquid, or semi-solid electrolyte materials.

[0226] Deterioration is likely to occur at interfaces within a secondary battery, such as the interface between an active material and an electrolyte. In a secondary battery according to one embodiment of the present invention, the use of a fluorine-containing electrolyte can prevent deterioration, typically electrolyte alteration or increased viscosity, that can occur at the interface between the active material and the electrolyte. DFEC, which has two fluorine atoms bonded, and F4EC, which has four fluorine atoms bonded, have lower viscosities and weaker coordination bonds with lithium than FEC, which has one fluorine atom bonded. This reduces the adhesion of viscous decomposition products to active material particles. When viscous decomposition products adhere to or cling to active material particles, lithium ions are less likely to migrate at the interface between the active material particles. Solvation of lithium ions in a fluorine-containing electrolyte reduces the formation of decomposition products on the surface of the active material (positive electrode active material or negative electrode active material). Furthermore, the use of a fluorine-containing electrolyte can prevent the adhesion of decomposition products, thereby preventing the formation and growth of dendrites.

[0227] Another feature is that a fluorine-containing electrolyte is used as the main component, and the fluorine-containing electrolyte is 5% by volume or more, 10% by volume or more, preferably 30% by volume or more and 100% by volume or less.

[0228] In this specification, the term "main component of the electrolyte" refers to 5% by volume or more of the total electrolyte of the secondary battery. Furthermore, "5% by volume or more of the total electrolyte of the secondary battery" refers to the proportion of the total electrolyte measured during the manufacture of the secondary battery. Furthermore, when disassembling a secondary battery after fabrication, it is difficult to quantify the proportion of each of multiple electrolytes, but it is possible to determine whether a certain type of organic compound accounts for 5% by volume or more of the total electrolyte.

[0229] By using an electrolyte containing fluorine, it is possible to realize a secondary battery that can operate over a wide temperature range, specifically, from -40°C to 150°C, preferably from -40°C to 85°C.

[0230] The electrolyte may also contain additives such as vinylene carbonate, propane sultone (PS), tert-butylbenzene (TBB), lithium bis(oxalato)borate (LiBOB), or dinitrile compounds such as succinonitrile and adiponitrile. The concentration of the additive may be, for example, 0.1% by volume or more and less than 5% by volume of the entire electrolyte.

[0231] In addition to the above, the electrolyte may contain one or more aprotic organic solvents such as γ-butyrolactone, acetonitrile, dimethoxyethane, and tetrahydrofuran.

[0232] Furthermore, the use of a gelling polymer material in the electrolyte increases safety against leakage, etc. Typical examples of gelling polymer materials include silicone gel, acrylic gel, acrylonitrile gel, polyethylene oxide gel, polypropylene oxide gel, and fluorine-based polymer gel.

[0233] Examples of polymeric materials that can be used include polymers having a polyalkylene oxide structure, such as polyethylene oxide (PEO), PVdF, and polyacrylonitrile, as well as copolymers containing these. For example, PVdF-HFP, a copolymer of PVdF and hexafluoropropylene (HFP), can be used. The polymeric material formed may also have a porous shape.

[0234] [Exterior body] The exterior body of the secondary battery can be made of a metal material such as aluminum and / or a resin material. Alternatively, a film-like exterior body can be used. Examples of the film include a three-layer structure film in which a thin, flexible metal film made of aluminum, stainless steel, copper, nickel, or the like is provided on a film made of a material such as polyethylene, polypropylene, polycarbonate, ionomer, or polyamide, and an insulating synthetic resin film made of polyamide resin, polyester resin, or the like is further provided on the thin metal film as the outer surface of the exterior body.

[0235] This embodiment mode can be implemented in appropriate combination with other embodiment modes.

[0236] (Embodiment 2) In this embodiment mode, a method for manufacturing a secondary battery will be described.

[0237] <Method 1 for producing laminated secondary batteries> An example of a method for producing a laminated secondary battery whose external views are shown in Figures 8A and 8B will now be described with reference to Figures 9A and 9B and Figures 10A and 10B. A secondary battery 500 shown in Figures 8A and 8B has a positive electrode 503, a negative electrode 506, a separator 507, an outer casing 509, a positive electrode lead electrode 510, and a negative electrode lead electrode 511.

[0238] First, a positive electrode 503, a negative electrode 506, and a separator 507 are prepared. FIG. 9A shows an example of the positive electrode 503 and the negative electrode 506. The positive electrode 503 has a positive electrode active material layer 502 on a positive electrode current collector 501. The positive electrode 503 preferably has a tab region where the positive electrode current collector 501 is exposed. The negative electrode 506 has a negative electrode active material layer 505 on a negative electrode current collector 504. The negative electrode 506 preferably has a tab region where the negative electrode current collector 504 is exposed.

[0239] Next, negative electrodes 506, separators 507, and positive electrodes 503 are stacked. Fig. 9B shows the stacked negative electrodes 506, separators 507, and positive electrodes 503. Here, an example is shown in which five pairs of negative electrodes and four pairs of positive electrodes are used. The stacked negative electrodes 506, separators 507, and positive electrodes 503 can also be called a laminate consisting of a negative electrode, separator, and positive electrode.

[0240] Next, the tab regions of the positive electrode 503 are joined together, and the positive electrode lead electrode 510 is joined to the tab region of the outermost positive electrode. For joining, ultrasonic welding, for example, may be used. Similarly, the tab regions of the negative electrode 506 are joined together, and the negative electrode lead electrode 511 is joined to the tab region of the outermost negative electrode.

[0241] Next, the negative electrode 506 , the separator 507 and the positive electrode 503 are placed on the exterior body 509 .

[0242] Next, as shown in Fig. 10A, the exterior body 509 is bent at the portion indicated by the dashed line. Thereafter, the outer periphery of the exterior body 509 is joined. For example, thermocompression bonding may be used for the joining. At this time, an area (hereinafter referred to as an inlet 516) that is not joined is provided in a part (or one side) of the exterior body 509 so that the electrolyte 508 can be introduced later.

[0243] Next, as shown in Fig. 10B, electrolyte 508 is introduced into exterior body 509 through inlet 516 provided in exterior body 509. Introduction of electrolyte 508 is preferably performed under a reduced pressure atmosphere or an inert atmosphere. Finally, inlet 516 is joined. In this manner, laminated secondary battery 500 can be fabricated.

[0244] In the above, the positive electrode lead electrode 510 and the negative electrode lead electrode 511 are led out of the exterior of the outer casing from the same side to produce the secondary battery 500 shown in Fig. 8A. The positive electrode lead electrode 510 and the negative electrode lead electrode 511 can also be led out of the exterior of the outer casing from opposite sides to produce the secondary battery 500 shown in Fig. 8B.

[0245] <Method 2 for producing laminated secondary batteries> Next, an example of a method for manufacturing a laminated secondary battery 600, the external view of which is shown in Fig. 11, will be described with reference to Fig. 12, Fig. 13, Fig. 14A to Fig. 14D, and Fig. 15A to Fig. 15F. The secondary battery 600 shown in Fig. 11 has a positive electrode 503, a negative electrode 506, a separator 507, an outer casing 509, a positive electrode lead electrode 510, and a negative electrode lead electrode 511. The outer casing 509 is sealed in a region 514.

[0246] The laminated secondary battery 600 can be fabricated using, for example, the manufacturing apparatus shown in FIG. 12 . The manufacturing apparatus 570 shown in FIG. 12 includes a material input chamber 571, a transfer chamber 572, a processing chamber 573, and a material removal chamber 576. Each chamber can be connected to various exhaust mechanisms depending on the intended use. Each chamber can be connected to various gas supply mechanisms depending on the intended use. To prevent impurities from entering the manufacturing apparatus 570, an inert gas is preferably supplied to the manufacturing apparatus 570. The gas supplied to the manufacturing apparatus 570 is preferably highly purified using a gas purifier before being introduced into the manufacturing apparatus 570. The material input chamber 571 is a chamber for loading a positive electrode, a separator, a negative electrode, an outer casing, and the like into the manufacturing apparatus 570. The transfer chamber 572 includes a transfer mechanism 580. The processing chamber 573 includes a stage and an electrolyte dripping mechanism. The component removal chamber 576 is a chamber for removing the fabricated secondary battery to the outside of the manufacturing apparatus 570.

[0247] The laminated secondary battery 600 is fabricated as follows.

[0248] First, an exterior body 509b is placed on a stage 591 of a processing chamber 573, and then a positive electrode 503 is placed on the exterior body 509b (FIGS. 14A and 14B). Next, an electrolyte 515a is dropped onto the positive electrode 503 from a nozzle 594 (FIGS. 14C and 14D). FIG. 14D is a cross section corresponding to the dashed-dotted line AB in FIG. 14C. Note that the illustration of the stage 591 may be omitted to avoid cluttering the drawings. The dropping method may be, for example, any one of a dispensing method, a spray method, an inkjet method, or the like. The electrolyte may be dropped using an ODF (One Drop Fill) method.

[0249] By moving the nozzle 594, the electrolyte 515a can be dropped over the entire surface of the positive electrode 503. Alternatively, by moving the stage 591, the electrolyte 515a may be dropped over the entire surface of the positive electrode 503.

[0250] The electrolyte is preferably dropped from a position whose shortest distance from the receiving surface is greater than 0 mm and equal to or less than 1 mm.

[0251] It is also preferable to appropriately adjust the viscosity of the electrolyte dropped from a nozzle, etc. If the viscosity of the entire electrolyte is within the range of 0.3 mPa·s to 1000 mPa·s at room temperature (25°C), it can be dropped from a nozzle.

[0252] In addition, since the viscosity of the electrolyte changes depending on the temperature of the electrolyte, it is preferable to appropriately adjust the temperature of the electrolyte to be dropped. The temperature of the electrolyte is preferably equal to or higher than the melting point and equal to or lower than the boiling point or flash point of the electrolyte.

[0253] Next, a separator 507 is placed on the positive electrode 503 so as to overlap one entire surface of the positive electrode 503 (FIG. 15A). Subsequently, an electrolyte 515b is dropped onto the separator 507 using a nozzle 594 (FIG. 15B). Thereafter, a negative electrode 506 is placed on the separator 507 (FIG. 15C). The negative electrode 506 is placed on top of the separator 507 so as not to protrude from the separator 507 in a top view. Subsequently, an electrolyte 515c is dropped onto the negative electrode 506 using a nozzle 594 (FIG. 15D). Thereafter, a stack of the positive electrode 503, the separator 507, and the negative electrode 506 is further stacked to produce the stack 512 shown in FIG. 13. Next, the positive electrode 503, the separator 507, and the negative electrode 506 are sealed with the exterior body 509a and the exterior body 509b (FIGS. 15E and 15F).

[0254] Multiple laminates 512 can be arranged on exterior body 509b to produce multiple panels. After sealing exterior bodies 509a and 509b at region 514 so as to surround the active material layer, each laminate 512 is cut outside region 514, allowing the multiple secondary batteries to be separated individually.

[0255] During sealing, first, a frame-shaped resin layer 513 is formed on exterior body 509b. Next, at least a portion of resin layer 513 is irradiated with light under reduced pressure to harden at least a portion of resin layer 513. Next, sealing is performed in region 514 by thermocompression bonding or welding under atmospheric pressure. Alternatively, only sealing by thermocompression bonding or welding may be performed without performing the above-mentioned sealing by light irradiation.

[0256] Although Figure 11 shows an example in which the exterior body 509 is sealed on all four sides (sometimes called four-sided sealing), it may also be sealed on three sides (sometimes called three-sided sealing) as shown in Figures 8A and 8B.

[0257] Through the above steps, the laminated secondary battery 600 can be fabricated.

[0258] <Other secondary batteries and their manufacturing methods 1> An example of a cross-sectional view of a stack of one embodiment of the present invention is shown in Figure 16. A stack 550 shown in Figure 16 is produced by placing one separator between a positive electrode and a negative electrode while folding it.

[0259] In the laminate 550, one separator 507 is folded multiple times so as to be sandwiched between the positive electrode active material layers 502 and the negative electrode active material layers 505. In FIG. 16, six layers of positive electrodes 503 and six layers of negative electrodes 506 are stacked, and therefore the separator 507 is folded at least five times. The separator 507 may not only be provided so as to be sandwiched between the positive electrode active material layers 502 and the negative electrode active material layers 505, but also have its extending portion further folded so that the plurality of positive electrodes 503 and negative electrodes 506 are bound together with tape or the like.

[0260] In the method for manufacturing a secondary battery of one embodiment of the present invention, after the positive electrode 503 is disposed, an electrolyte can be dropped onto the positive electrode 503. Similarly, after the negative electrode 506 is disposed, an electrolyte can be dropped onto the negative electrode 506. Furthermore, in the method for manufacturing a secondary battery of one embodiment of the present invention, an electrolyte can be dropped onto the separator 507 before folding the separator or after folding the separator 507 and overlapping it with the negative electrode 506 or the positive electrode 503. By dropping the electrolyte onto at least one of the negative electrode 506, the separator 507, and the positive electrode 503, the negative electrode 506, the separator 507, or the positive electrode 503 can be impregnated with the electrolyte.

[0261] 17A has a laminate 972 inside a housing 971. Terminals 973b and 974b are electrically connected to the laminate 972. At least a portion of terminal 973b and at least a portion of terminal 974b are exposed to the outside of the housing 971.

[0262] A structure in which a positive electrode, a negative electrode, and a separator are stacked can be used as the stack body 972. Alternatively, a structure in which a positive electrode, a negative electrode, and a separator are wound can be used as the stack body 972.

[0263] For example, the laminate 972 may be a laminate having a structure in which the separator is folded back as shown in FIG.

[0264] An example of a method for manufacturing the stacked body 972 will be described with reference to FIGS. 17B and 17C.

[0265] First, as shown in FIG. 17B, a strip-shaped separator 976 is placed on top of a positive electrode 975a, and then a negative electrode 977a is placed on top of the positive electrode 975a with the separator 976 sandwiched between them. Thereafter, the separator 976 is folded back and placed on top of the negative electrode 977a. Next, as shown in FIG. 17C, a positive electrode 975b is placed on top of the negative electrode 977a with the separator 976 sandwiched between them. In this way, by folding back the separator and arranging the positive electrode and negative electrode in order, a laminate 972 can be produced. A structure including a laminate produced in this way is sometimes called a "zigzag structure."

[0266] Next, an example of a method for manufacturing the secondary battery 970 will be described with reference to FIGS. 18A to 18C.

[0267] 18A, a positive electrode lead electrode 973a is electrically connected to the positive electrode of the laminate 972. Specifically, for example, a tab region may be provided on each positive electrode of the laminate 972, and each tab region may be electrically connected to the positive electrode lead electrode 973a by welding or the like. In addition, a negative electrode lead electrode 974a is electrically connected to the negative electrode of the laminate 972.

[0268] One stacked body 972 may be arranged inside housing 971, or a plurality of stacked bodies 972 may be arranged inside housing 971. Fig. 18B shows an example in which two sets of stacked bodies 972 are prepared.

[0269] Next, as shown in FIG. 18C , the prepared laminate 972 is housed in a housing 971, terminals 973b and 974b are attached, and the housing 971 is sealed. It is preferable that a conductor 973c is electrically connected to each positive electrode lead electrode 973a of the plurality of laminates 972. It is also preferable that a conductor 974c is electrically connected to each negative electrode lead electrode 974a of the plurality of laminates 972. The terminal 973b is electrically connected to the conductor 973c, and the terminal 974b is electrically connected to the conductor 974c. The conductor 973c may have a conductive region and an insulating region. The conductor 974c may have a conductive region and an insulating region.

[0270] A metal material (such as aluminum) can be used for the housing 971. When a metal material is used for the housing 971, the surface is preferably covered with resin or the like. Alternatively, a resin material can be used for the housing 971.

[0271] It is preferable to provide a safety valve, an overcurrent protection element, or the like in the housing 971. The safety valve is a valve that releases gas when the pressure inside the housing 971 reaches a predetermined level in order to prevent the battery from exploding.

[0272] <Other secondary batteries and their manufacturing methods 2> 19C shows an example of a cross-sectional view of a secondary battery of another embodiment of the present invention. A secondary battery 560 shown in Fig. 19C is fabricated using the stack 130 shown in Fig. 19A and the stack 131 shown in Fig. 19B. Note that for clarity, Fig. 19C only shows the stack 130, the stack 131, and the separator 507.

[0273] As shown in FIG. 19A, the laminate 130 includes a positive electrode 503 having a positive electrode active material layer on both sides of a positive electrode current collector, a separator 507, a negative electrode 506 having a negative electrode active material layer on both sides of a negative electrode current collector, the separator 507, and a positive electrode 503 having a positive electrode active material layer on both sides of a positive electrode current collector, stacked in this order.

[0274] As shown in FIG. 19B , the laminate 131 includes a negative electrode 506 having a negative electrode active material layer on both sides of a negative electrode current collector, a separator 507, a positive electrode 503 having a positive electrode active material layer on both sides of a positive electrode current collector, the separator 507, and a negative electrode 506 having a negative electrode active material layer on both sides of a negative electrode current collector laminated in this order.

[0275] The method for manufacturing a secondary battery according to one embodiment of the present invention can be applied to manufacturing a stack. Specifically, when stacking the negative electrode 506, the separator 507, and the positive electrode 503 to manufacture a stack, an electrolyte is dropped onto at least one of the negative electrode 506, the separator 507, and the positive electrode 503. By dropping multiple drops of the electrolyte, the negative electrode 506, the separator 507, or the positive electrode 503 can be impregnated with the electrolyte.

[0276] As shown in FIG. 19C, the plurality of stacks 130 and the plurality of stacks 131 are covered with a wound separator 507.

[0277] In addition, in the method for manufacturing a secondary battery of one embodiment of the present invention, after the stack 130 is arranged, an electrolyte can be dropped onto the stack 130. Similarly, after the stack 131 is arranged, an electrolyte can be dropped onto the stack 131. Furthermore, before the separator 507 is folded, or after the separator 507 is folded and overlapped with the stack, an electrolyte can be dropped onto the separator 507. By dropping multiple drops of the electrolyte, the stack 130, the stack 131, or the separator 507 can be impregnated with the electrolyte.

[0278] <Other secondary batteries and their manufacturing methods 3> A secondary battery of another embodiment of the present invention will be described with reference to Figures 20 and 21. The secondary battery described here can be called a wound-type secondary battery, or the like.

[0279] A secondary battery 913 shown in FIG. 20A has a wound body 950 provided with terminals 951 and 952 inside a housing 930. The wound body 950 is immersed in an electrolyte inside the housing 930. The terminal 952 contacts the housing 930, and the terminal 951 is not in contact with the housing 930 by using an insulating material or the like. Note that in FIG. 20A, for convenience, the housing 930 is shown separated, but in reality, the wound body 950 is covered by the housing 930, and the terminals 951 and 952 extend outside the housing 930. The housing 930 can be made of a metal material (such as aluminum) or a resin material.

[0280] 20B, the housing 930 shown in Fig. 20A may be formed from a plurality of materials. For example, the secondary battery 913 shown in Fig. 20B has housings 930a and 930b bonded together, and a wound body 950 is provided in the area surrounded by the housings 930a and 930b.

[0281] The housing 930a can be made of an insulating material such as organic resin. In particular, by using a material such as organic resin on the surface on which the antenna is formed, it is possible to prevent the secondary battery 913 from blocking the electric field. Note that if the electric field blocking effect of the housing 930a is small, the antenna may be provided inside the housing 930a. The housing 930b can be made of, for example, a metal material.

[0282] 20C shows the structure of wound body 950. Winding body 950 has a negative electrode 931, a positive electrode 932, and a separator 933. Winding body 950 is a wound body in which negative electrode 931 and positive electrode 932 are stacked on top of each other with separator 933 sandwiched therebetween, and the stacked sheet is wound. Note that multiple stacks of negative electrode 931, positive electrode 932, and separator 933 may be stacked.

[0283] In a method for manufacturing a secondary battery according to one embodiment of the present invention, when the negative electrode 931, the separator 933, and the positive electrode 932 are stacked, an electrolyte is dropped onto at least one of the negative electrode 931, the separator 933, and the positive electrode 932. That is, the electrolyte is preferably dropped onto at least one of the negative electrode 931, the separator 933, and the positive electrode 932 before the laminate sheet is wound. By dropping multiple drops of the electrolyte, the negative electrode 931, the separator 933, or the positive electrode 932 can be impregnated with the electrolyte.

[0284] Alternatively, a secondary battery 913 may be provided that has a wound body 950a as shown in Fig. 21A. The wound body 950a shown in Fig. 21A has a negative electrode 931, a positive electrode 932, and a separator 933. The negative electrode 931 has a negative electrode active material layer 931a. The positive electrode 932 has a positive electrode active material layer 932a.

[0285] The separator 933 has a width wider than the negative electrode active material layer 931a and the positive electrode active material layer 932a, and is wound so as to overlap the negative electrode active material layer 931a and the positive electrode active material layer 932a. From the standpoint of safety, it is preferable that the negative electrode active material layer 931a be wider than the positive electrode active material layer 932a. A wound body 950a having such a shape is preferable in terms of safety and productivity.

[0286] 21B, the negative electrode 931 is electrically connected to a terminal 951. The terminal 951 is electrically connected to a terminal 911a. The positive electrode 932 is electrically connected to a terminal 952. The terminal 952 is electrically connected to a terminal 911b.

[0287] 21C, wound body 950a and the electrolyte are covered by casing 930 to form secondary battery 913. It is preferable to provide casing 930 with a safety valve, an overcurrent protection element, etc. The safety valve opens temporarily only when the internal pressure of casing 930 exceeds a predetermined value, in order to prevent the battery from exploding.

[0288] 21B, the secondary battery 913 may have a plurality of wound bodies 950a. By using a plurality of wound bodies 950a, the secondary battery 913 can have a larger charge / discharge capacity.

[0289] This embodiment mode can be combined with other embodiment modes as appropriate.

[0290] (Embodiment 3) In this embodiment, application examples of a secondary battery of one embodiment of the present invention will be described with reference to FIGS.

[0291] [vehicle] First, an example in which the secondary battery of one embodiment of the present invention is applied to an electric vehicle (EV) will be described.

[0292] 22C shows a block diagram of a vehicle having a motor. The electric vehicle is equipped with first batteries 1301a and 1301b as main driving secondary batteries, and a second battery 1311 that supplies power to an inverter 1312 that starts a motor 1304. The second battery 1311 is also called a cranking battery or starter battery. The second battery 1311 only needs to have high output, and does not need to have a large capacity, and the capacity of the second battery 1311 is smaller than that of the first batteries 1301a and 1301b.

[0293] For example, one or both of the first batteries 1301a and 1301b can be a secondary battery manufactured using a method for manufacturing a secondary battery according to one embodiment of the present invention.

[0294] In this embodiment, an example is shown in which two first batteries 1301a and 1301b are connected in parallel, but three or more may be connected in parallel. Also, if the first battery 1301a can store sufficient power, the first battery 1301b may not be necessary. By configuring a battery pack having multiple secondary batteries, it is possible to extract large amounts of power. The multiple secondary batteries may be connected in parallel, in series, or in series after being connected in parallel. A plurality of secondary batteries is also called a battery pack.

[0295] In addition, in order to cut off power from a plurality of secondary batteries in a vehicle, a service plug or circuit breaker that can cut off high voltage without using tools is provided in the first battery 1301a.

[0296] The power of the first batteries 1301a and 1301b is mainly used to rotate the motor 1304, but also supplies power to 42V (high voltage) on-board components (such as an electric power steering 1307, a heater 1308, and a defogger 1309) via a DC-DC circuit 1306. When a rear motor 1317 is provided for the rear wheels, the first battery 1301a is also used to rotate the rear motor 1317.

[0297] The second battery 1311 also supplies power via the DC-DC circuit 1310 to 14V (low voltage) in-vehicle components (audio 1313, power windows 1314, lamps 1315, etc.).

[0298] The first battery 1301a will be described with reference to FIG. 22A.

[0299] 22A shows an example of a large battery pack 1415. One electrode of the battery pack 1415 is electrically connected to the control circuit unit 1320 by a wiring 1421. The other electrode is electrically connected to the control circuit unit 1320 by a wiring 1422. The battery pack may have a configuration in which a plurality of secondary batteries are connected in series.

[0300] A memory circuit including a transistor using an oxide semiconductor may be used for the control circuit unit 1320. A charge control circuit or a battery control system having a memory circuit including a transistor using an oxide semiconductor may be referred to as a battery operating system (BTOS) or a battery oxide semiconductor.

[0301] The control circuit 1320 detects the terminal voltage of the secondary battery and manages the charge / discharge state of the secondary battery. For example, to prevent overcharging, it can turn off both the output transistor and the cutoff switch of the charging circuit almost simultaneously.

[0302] FIG. 22B shows an example of a block diagram of the battery pack 1415 shown in FIG. 22A.

[0303] The control circuit unit 1320 includes a switch unit 1324 including at least a switch for preventing overcharging and a switch for preventing overdischarging, a control circuit 1322 for controlling the switch unit 1324, and a voltage measurement unit for the first battery 1301a. The control circuit unit 1320 sets upper and lower voltage limits for the secondary battery used and limits the upper limit of the current from the outside or the upper limit of the output current to the outside. The range between the lower limit and the upper limit of the secondary battery's voltage is within the recommended voltage range. If the secondary battery falls outside this range, the switch unit 1324 activates and functions as a protection circuit. The control circuit unit 1320 can also be called a protection circuit because it controls the switch unit 1324 to prevent overcharging or overdischarging. For example, if the control circuit 1322 detects a voltage that could cause overcharging, it turns off the switch unit 1324 to cut off the current. A PTC element may also be provided in the charge / discharge path to provide a function for cutting off the current in response to a rise in temperature. The control circuit section 1320 also has an external terminal 1325 (+IN) and an external terminal 1326 (-IN).

[0304] The switch unit 1324 can be configured by combining one or both of n-channel transistors and p-channel transistors. The switch unit 1324 is not limited to a switch having a Si transistor using single crystal silicon. For example, the switch unit 1324 may be formed of a power transistor having Ge (germanium), SiGe (silicon germanium), GaAs (gallium arsenide), GaAlAs (gallium aluminum arsenide), InP (indium phosphide), SiC (silicon carbide), ZnSe (zinc selenide), GaN (gallium nitride), or GaOx (gallium oxide; x is a real number greater than 0). Furthermore, memory elements using OS transistors can be freely arranged by stacking them on circuits using Si transistors, facilitating integration. Furthermore, OS transistors can be fabricated using the same manufacturing equipment as Si transistors, allowing for low-cost fabrication. That is, a control circuit unit 1320 using OS transistors can be stacked on the switch unit 1324 and integrated into a single chip. The volume occupied by the control circuit section 1320 can be reduced, which allows for miniaturization.

[0305] The first batteries 1301a and 1301b mainly supply power to 42V (high voltage) in-vehicle devices, and the second battery 1311 supplies power to 14V (low voltage) in-vehicle devices. A lead-acid battery is often used as the second battery 1311 because of its cost advantage.

[0306] In this embodiment, an example is shown in which lithium ion secondary batteries are used as both the first battery 1301a and the second battery 1311. The second battery 1311 may be a lead storage battery, an all-solid-state battery, or an electric double layer capacitor.

[0307] Furthermore, regenerated energy generated by the rotation of the tire 1316 is sent to the motor 1304 via the gear 1305, and is then charged into the second battery 1311 from the motor controller 1303 or the battery controller 1302 via the control circuit unit 1321. Alternatively, the first battery 1301a is charged from the battery controller 1302 via the control circuit unit 1320. Alternatively, the first battery 1301b is charged from the battery controller 1302 via the control circuit unit 1320. In order to efficiently charge the regenerated energy, it is desirable that the first batteries 1301a and 1301b be capable of being rapidly charged.

[0308] The battery controller 1302 can set the charging voltage and charging current of the first batteries 1301a and 1301b. The battery controller 1302 can set charging conditions in accordance with the charging characteristics of the secondary battery used, and can perform rapid charging.

[0309] Although not shown, when an external charger is connected, the charger's outlet or the charger's connection cable is electrically connected to the battery controller 1302. The power supplied from the external charger is charged to the first batteries 1301a, 1301b via the battery controller 1302. Some chargers are provided with a control circuit, and although the function of the battery controller 1302 may not be used, it is preferable to charge the first batteries 1301a, 1301b via a control circuit unit 1320 to prevent overcharging. In some cases, the connection cable or the charger's connection cable is provided with a control circuit. The control circuit unit 1320 is also called an ECU (Electronic Control Unit). The ECU is connected to a CAN (Controller Area Network) provided in the electric vehicle. CAN is one of the serial communication standards used as an in-vehicle LAN. The ECU includes a microcomputer. The ECU uses a CPU or a GPU.

[0310] Next, an example in which the secondary battery of one embodiment of the present invention is mounted on a vehicle, typically a transportation vehicle, will be described.

[0311] When a secondary battery according to one embodiment of the present invention is installed in a vehicle, next-generation clean energy vehicles such as hybrid vehicles (HVs), electric vehicles (EVs), and plug-in hybrid vehicles (PHVs) can be realized. Furthermore, the secondary battery can also be installed in agricultural machinery such as electric tractors, mopeds including electrically assisted bicycles, motorcycles, electric wheelchairs, electric carts, small or large ships, submarines, aircraft such as fixed-wing aircraft and rotary-wing aircraft, rockets, artificial satellites, space probes or planetary probes, and spacecraft. A large secondary battery can be fabricated by using a manufacturing method for a secondary battery according to one embodiment of the present invention. Therefore, the secondary battery according to one embodiment of the present invention can be suitably used in transportation vehicles.

[0312] 23A to 23E show transportation vehicles using a secondary battery of one embodiment of the present invention. The automobile 2001 shown in FIG. 23A is an electric automobile using an electric motor as a power source for running. Alternatively, it is a hybrid automobile that can appropriately select and use an electric motor or an engine as a power source for running. When a secondary battery is installed in a vehicle, the secondary battery is installed in one or more locations. The automobile 2001 shown in FIG. 23A includes the battery pack 1415 shown in FIG. 22A. The battery pack 1415 includes a secondary battery module. The battery pack 1415 preferably further includes a charge control device electrically connected to the secondary battery module. The secondary battery module includes one or more secondary batteries.

[0313] Furthermore, automobile 2001 can charge its secondary battery by receiving power supply from an external charging facility using a plug-in system, a contactless power supply system, or the like. Charging can be performed using a predetermined charging method or connector standard, such as CHAdeMO (registered trademark) or Combo, as appropriate. The charging device may be a charging station installed in a commercial facility or a household power source. For example, plug-in technology can be used to charge the secondary battery installed in automobile 2001 using external power supply. Charging can be performed by converting AC power to DC power via a conversion device such as an AC-DC converter.

[0314] Although not shown, a power receiving device can be mounted on a vehicle and power can be supplied contactlessly from a ground-based power transmitting device for charging. In the case of this contactless power supply method, by incorporating a power transmitting device into the road or an exterior wall, charging can be performed not only while the vehicle is stopped but also while the vehicle is moving. This contactless power supply method can also be used to transmit and receive power between two vehicles. Furthermore, a solar cell can be installed on the exterior of the vehicle, and the secondary battery can be charged while the vehicle is stopped or moving. For such contactless power supply, an electromagnetic induction method or a magnetic field resonance method can be used.

[0315] 23B shows a large transport vehicle 2002 having an electrically controlled motor as an example of a transport vehicle. The secondary battery module of the transport vehicle 2002 is, for example, a four-cell unit of secondary batteries of 3.5V to 4.7V, with 48 cells connected in series for a maximum voltage of 170V. Apart from the number of secondary batteries constituting the secondary battery module of the battery pack 2201, the transport vehicle 2002 has the same functions as those shown in FIG. 23A, and therefore a description thereof will be omitted.

[0316] FIG. 23C shows, as an example, a large transport vehicle 2003 having an electrically controlled motor. The secondary battery module of the transport vehicle 2003 has, for example, a maximum voltage of 600 V, which is obtained by connecting in series one hundred or more secondary batteries with a voltage of 3.5 V to 4.7 V. Therefore, a secondary battery with little variation in characteristics is required. By using the method for manufacturing a secondary battery according to one embodiment of the present invention, a secondary battery with stable battery characteristics can be manufactured, and mass production at low cost is possible from the viewpoint of yield. Furthermore, except for the number of secondary batteries constituting the secondary battery module of the battery pack 2202, the same functions as those shown in FIG. 23A are provided, and therefore description thereof will be omitted.

[0317] As an example, Fig. 23D shows an aircraft 2004 having an engine that burns fuel. Since the aircraft 2004 shown in Fig. 23D has wheels for takeoff and landing, it can also be said to be part of a transportation vehicle, and has a battery pack 2203 that includes a secondary battery module configured by connecting multiple secondary batteries and a charge control device.

[0318] The secondary battery module of the aircraft 2004 has, for example, eight 4 V secondary batteries connected in series to produce a maximum voltage of 32 V. Other than the number of secondary batteries constituting the secondary battery module of the battery pack 2203, it has the same functions as those in Fig. 23A, and therefore a description thereof will be omitted.

[0319] FIG. 23E shows an example of a transport vehicle 2005 for transporting cargo. The transport vehicle 2005 has an electrically controlled motor and performs various tasks by receiving power from a secondary battery constituting a secondary battery module of a battery pack 2204. Furthermore, the transport vehicle 2005 does not necessarily have to be driven by a human driver and can be unmanned using CAN communication or the like. While FIG. 23E illustrates a forklift, this is not a limitation, and a battery pack having a secondary battery according to one embodiment of the present invention can be mounted on industrial machinery that can be operated using CAN communication or the like, such as an automated transporter, a work robot, or a small construction machine.

[0320] 24A shows an example of an electric bicycle using the secondary battery of one embodiment of the present invention. The secondary battery of one embodiment of the present invention can be applied to the electric bicycle 2100 shown in Fig. 24A. A power storage device 2102 shown in Fig. 24B includes, for example, a plurality of secondary batteries and a protection circuit.

[0321] The electric bicycle 2100 includes a power storage device 2102. The power storage device 2102 can supply electricity to a motor that assists a rider. The power storage device 2102 is portable and is shown in a state removed from the bicycle in FIG. 24B . The power storage device 2102 includes a plurality of secondary batteries 2101 of one embodiment of the present invention, and a display 2103 can display the remaining battery charge and other information. The power storage device 2102 also includes a control circuit 2104 that can control charging or detect an abnormality of the secondary battery, which is an example of one embodiment of the present invention. The control circuit 2104 is electrically connected to the positive and negative electrodes of the secondary battery 2101. A small solid-state secondary battery may be provided in the control circuit 2104. Providing a small solid-state secondary battery in the control circuit 2104 can also supply power to retain data in a memory circuit of the control circuit 2104 for a long period of time. Furthermore, a synergistic effect in terms of safety can be obtained by combining a secondary battery using the positive electrode active material of one embodiment of the present invention as its positive electrode. A secondary battery and the control circuit 2104 in which the positive electrode active material according to one embodiment of the present invention is used for a positive electrode can significantly contribute to preventing accidents such as fires caused by secondary batteries.

[0322] 24C illustrates an example of a two-wheeled vehicle using the secondary battery of one embodiment of the present invention. A scooter 2300 illustrated in FIG. 24C includes a power storage device 2302, a side mirror 2301, and a turn signal light 2303. The power storage device 2302 can supply electricity to the turn signal light 2303. The power storage device 2302, which includes a plurality of secondary batteries each using the positive electrode active material of one embodiment of the present invention for its positive electrode, can have a high capacity and contribute to miniaturization. To improve safety, a protection circuit that prevents overcharging and / or overdischarging of the secondary battery may be electrically connected to the secondary battery.

[0323] 24C, the power storage device 2302 can be stored in the under-seat storage compartment 2304. The power storage device 2302 can be stored in the under-seat storage compartment 2304 even if the under-seat storage compartment 2304 is small.

[0324] [Buildings] Next, an example in which the secondary battery of one embodiment of the present invention is mounted in a building will be described with reference to FIG.

[0325] 25A includes a power storage device 2612 including a secondary battery with stable battery characteristics obtained by using a manufacturing method for a secondary battery according to one embodiment of the present invention, and a solar panel 2610. The power storage device 2612 is electrically connected to the solar panel 2610 through wiring 2611 or the like. The power storage device 2612 may also be electrically connected to a ground-mounted charging device 2604. The power obtained by the solar panel 2610 can be charged to the power storage device 2612. The power stored in the power storage device 2612 can be charged to a secondary battery included in a vehicle 2603 via the charging device 2604. The power storage device 2612 is preferably installed in an underfloor space. By installing the power storage device 2612 in the underfloor space, the space above the floor can be effectively utilized. Alternatively, the power storage device 2612 may be installed on the floor.

[0326] The power stored in the power storage device 2612 can be supplied to other electronic devices in the house. Therefore, even when power cannot be supplied from a commercial power source due to a power outage or the like, the power storage device 2612 can be used as an uninterruptible power supply, allowing the use of electronic devices.

[0327] 25B illustrates an example of a power storage device according to one embodiment of the present invention. As illustrated in FIG. 25B, a large-sized power storage device 791 obtained by the method for manufacturing a secondary battery according to one embodiment of the present invention is installed in an underfloor space 796 of a building 799.

[0328] A control device 790 is installed in the power storage device 791, and the control device 790 is electrically connected to a distribution board 703, a power storage controller 705 (also called a control device), a display 706, and a router 709 by wiring.

[0329] Electric power is sent from commercial power source 701 to distribution board 703 via service line attachment section 710. Electric power is also sent to distribution board 703 from power storage device 791 and commercial power source 701, and distribution board 703 supplies the sent electric power to general load 707 and power storage load 708 via an outlet (not shown).

[0330] The general load 707 is, for example, an electrical appliance such as a television or a personal computer, and the power storage load 708 is, for example, an electrical appliance such as a microwave oven, a refrigerator, or an air conditioner.

[0331] The power storage controller 705 has a measurement unit 711, a prediction unit 712, and a planning unit 713. The measurement unit 711 has a function of measuring the amount of power consumed by the general load 707 and the power storage load 708 during one day (for example, from midnight to midnight). The measurement unit 711 may also have a function of measuring the amount of power of the power storage device 791 and the amount of power supplied from the commercial power source 701. The prediction unit 712 has a function of predicting the amount of power demand to be consumed by the general load 707 and the power storage load 708 during the next day, based on the amount of power consumed by the general load 707 and the power storage load 708 during the previous day. The planning unit 713 has a function of creating a plan for charging and discharging the power storage device 791, based on the amount of power demand predicted by the prediction unit 712.

[0332] The amount of power consumed by the general load 707 and the power storage load 708 measured by the measurement unit 711 can be confirmed on the display 706. It can also be confirmed on an electrical device such as a television or a personal computer via the router 709. It can also be confirmed on a mobile electronic device such as a smartphone or a tablet via the router 709. The amount of power demand for each time period (or each hour) predicted by the prediction unit 712 can also be confirmed on the display 706, the electrical device, or the mobile electronic device.

[0333] [Electronic equipment] The secondary battery of one embodiment of the present invention can be used in, for example, one or both of an electronic device and a lighting device, such as a mobile phone, a smartphone, a portable information terminal such as a laptop computer, a portable game console, a portable music player, a digital camera, or a digital video camera.

[0334] 26A includes a housing 2801, a housing 2802, a display unit 2803, a keyboard 2804, a pointing device 2805, and the like. A secondary battery 2807 is provided inside the housing 2801, and a secondary battery 2806 is provided inside the housing 2802. To improve safety, a protection circuit that prevents overcharging and / or over-discharging of the secondary battery 2807 may be electrically connected to the secondary battery 2807. A touch panel is also applied to the display unit 2803. As shown in FIG. 26B, the housings 2801 and 2802 can be removed from the personal computer 2800, and the personal computer 2800 can be used as a tablet terminal using only the housing 2802.

[0335] A large secondary battery obtained by the method for manufacturing a secondary battery according to one embodiment of the present invention can be used as one or both of the secondary battery 2806 and the secondary battery 2807. The shape of the secondary battery obtained by the method for manufacturing a secondary battery according to one embodiment of the present invention can be freely changed by changing the shape of the exterior body. For example, by forming the secondary batteries 2806 and 2807 to match the shapes of the housings 2801 and 2802, the capacity of the secondary battery can be increased and the operating time of the personal computer 2800 can be extended. Furthermore, the weight of the personal computer 2800 can be reduced.

[0336] A flexible display is used for the display portion 2803 of the housing 2802. A large-sized secondary battery obtained by the manufacturing method of a secondary battery according to one embodiment of the present invention is used as the secondary battery 2806. A large-sized secondary battery obtained by the manufacturing method of a secondary battery according to one embodiment of the present invention can be made bendable by using a flexible film for the exterior body of the large-sized secondary battery. This allows the housing 2802 to be folded for use, as shown in FIG. 26C . In this case, part of the display portion 2803 can also be used as a keyboard, as shown in FIG. 26C .

[0337] Furthermore, the housing 2802 can be folded so that the display portion 2803 faces inward as shown in FIG. 26D, or so that the display portion 2803 faces outward as shown in FIG. 26E.

[0338] 27A illustrates an example of a mobile phone. The mobile phone 7400 includes a display portion 7402 built into a housing 7401, operation buttons 7403, an external connection port 7404, a speaker 7405, a microphone 7406, and the like. Note that the mobile phone 7400 includes a secondary battery 7407. By using the secondary battery of one embodiment of the present invention as the secondary battery 7407, a lightweight mobile phone with a long life can be provided. To improve safety, a protection circuit that prevents overcharging and / or overdischarging of the secondary battery 7407 may be electrically connected to the secondary battery 7407.

[0339] FIG. 27B shows the mobile phone 7400 in a bent state. When the mobile phone 7400 is deformed by an external force and bent as a whole, the secondary battery 7407 installed inside is also bent. FIG. 27C shows the state of the bent secondary battery 7407 at that time. The secondary battery 7407 is a thin storage battery. The secondary battery 7407 is fixed in a bent state. The secondary battery 7407 has a lead electrode electrically connected to the current collector. For example, the current collector is copper foil, and a portion of the current collector is alloyed with gallium to improve adhesion with the active material layer in contact with the current collector, resulting in a configuration with high reliability when the secondary battery 7407 is bent.

[0340] FIG. 27D shows an example of a bangle-type display device. The portable display device 7100 includes a housing 7101, a display unit 7102, operation buttons 7103, and a secondary battery 7104. To enhance safety, a protection circuit that prevents overcharging and / or overdischarging of the secondary battery 7104 may be electrically connected to the secondary battery 7104. FIG. 27E shows a bent secondary battery 7104. When the secondary battery 7104 is worn on a user's wrist in a bent state, the housing deforms, changing the curvature of part or all of the secondary battery 7104. The degree of bending at any point on the curve, expressed as the radius of the corresponding circle, is called the radius of curvature, and the reciprocal of the radius of curvature is called the curvature. Specifically, part or all of the main surfaces of the housing or secondary battery 7104 change within a radius of curvature range of 40 mm to 150 mm. High reliability can be maintained if the radius of curvature of the main surfaces of the secondary battery 7104 is within a range of 40 mm to 150 mm. By using the secondary battery of one embodiment of the present invention as the secondary battery 7104, a lightweight and long-life portable display device can be provided.

[0341] 27F shows an example of a wristwatch-type portable information terminal 7200. The portable information terminal 7200 includes a housing 7201, a display portion 7202, a band 7203, a buckle 7204, operation buttons 7205, an input / output terminal 7206, and the like.

[0342] The portable information terminal 7200 can execute various applications such as mobile phone calls, e-mail, document browsing and creation, music playback, internet communication, and computer games.

[0343] The display surface of the display portion 7202 is curved, and a display can be performed along the curved display surface. The display portion 7202 is also provided with a touch sensor, and can be operated by touching the screen with a finger or a stylus. For example, an application can be started by touching an icon 7207 displayed on the display portion 7202.

[0344] The operation button 7205 can be provided with various functions, such as time setting, power on / off operation, wireless communication on / off operation, silent mode activation / deactivation, power saving mode activation / deactivation, etc. For example, the functions of the operation button 7205 can be freely set by an operating system incorporated in the mobile information terminal 7200.

[0345] The mobile information terminal 7200 is also capable of performing standardized short-range wireless communication. For example, hands-free conversation is also possible by communicating with a wirelessly enabled headset.

[0346] The portable information terminal 7200 also includes an input / output terminal 7206, and can directly exchange data with another information terminal via a connector. Charging can also be performed via the input / output terminal 7206. Note that charging may be performed by wireless power supply without using the input / output terminal 7206.

[0347] The display portion 7202 of the mobile information terminal 7200 includes the secondary battery of one embodiment of the present invention. By using the secondary battery of one embodiment of the present invention, a lightweight mobile information terminal with a long life can be provided. To improve safety, a protection circuit that prevents overcharging and / or overdischarging of the secondary battery may be electrically connected to the secondary battery. For example, the secondary battery 7104 shown in FIG. 27E can be installed in a curved state inside the housing 7201 or in a bendable state inside the band 7203.

[0348] The portable information terminal 7200 preferably has a sensor, such as a fingerprint sensor, a pulse sensor, a body temperature sensor, a touch sensor, a pressure sensor, or an acceleration sensor.

[0349] 27G illustrates an example of a wristband-type display device. The display device 7300 includes a display portion 7304 and a secondary battery of one embodiment of the present invention. To improve safety, a protection circuit that prevents overcharging and / or overdischarging of the secondary battery may be electrically connected to the secondary battery. The display device 7300 may also include a touch sensor in the display portion 7304 and function as a portable information terminal.

[0350] The display surface of the display portion 7304 is curved, and display can be performed along the curved display surface. The display state of the display device 7300 can be changed by short-range wireless communication according to a communication standard.

[0351] The display device 7300 also includes an input / output terminal, allowing direct data exchange with other information terminals via a connector. Charging can also be performed via the input / output terminal. Note that charging may also be performed by wireless power supply without using the input / output terminal.

[0352] By using the secondary battery of one embodiment of the present invention as the secondary battery included in the display device 7300, a lightweight display device with a long lifetime can be provided.

[0353] Furthermore, examples in which a secondary battery with good cycle characteristics according to one embodiment of the present invention is mounted on an electronic device will be described with reference to FIGS. 27H, 28, and 29. FIG.

[0354] By using the secondary battery of one embodiment of the present invention as a secondary battery in an electronic device, a lightweight product with a long life can be provided. For example, examples of daily electronic devices include electric toothbrushes, electric shavers, and electric beauty devices. For the secondary battery of these products, a small, lightweight, and large-capacity stick-shaped secondary battery is desired for ease of holding by users.

[0355] FIG. 27H is a perspective view of a device also known as a tobacco-containing smoking device (electronic cigarette). In FIG. 27H, electronic cigarette 7500 includes atomizer 7501 including a heating element, secondary battery 7504 that supplies power to the atomizer, and cartridge 7502 including a liquid supply bottle or a sensor. To enhance safety, a protection circuit that prevents overcharging and / or over-discharging of secondary battery 7504 may be electrically connected to secondary battery 7504. Secondary battery 7504 shown in FIG. 27H has external terminals that allow connection to a charging device. Because secondary battery 7504 is the tip portion when held, it is desirable that its total length be short and its weight be light. The secondary battery of one embodiment of the present invention has high capacity and good cycle characteristics, making it possible to provide a compact and lightweight electronic cigarette 7500 that can be used for a long period of time.

[0356] Next, an example of a foldable tablet terminal is shown in Figures 28A and 28B. Tablet terminal 7600 shown in Figures 28A and 28B includes a housing 7630a, a housing 7630b, a movable portion 7640 connecting housings 7630a and 7630b, a display portion 7631 including display portions 7631a and 7631b, switches 7625 to 7627, a fastener 7629, and an operation switch 7628. Using a flexible panel for display portion 7631 allows for a tablet terminal with a larger display area. Figure 28A shows tablet terminal 7600 in an open state, and Figure 28B shows tablet terminal 7600 in a closed state.

[0357] The tablet terminal 7600 also includes a power storage unit 7635 inside the housing 7630a and the housing 7630b. The power storage unit 7635 passes through the movable portion 7640 and is provided across the housings 7630a and 7630b.

[0358] All or part of the display portion 7631 can be a touch panel area, and data can be input by touching images including icons, characters, input forms, etc. displayed in the area. For example, keyboard buttons may be displayed on the entire surface of the display portion 7631a on the housing 7630a side, and information such as characters and images may be displayed on the display portion 7631b on the housing 7630b side.

[0359] A keyboard may be displayed on the display portion 7631b of the housing 7630b, and information such as text and images may be displayed on the display portion 7631a of the housing 7630a. A keyboard display switch button of a touch panel may be displayed on the display portion 7631, and the keyboard may be displayed on the display portion 7631 by touching the button with a finger or a stylus.

[0360] In addition, touch input can be simultaneously performed on the touch panel area of ​​the display portion 7631a on the housing 7630a side and the touch panel area of ​​the display portion 7631b on the housing 7630b side.

[0361] The switches 7625 to 7627 may be interfaces capable of switching various functions in addition to interfaces for operating the tablet terminal 7600. For example, at least one of the switches 7625 to 7627 may function as a switch for turning on and off the power of the tablet terminal 7600. For example, at least one of the switches 7625 to 7627 may have a function for switching the display orientation, such as portrait or landscape, or a function for switching between black and white and color display. For example, at least one of the switches 7625 to 7627 may have a function for adjusting the brightness of the display unit 7631. The brightness of the display unit 7631 can be optimized depending on the amount of external light detected by an optical sensor built into the tablet terminal 7600 during use. Note that the tablet terminal may have built-in not only an optical sensor but also other detection devices, such as a gyroscope, an acceleration sensor, or other sensors for detecting tilt.

[0362] 28A shows an example in which the display areas of the display portion 7631a on the housing 7630a and the display portion 7631b on the housing 7630b are substantially the same, the display areas of the display portion 7631a and the display portion 7631b are not particularly limited, and the sizes of one and the other may be different, and the display qualities may also be different. For example, one display panel may be capable of displaying at a higher resolution than the other.

[0363] 28B shows a tablet terminal 7600 folded in half, and the tablet terminal 7600 includes a housing 7630, a solar cell 7633, and a charge / discharge control circuit 7634 including a DC-DC converter 7636. The power storage unit 7635 is a secondary battery according to one embodiment of the present invention.

[0364] As described above, the tablet terminal 7600 can be folded in half, and thus can be folded so that the housing 7630a and the housing 7630b overlap when not in use. By folding, the display portion 7631 can be protected, thereby improving the durability of the tablet terminal 7600. Furthermore, the power storage unit 7635 using the secondary battery of one embodiment of the present invention has a high capacity and favorable cycle characteristics, and therefore the tablet terminal 7600 can be used for a long period of time. To improve safety, a protection circuit that prevents overcharging and / or overdischarging of the secondary battery included in the power storage unit 7635 may be electrically connected to the secondary battery.

[0365] In addition, the tablet terminal 7600 shown in Figures 28A and 28B can have functions such as displaying various information (still images, videos, text images, etc.), displaying a calendar, date, time, etc. on the display unit, a touch input function for touch input operations or editing information displayed on the display unit, and a function for controlling processing using various software (programs).

[0366] A solar cell 7633 attached to the surface of the tablet terminal 7600 can supply power to a touch panel, a display unit, a video signal processor, or the like. The solar cell 7633 can be provided on one or both surfaces of the housing 7630, and can be configured to efficiently charge the power storage unit 7635. Note that using a lithium-ion battery as the power storage unit 7635 has advantages such as miniaturization.

[0367] The configuration and operation of the charge / discharge control circuit 7634 shown in Fig. 28B are described with reference to a block diagram in Fig. 28C. Fig. 28C shows a solar cell 7633, a power storage unit 7635, a DC-DC converter 7636, a converter 7637, switches SW1 to SW3, and a display unit 7631. The power storage unit 7635, the DC-DC converter 7636, the converter 7637, and switches SW1 to SW3 correspond to the charge / discharge control circuit 7634 shown in Fig. 28B.

[0368] First, an example of operation when power is generated by the solar cell 7633 using external light will be described. The power generated by the solar cell is stepped up or down by a DC-DC converter 7636 to a voltage for charging a power storage unit 7635. When power from the solar cell 7633 is used to operate the display unit 7631, a switch SW1 is turned on, and the converter 7637 steps up or steps down the voltage to a voltage required for the display unit 7631. When no display is to be performed on the display unit 7631, the switch SW1 may be turned off and the switch SW2 may be turned on to charge the power storage unit 7635.

[0369] Note that the solar cell 7633 is shown as an example of a power generating means, but is not particularly limited thereto, and the power storage unit 7635 may be charged by other power generating means such as a piezoelectric element (piezo element) or a thermoelectric conversion element (Peltier element). For example, a contactless power transmission module that transmits and receives power wirelessly (contactlessly) for charging, or a combination of other charging means may be used.

[0370] FIG. 29 illustrates an example of another electronic device. In FIG. 29, a display device 8000 is an example of an electronic device using a secondary battery 8004 according to one embodiment of the present invention. Specifically, the display device 8000 corresponds to a display device for receiving TV broadcasts and includes a housing 8001, a display unit 8002, a speaker unit 8003, a secondary battery 8004, and the like. To enhance safety, a protection circuit for preventing overcharging and / or overdischarging of the secondary battery 8004 may be electrically connected to the secondary battery 8004. The secondary battery 8004 according to one embodiment of the present invention is provided inside the housing 8001. The display device 8000 can receive power from a commercial power source or can use power stored in the secondary battery 8004. Therefore, even when power cannot be supplied from the commercial power source due to a power outage or the like, the display device 8000 can be used by using the secondary battery 8004 according to one embodiment of the present invention as an uninterruptible power source.

[0371] The display unit 8002 can be a liquid crystal display device, a light-emitting device having a light-emitting element such as an organic EL element in each pixel, an electrophoretic display device, a semiconductor display device such as a DMD (Digital Micromirror Device), a PDP (Plasma Display Panel), or an FED (Field Emission Display).

[0372] The display device includes all display devices for displaying information, such as those for receiving TV broadcasts, those for personal computers, and those for displaying advertisements.

[0373] 29 , a stationary lighting device 8100 is an example of an electronic device using a secondary battery 8103 according to one embodiment of the present invention. Specifically, the lighting device 8100 includes a housing 8101, a light source 8102, a secondary battery 8103, and the like. To improve safety, a protection circuit that prevents overcharging and / or overdischarging of the secondary battery 8103 may be electrically connected to the secondary battery 8103. FIG. 29 illustrates the case where the secondary battery 8103 is provided inside a ceiling 8104 on which the housing 8101 and the light source 8102 are installed; however, the secondary battery 8103 may be provided inside the housing 8101. The lighting device 8100 can receive power from a commercial power source or can use power stored in the secondary battery 8103. Therefore, even when power cannot be supplied from the commercial power source due to a power outage or the like, the lighting device 8100 can be used by using the secondary battery 8103 according to one embodiment of the present invention as an uninterruptible power supply.

[0374] Note that although Figure 29 illustrates an example of a stationary lighting device 8100 provided on the ceiling 8104, the secondary battery of one embodiment of the present invention can also be used in a stationary lighting device provided in places other than the ceiling 8104, such as a side wall 8105, a floor 8106, or a window 8107, or can also be used in a tabletop lighting device.

[0375] Furthermore, an artificial light source that artificially obtains light using electric power can be used as the light source 8102. Specifically, examples of the artificial light source include a discharge lamp such as an incandescent lamp or a fluorescent lamp, an LED, and / or an organic EL element.

[0376] In FIG. 29 , an air conditioner including an indoor unit 8200 and an outdoor unit 8204 is an example of an electronic device using a secondary battery 8203 according to one embodiment of the present invention. Specifically, the indoor unit 8200 includes a housing 8201, an air outlet 8202, a secondary battery 8203, and the like. To improve safety, a protection circuit that prevents overcharging and / or overdischarging of the secondary battery 8203 may be electrically connected to the secondary battery 8203. Although FIG. 29 illustrates the case where the secondary battery 8203 is provided in the indoor unit 8200, the secondary battery 8203 may also be provided in the outdoor unit 8204. Alternatively, the secondary battery 8203 may be provided in both the indoor unit 8200 and the outdoor unit 8204. The air conditioner can receive power from a commercial power source or can use power stored in the secondary battery 8203. In particular, when the secondary battery 8203 is provided in both the indoor unit 8200 and the outdoor unit 8204, the air conditioner can be used by using the secondary battery 8203 of one embodiment of the present invention as an uninterruptible power supply even when power cannot be supplied from a commercial power source due to a power outage or the like.

[0377] Note that although FIG. 29 illustrates an example of a separate-type air conditioner including an indoor unit and an outdoor unit, a secondary battery according to one embodiment of the present invention can also be used in an integrated-type air conditioner that has the functions of both the indoor unit and the outdoor unit in a single housing.

[0378] 29 , an electric refrigerator-freezer 8300 is an example of an electronic device using a secondary battery 8304 according to one embodiment of the present invention. Specifically, the electric refrigerator-freezer 8300 includes a housing 8301, a refrigerator door 8302, a freezer door 8303, a secondary battery 8304, and the like. To improve safety, a protection circuit that prevents overcharging and / or overdischarging of the secondary battery 8304 may be electrically connected to the secondary battery 8304. In FIG. 29 , the secondary battery 8304 is provided inside the housing 8301. The electric refrigerator-freezer 8300 can receive power from a commercial power source or can use power stored in the secondary battery 8304. Therefore, even when power cannot be supplied from the commercial power source due to a power outage or the like, the electric refrigerator-freezer 8300 can be used by using the secondary battery 8304 according to one embodiment of the present invention as an uninterruptible power source.

[0379] Among the electronic devices described above, electronic devices such as microwave ovens and other high-frequency heating devices and electric rice cookers require a large amount of power for a short period of time. Therefore, by using a secondary battery according to one embodiment of the present invention as an auxiliary power source for supplementing the power that cannot be supplied by the commercial power source, it is possible to prevent the breaker of the commercial power source from tripping when the electronic device is in use.

[0380] Furthermore, by storing power in the secondary battery during time periods when electronic devices are not in use, particularly during time periods when the ratio of the amount of power actually used to the total amount of power that can be supplied by the commercial power supplier (referred to as the power usage rate) is low, it is possible to prevent the power usage rate from increasing outside of these time periods. For example, in the case of electric refrigerator-freezer 8300, power is stored in secondary battery 8304 during the night when the temperature is low and refrigerator door 8302 and freezer door 8303 are not opened or closed. Then, during the daytime when the temperature rises and refrigerator door 8302 and freezer door 8303 are opened and closed, secondary battery 8304 is used as an auxiliary power source, thereby making it possible to keep the daytime power usage rate low.

[0381] According to one embodiment of the present invention, the cycle characteristics of the secondary battery can be improved, and the reliability can be improved. Furthermore, according to one embodiment of the present invention, a high-capacity secondary battery can be obtained, and therefore the characteristics of the secondary battery can be improved, and therefore the secondary battery itself can be made smaller and lighter. Therefore, by incorporating the secondary battery according to one embodiment of the present invention in the electronic device described in this embodiment, the electronic device can have a longer life and be lighter.

[0382] Figure 30A shows an example of a wearable device. The wearable device uses a secondary battery as a power source. Furthermore, in order to improve splash-proof, water-resistant, or dust-proof performance when used at home or outdoors, there is a demand for a wearable device that can be charged wirelessly as well as via a wired connection with an exposed connector.

[0383] For example, a secondary battery according to one embodiment of the present invention can be mounted on an eyeglasses-type device 9000 as shown in FIG. 30A . The eyeglasses-type device 9000 includes a frame 9000a and a display unit 9000b. Mounting a secondary battery on the temples of the curved frame 9000a makes it possible to provide an eyeglasses-type device 9000 that is lightweight, has a good weight balance, and has a long continuous use time. To improve safety, a protection circuit that prevents overcharging and / or overdischarging of the secondary battery may be electrically connected to the secondary battery. By including a secondary battery according to one embodiment of the present invention, a configuration that can accommodate space savings associated with a smaller housing can be realized.

[0384] Furthermore, the secondary battery according to one embodiment of the present invention can be mounted on a headset-type device 9001. The headset-type device 9001 includes at least a microphone unit 9001a, a flexible pipe 9001b, and an earphone unit 9001c. The secondary battery can be provided in the flexible pipe 9001b or the earphone unit 9001c. To enhance safety, a protection circuit that prevents overcharging and / or overdischarging of the secondary battery may be electrically connected to the secondary battery. By including the secondary battery according to one embodiment of the present invention, a configuration that can accommodate space savings due to a smaller housing can be realized.

[0385] Furthermore, a secondary battery according to one embodiment of the present invention can be mounted on a device 9002 that can be directly attached to the body. A secondary battery 9002b can be provided in a thin housing 9002a of the device 9002. To improve safety, a protection circuit that prevents overcharging and / or overdischarging of the secondary battery 9002b may be electrically connected to the secondary battery 9002b. By including a secondary battery according to one embodiment of the present invention, a configuration that can accommodate space savings due to a smaller housing can be realized.

[0386] Furthermore, a secondary battery according to one embodiment of the present invention can be mounted on a device 9003 that can be attached to clothing. A secondary battery 9003b can be provided in a thin housing 9003a of the device 9003. To improve safety, a protection circuit that prevents overcharging and / or overdischarging of the secondary battery 9003b may be electrically connected to the secondary battery 9003b. By including the secondary battery according to one embodiment of the present invention, a configuration that can accommodate space savings due to a smaller housing can be realized.

[0387] Furthermore, the secondary battery according to one embodiment of the present invention can be mounted on a belt-type device 9006. The belt-type device 9006 has a belt portion 9006a and a wireless power receiving portion 9006b, and the secondary battery can be mounted inside the belt portion 9006a. To improve safety, a protection circuit that prevents overcharging and / or overdischarging of the secondary battery may be electrically connected to the secondary battery. By including the secondary battery according to one embodiment of the present invention, a configuration that can accommodate space savings due to a smaller housing can be realized.

[0388] Furthermore, the secondary battery of one embodiment of the present invention can be mounted on a wristwatch device 9005. The wristwatch device 9005 has a display portion 9005a and a belt portion 9005b, and the secondary battery can be provided on the display portion 9005a or the belt portion 9005b. To improve safety, a protection circuit that prevents overcharging and / or overdischarging of the secondary battery may be electrically connected to the secondary battery. By providing the secondary battery of one embodiment of the present invention, a space-saving configuration can be realized that accompanies a miniaturized housing.

[0389] The display unit 9005a can display not only the time but also various information such as incoming emails and / or phone calls.

[0390] Furthermore, since the wristwatch type device 9005 is a wearable device that is worn directly on the wrist, it may be equipped with sensors that measure the user's pulse, blood pressure, etc. Data on the user's exercise amount and health can be accumulated to manage the user's health.

[0391] FIG. 30B shows a perspective view of the wristwatch type device 9005 removed from the wrist.

[0392] 30C shows a side view of the display device 9005. The display device 9005 includes a secondary battery 913 according to one embodiment of the present invention. The secondary battery 913 is small and lightweight and is provided so as to overlap with the display portion 9005a.

[0393] 31A shows an example of a cleaning robot. The cleaning robot 9300 has a display unit 9302 arranged on the top surface of a housing 9301, multiple cameras 9303 arranged on the side, a brush 9304, operation buttons 9305, a secondary battery 9306, various sensors, and the like. To enhance safety, a protection circuit that prevents overcharging and / or over-discharging of the secondary battery 9306 may be electrically connected to the secondary battery 9306. Although not shown, the cleaning robot 9300 is provided with tires, a suction port, and the like. The cleaning robot 9300 can move by itself, detect dust 9310, and suck up the dust from a suction port provided on the bottom surface.

[0394] For example, the cleaning robot 9300 can analyze an image captured by the camera 9303 to determine whether or not there is an obstacle such as a wall, furniture, or a step. Furthermore, if an object that may become entangled in the brush 9304, such as a wire, is detected through image analysis, the cleaning robot 9300 can stop the rotation of the brush 9304. The cleaning robot 9300 includes a secondary battery 9306 according to one embodiment of the present invention and a semiconductor device or an electronic component. By using the secondary battery 9306 according to one embodiment of the present invention in the cleaning robot 9300, the cleaning robot 9300 can be a highly reliable electronic device with a long operating time.

[0395] Fig. 31B shows an example of a robot. The robot 9400 shown in Fig. 31B includes a secondary battery 9409, an illuminance sensor 9401, a microphone 9402, an upper camera 9403, a speaker 9404, a display unit 9405, a lower camera 9406, an obstacle sensor 9407, a movement mechanism 9408, a computing device, etc. To enhance safety, a protection circuit that prevents overcharging and / or over-discharging of the secondary battery 9409 may be electrically connected to the secondary battery 9409.

[0396] The microphone 9402 has a function of detecting the user's voice, environmental sounds, etc. The speaker 9404 has a function of emitting sound. The robot 9400 can communicate with the user using the microphone 9402 and the speaker 9404.

[0397] The display unit 9405 has a function of displaying various types of information. The robot 9400 can display information desired by the user on the display unit 9405. The display unit 9405 may be equipped with a touch panel. The display unit 9405 may also be a detachable information terminal, which can be installed in a fixed position on the robot 9400 to enable charging and data transfer.

[0398] The upper camera 9403 and the lower camera 9406 have the function of capturing images of the surroundings of the robot 9400. In addition, the obstacle sensor 9407 can detect the presence or absence of obstacles in the direction of travel when the robot 9400 moves forward using the movement mechanism 9408. The robot 9400 can recognize the surrounding environment and move safely using the upper camera 9403, the lower camera 9406, and the obstacle sensor 9407.

[0399] The robot 9400 includes a secondary battery 9409 according to one embodiment of the present invention and a semiconductor device or an electronic component inside the robot 9400. By using the secondary battery according to one embodiment of the present invention in the robot 9400, the robot 9400 can be a highly reliable electronic device with a long operating time.

[0400] Fig. 31C shows an example of an air vehicle. Air vehicle 9500 shown in Fig. 31C has a propeller 9501, a camera 9502, a secondary battery 9503, and the like, and has the ability to fly autonomously. To enhance safety, a protection circuit that prevents overcharging and / or over-discharging of secondary battery 9503 may be electrically connected to secondary battery 9503.

[0401] For example, image data captured by a camera 9502 is stored in an electronic component 9504. The electronic component 9504 can analyze the image data and detect the presence or absence of an obstacle when moving. The electronic component 9504 can also estimate the remaining battery charge from a change in the storage capacity of the secondary battery 9503. The flying object 9500 includes therein a secondary battery 9503 according to one embodiment of the present invention. By using the secondary battery according to one embodiment of the present invention in the flying object 9500, the flying object 9500 can be an electronic device with a long operating time and high reliability.

[0402] This embodiment mode can be implemented in appropriate combination with other embodiment modes. [Example]

[0403] In this example, in order to confirm whether the ceramic material traps cobalt ions, the powdered ceramic material was stirred in a cobalt solution and the concentration of the cobalt solution was measured.

[0404] First, to mix the organic solvents, Li-TFSI was added to EC:DEC = 3:7 (volume ratio) (Kishida Chemical) in an argon atmosphere glove box to give a concentration of 1 mol / L, and the mixture was stirred at room temperature for approximately 18 hours.

[0405] Next, in an argon-atmosphere glove box, two sample cells were prepared: one containing lithium metal immersed in organic solvent, and the other containing cobalt foil immersed in organic solvent. The two cells were connected, and a glass filter was placed between them. Ohara's lithium ion conductive glass ceramics (LICGC) was used as the glass filter. The glass filter was placed to prevent the products produced by electrolysis from being reduced at the counter electrode. DC 3.6 V was applied between the lithium metal and the cobalt foil for 20 hours, producing approximately 15 mL of a 50 ppm cobalt solution.

[0406] Next, a cobalt solution was added to each ceramic material and stirred. Specifically, a stir bar was placed in each of six 5 mL sample bottles, and approximately 30 mg of magnesium oxide (MgO), magnesium hydroxide (Mg(OH)2), alumina (Al2O3), boehmite (AlOOH), rutile titanium dioxide (TiO2), and anatase titanium dioxide were each placed in separate sample bottles. These sample bottles were placed in a glove box, and 2 mL of cobalt solution was added to each bottle. The bottles were then stirred at room temperature at 300 rpm for approximately 16 hours.

[0407] After stirring, the sample bottle was removed from the glove box. The stirred suspension was filtered using a membrane filter to separate it into a cobalt solution (filtrate) and a ceramic material (filtered residue).

[0408] The cobalt concentration in the cobalt solution separated from each ceramic material was measured using an atomic absorption spectrometer (ContrAA600, manufactured by Analytik Jena). Measurements were performed twice for each cobalt solution separated from each ceramic material, and the average value was calculated. The measurement results are shown in Figure 32.

[0409] The cobalt concentrations obtained for the MgO sample were 32.55 ppm for the first run and 30.82 ppm for the second run, with an average of 31.69 ppm. For the Mg(OH)2 sample, the cobalt concentrations were 23.40 ppm for the first run and 26.72 ppm for the second run, with an average of 25.06 ppm. For the Al2O3 sample, the cobalt concentrations were 37.63 ppm for the first run and 40.27 ppm for the second run, with an average of 38.95 ppm. For the AlOOH sample, the cobalt concentrations were 40.20 ppm for the first run and 43.18 ppm for the second run, with an average of 41.69 ppm. For the rutile TiO2 sample, the cobalt concentrations were 36.56 ppm for the first run and 34.59 ppm for the second run, with an average of 35.58 ppm. For the anatase TiO2 sample, the first run had 31.05 ppm, the second run had 31.07 ppm, and the average was 31.06 ppm. For a comparative example, a cobalt solution without added ceramic material had 40.65 ppm for the first run and 41.40 ppm for the second run, with an average of 41.03 ppm. For a sample obtained by filtering a cobalt solution without added ceramic material, the first run had 42.97 ppm, the second run had 42.40 ppm, and the average was 42.69 ppm.

[0410] These measurement results show that the cobalt concentration in the filtered Mg(OH)2 sample is low, suggesting that Mg(OH)2 may be trapping cobalt ions. [Example]

[0411] In this example, a polypropylene separator coated with an MgO layer was produced by the following method.

[0412] First, 2 g of MgO and 0.96296 g of NMP were mixed in a kneader (Thinky Corporation, planetary centrifugal mixer, Awatori Rentaro) at 2000 rpm for 3 minutes. By first mixing the MgO and NMP, the MgO was dispersed. 0.2 g of an NMP solution containing 5 wt% PVdF was added to the resulting mixture and mixed using the kneader. Next, 4.24444 g of an NMP solution containing 5 wt% PVdF was added to the resulting mixture and mixed using the kneader. The PVdF was added little by little to prevent aggregation of the PVdF. Through these steps, a slurry with a solids ratio of 30% (MgO:PVdF = 90:10) was prepared.

[0413] Next, the slurry was applied onto a 20 μm thick polypropylene separator using a coating device (applicator) with a 40 μm gap between the coating blade of the coating device and the surface to be coated (surface of the polypropylene separator) and a coating speed of 10 mm / sec.

[0414] The polypropylene separator coated with the slurry was dried in a ventilation drying oven at 80° C. for 30 minutes.

[0415] The thickness of the MgO layer of the polypropylene separator coated with the MgO layer obtained by the above process was measured using a micrometer. The thickness of the separator coated with the MgO layer was 45 μm to 60 μm, and the thickness of the polypropylene separator was 20 μm. Therefore, the thickness of the MgO layer was approximately 25 μm to 40 μm. [Example]

[0416] In this example, a polypropylene separator coated with an Mg(OH)2 layer was produced by the following method.

[0417] First, 2 g of Mg(OH)2 and 2 g of NMP were mixed in a kneader (Thinky Corporation, planetary rotation / revolution type mixer, Awatori Rentaro) at 2000 rpm for 3 minutes. The average particle size of the Mg(OH)2 particles used was approximately 7 μm. A laser diffraction particle size analyzer (Shimadzu Corporation, SALD-2200) was used to measure the average particle size of the Mg(OH)2 particles. Mg(OH)2 was dispersed by first mixing the Mg(OH)2 and NMP. 0.2 g of an NMP solution containing 5 wt% PVdF was added to the resulting mixture and mixed using the kneader. Next, 4.24444 g of an NMP solution containing 5 wt% PVdF was added to the resulting mixture and mixed using the kneader. PVdF was added little by little to prevent PVdF aggregation. Through the above steps, a slurry with a solid content of 26% (Mg(OH)2:PVdF=90:10) was prepared.

[0418] Next, the slurry was applied onto a 20 μm thick polypropylene separator using a coating device (applicator) with a distance of 30 μm between the coating blade of the coating device and the surface to be coated (surface of the polypropylene separator) and a coating speed of 10 mm / sec.

[0419] The polypropylene separator coated with the slurry was dried in a ventilation drying oven at 80° C. for 30 minutes.

[0420] The thickness of the Mg(OH)2 layer of the separator coated with the Mg(OH)2 layer obtained by the above process was measured using a micrometer. The thickness of the separator coated with the Mg(OH)2 layer was 70 μm to 80 μm, and the thickness of the polypropylene separator was 20 μm. Therefore, the thickness of the Mg(OH)2 layer was 50 μm to 60 μm.

[0421] The density of the Mg(OH)2 layer was determined as follows. First, a polypropylene separator coated with an Mg(OH)2 layer and a polypropylene separator not coated with an Mg(OH)2 layer were each punched out into a circle with a diameter of 18 mm, and then the weight and film thickness were measured. The weight and film thickness of the polypropylene separator coated with an Mg(OH)2 layer were 9.271 mg and 75 μm, respectively, and the weight and film thickness of the polypropylene separator alone were 3.536 mg and 20 μm, respectively. Therefore, the weight and film thickness of the Mg(OH)2 layer were 5.735 mg and 55 μm, respectively. The calculated weight and film thickness of the Mg(OH)2 layer and the area of ​​the 18 mm diameter circle, 2.5434 cm 2 By substituting this into the equation density = weight ÷ film thickness ÷ area, the density of the Mg(OH)2 layer was calculated to be approximately 410 mg / cm 3 It was.

[0422] The porosity of the Mg(OH)2 layer is the density of the Mg(OH)2 layer divided by the density of the Mg(OH)2 layer when the porosity is 0, minus 1. The density of the Mg(OH)2 layer when the porosity is 0 is calculated when the densities of Mg(OH)2 and PVdF as materials are 2360 mg / cm3. 3 , 1780 mg / cm 3 Therefore, 2300 mg / cm 3 Therefore, the porosity of the Mg(OH)2 layer was approximately 82.2% by volume. [Explanation of symbols]

[0423] 102: space inside heating furnace, 104: hot plate, 106: heater part, 108: heat insulating material, 116: container, 118: lid, 119: space, 120: heating furnace, 130: laminate, 131: laminate, 500: secondary battery, 501: positive electrode current collector, 502a: region, 502: positive electrode active material layer, 503: positive electrode, 504: negative electrode current collector, 505a: region, 505: negative electrode active material layer, 506: negative electrode, 507a: region, 507b: region, 507: separator, 508: electrolyte, 509a: exterior body, 509b: exterior body, 509: exterior body, 510: positive electrode lead electrode, 511: negative electrode lead electrode, 512 : laminate, 513: resin layer, 514: region, 515a: electrolyte, 515b: electrolyte, 515c: electrolyte, 516: inlet, 521a: region, 521b: region, 521: polymer porous membrane, 522: layer, 550: laminate, 553: acetylene black, 554: graphene, 556: acetylene black, 557: graphene, 560: secondary battery, 561: positive electrode active material, 563: negative electrode active material, 570: manufacturing apparatus, 571: component input chamber, 572: transfer chamber, 573: treatment chamber, 576: component removal chamber, 580: transfer mechanism, 581: polymer membrane, 582: hole, 58 4: polymer film, 585: hole, 591: stage, 594: nozzle, 600: secondary battery, 701: commercial power supply, 703: distribution board, 705: power storage controller, 706: display, 707: general load, 708: power storage load, 709: router, 710: service line attachment section, 711: measurement section, 712: prediction section, 713: planning section, 790: control device, 791: power storage device, 796: underfloor space section, 799: building, 801: complex oxide, 802: fluoride, 803: compound, 804: mixture, 808: cobalt-containing material, 911a: terminal, 911b: terminal, 913: secondary battery , 930a: housing, 930b: housing, 930: housing, 931a: negative electrode active material layer, 931: negative electrode, 932a: positive electrode active material layer, 932: positive electrode, 933: separator, 950a: wound body, 950: wound body, 951: terminal, 952: terminal, 970: secondary battery, 971: housing, 972: laminate, 973a: positive electrode lead electrode, 973b: terminal, 973c: conductor, 974a: negative electrode lead electrode, 974b: terminal, 974c: conductor, 975a: positive electrode, 975b: positive electrode, 976: separator, 977a: negative electrode, 1301a: first battery, 1301b: first battery,1302: Battery controller, 1303: Motor controller, 1304: Motor, 1305: Gear, 1306: DCDC circuit, 1307: Electric power steering, 1308: Heater, 1309: Defogger, 1310: DCDC circuit, 1311: Second battery, 1312: Inverter, 1313: Audio, 1314: Power window, 1315: Lamps, 1316: Tire, 1317: Rear motor, 1320: Control circuit section, 1321: Control circuit section, 1322: Control circuit, 1324: Switch section, 1325: External terminal, 1326: External terminal, 1 415: battery pack, 1421: wiring, 1422: wiring, 2001: automobile, 2002: transport vehicle, 2003: transport vehicle, 2004: aircraft, 2005: transport vehicle, 2100: electric bicycle, 2101: secondary battery, 2102: power storage device, 2103: display unit, 2104: control circuit, 2201: battery pack, 2202: battery pack, 2203: battery pack, 2204: battery pack, 2300: scooter, 2301: side mirror, 2302: power storage device, 2303: turn signal light, 2304: under-seat storage, 2603: vehicle, 2604: charging device, 2610: solar Panel, 2611: wiring, 2612: power storage device, 2800: personal computer, 2801: housing, 2802: housing, 2803: display unit, 2804: keyboard, 2805: pointing device, 2806: secondary battery, 2807: secondary battery, 7100: portable display device, 7101: housing, 7102: display unit, 7103: operation button, 7104: secondary battery, 7200: portable information terminal, 7201: housing, 7202: display unit, 7203: band, 7204: buckle, 7205: operation button, 7206: input / output terminal, 7207: icon, 7300: table display device, 7304: display unit, 7400: mobile phone, 7401: housing, 7402: display unit, 7403: operation button, 7404: external connection port, 7405: speaker, 7406: microphone, 7407: secondary battery, 7500: electronic cigarette, 7501: atomizer, 7502: cartridge, 7504: secondary battery, 7600: tablet terminal, 7625: switch, 7627: switch, 7628: operation switch, 7629: fastener, 7630a: housing, 7630b: housing, 7630: housing, 7631a: display unit, 7631b: display unit, 7631: display unit,7633: Solar cell, 7634: Charge / discharge control circuit, 7635: Power storage body, 7636: DCDC converter, 7637: Converter, 7640: Movable part, 8000: Display device, 8001: Housing, 8002: Display part, 8003: Speaker part, 8004: Secondary battery, 8100: Lighting device, 8101: Housing, 8102: Light source, 8103: Secondary battery, 8104: Ceiling, 8105: Side wall, 8106: Floor, 8107: Window, 820 0: indoor unit, 8201: housing, 8202: air outlet, 8203: secondary battery, 8204: outdoor unit, 8300: electric refrigerator-freezer, 8301: housing, 8302: refrigerator compartment door, 8303: freezer compartment door, 8304: secondary battery, 9000a: frame, 9000b: display unit, 9000: eyeglass-type device, 9001a: microphone unit, 9001b: flexible pipe, 9001c: earphone unit, 9001: headset-type device , 9002a: housing, 9002b: secondary battery, 9002: device, 9003a: housing, 9003b: secondary battery, 9003: device, 9005a: display unit, 9005b: belt unit, 9005: wristwatch type device, 9006a: belt unit, 9006b: wireless power supply receiving unit, 9006: belt type device, 9300: cleaning robot, 9301: housing, 9302: display unit, 9303: camera, 9304: brush ,9305: Operation button, 9306: Secondary battery, 9310: Garbage, 9400: Robot, 9401: Illuminance sensor, 9402: Microphone, 9403: Upper camera, 9404: Speaker, 9405: Display unit, 9406: Lower camera, 9407: Obstacle sensor, 9408: Moving mechanism, 9409: Secondary battery, 9500: Flying object, 9501: Propeller, 9502: Camera, 9503: Secondary battery, 9504: Electronic component,

Claims

1. A separator in which a porous polymer membrane and a layer having a ceramic material containing metal oxide fine particles are laminated, the layer containing the ceramic material has a thickness of 1 μm or more and 100 μm or less, The polymer porous membrane has a thickness of 4 μm or more and 50 μm or less, The metal oxide fine particles include magnesium hydroxide, The density of the layer having the ceramic material is 0.1 g / cm ３ 0.5g / cm or more ３ Below is the separator.

2. 2. The separator according to claim 1, wherein the metal oxide fine particles have an average particle size of 0.01 μm or more and 50 μm or less.

3. 3. The separator according to claim 1, wherein the layer containing the ceramic material is in contact with one surface of the porous polymer membrane.

4. A separator in which a porous polymer membrane and a layer having a plurality of ceramic materials containing metal oxide fine particles are laminated, the plurality of layers having ceramic materials are positioned so as to sandwich the porous polymer membrane; the layer containing the ceramic material has a thickness of 1 μm or more and 100 μm or less, The polymer porous membrane has a thickness of 4 μm or more and 50 μm or less, The metal oxide fine particles include magnesium hydroxide, The density of the layer having the ceramic material is 0.1 g / cm ３ 0.5g / cm or more ３ Below is the separator.

5. 5. The separator according to claim 4, wherein the metal oxide fine particles have an average particle size of 0.01 μm or more and 50 μm or less.

6. 6. The separator according to claim 4, wherein the layer containing the ceramic material is in contact with one surface of the porous polymer membrane.

7. A secondary battery comprising: a positive electrode; a negative electrode; the separator according to claim 1 sandwiched between the positive electrode and the negative electrode; and an electrolyte.

8. The secondary battery according to claim 7 , wherein the electrolyte is disposed inside the pores of the porous polymer membrane.

Images