Battery and method for manufacturing battery

Abstract

Provided is a lightweight battery. The battery includes a separator-integrated electrode in which a separator and an electrode are integrated. The separator-integrated electrode includes a separator, a carbon particle layer, and a silicon layer located between the separator and the carbon particle layer. The silicon layer may be produced by a sputtering method, and the carbon particle layer may be produced by a coating method. The separator preferably contains polypropylene, the silicon layer preferably has a thickness of 100-200 nm, and the carbon particle layer preferably contains graphite particles.

Description

Technical Field

[0001] One embodiment of the present invention relates to a power storage device (also referred to as a battery or a secondary battery). In addition, the present invention is not limited to the above-mentioned fields, but relates to a semiconductor device, a display device, a light-emitting device, a lighting device, an electronic device, a vehicle, and a method for manufacturing the same. The above-mentioned semiconductor device, display device, light-emitting device, lighting device, electronic device, and vehicle can use the battery of the present invention as a required power source. Batteries include secondary batteries such as lithium-ion batteries and sodium-ion batteries. For example, the above-mentioned electronic device includes an information terminal device equipped with a lithium-ion battery, etc. Furthermore, the above-mentioned power storage device includes a fixed-type power storage device, etc. Background Art

[0002] In recent years, the research and development of various storage batteries such as lithium-ion batteries, lithium-ion capacitors, air batteries and all-solid-state batteries has become increasingly popular. In particular, with the development of the semiconductor industry, the demand for high-output and high-capacity lithium-ion batteries has increased dramatically. As a rechargeable energy supply source, it has become a necessity in the modern information society.

[0003] As such, lithium-ion batteries are used in various fields and applications. Among them, lithium-ion batteries are required to have characteristics such as high energy density per unit weight, high energy density per unit volume, excellent cycle characteristics, and safety in various operating environments, and research and development of lithium-ion batteries are actively being carried out in various aspects.

[0004] For example, Patent Document 1 has discussed the electrode structure of a lithium ion battery.

[0005] [Prior technical literature]

[0006] [Patent Document]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 2015-109270 Summary of the invention

[0008] Technical problem to be solved by the invention

[0009] Lithium-ion batteries are required to be lightweight and small. However, lithium-ion batteries are also required to have a high discharge capacity. Therefore, among the components constituting lithium-ion batteries, the thickness of the current collector (using a metal foil with a thickness of about 10 μm), separator, and outer packaging that do not contribute to the discharge capacity is reduced to achieve lightweight and miniaturization of lithium-ion batteries.

[0010] Patent Document 1 discloses a battery structure and a manufacturing method thereof that do not include a metal foil as a current collector. However, the battery structure and the manufacturing method still have room for improvement.

[0011] One of the objects of one embodiment of the present invention is to provide a lightweight battery. Another object of one embodiment of the present invention is to provide a method for manufacturing a lightweight battery. Another object of one embodiment of the present invention is to provide a lightweight electrode. Another object of one embodiment of the present invention is to provide a method for manufacturing a lightweight electrode. Another object of one embodiment of the present invention is to provide a small battery. Another object of one embodiment of the present invention is to provide a method for manufacturing a small battery. Another object of one embodiment of the present invention is to provide a small electrode. Another object of one embodiment of the present invention is to provide a method for manufacturing a small electrode.

[0012] In addition, one of the purposes of one embodiment of the present invention is to provide a battery structure that does not include metal foil as a current collector for at least one of the positive electrode and the negative electrode. In addition, one of the purposes of one embodiment of the present invention is to provide a method for manufacturing a battery that does not include metal foil as a current collector for at least one of the positive electrode and the negative electrode.

[0013] In addition, one of the purposes of one embodiment of the present invention is to provide a battery structure that does not include copper foil as a current collector. In addition, one of the purposes of one embodiment of the present invention is to provide a method for manufacturing a battery that does not include copper foil as a current collector. In addition, one of the purposes of one embodiment of the present invention is to prevent copper ions from dissolving out of an electrolyte in an overdischarge state by using a battery that does not include copper foil as a current collector.

[0014] Another object of one embodiment of the present invention is to provide a novel electrode, a battery, or a method for producing the same.

[0015] Note that the description of these objects does not prevent the existence of other objects. Note that one embodiment of the present invention does not necessarily achieve all of the above objects. Note that objects other than the above objects can be extracted from the description of the specification, drawings, and claims.

[0016] Solutions to technical problems

[0017] One embodiment of the present invention is a battery including: a separator-integrated electrode, wherein the separator-integrated electrode includes a separator, a carbon particle layer, and a silicon layer located between the separator and the carbon particle layer.

[0018] One embodiment of the present invention is a battery comprising: an insulator-integrated electrode and an outer packaging body, wherein the insulator-integrated electrode comprises an insulator, a carbon particle layer, and a silicon layer located between the insulator and the carbon particle layer, and the carbon particle layer and the outer packaging body have an area in contact with each other.

[0019] In the above battery, the thickness of the silicon layer is preferably greater than or equal to 100 nm and less than or equal to 200 nm.

[0020] In the above battery, the separator preferably comprises polypropylene.

[0021] In addition, one embodiment of the present invention is a method for manufacturing a battery including an insulator-integrated electrode, wherein the insulator-integrated electrode includes an insulator, a carbon particle layer, and a silicon layer located between the insulator and the carbon particle layer, the manufacturing method comprising the following steps: a first process of manufacturing a silicon layer on the insulator by sputtering and a second process of manufacturing the carbon particle layer by coating a slurry containing carbon particles on the silicon layer, wherein the thickness of the silicon layer is greater than 100 nm and less than 200 nm.

[0022] In the above-mentioned method for manufacturing a battery, the slurry preferably contains N-methyl-pyrrolidone.

[0023] In the above-mentioned method for manufacturing a battery, the separator preferably comprises polypropylene.

[0024] Effects of the Invention

[0025] According to one embodiment of the present invention, a lightweight battery can be provided. In addition, a method for manufacturing a lightweight battery can be provided. In addition, according to one embodiment of the present invention, a lightweight electrode can be provided. In addition, a method for manufacturing a lightweight electrode can be provided. In addition, according to one embodiment of the present invention, a small battery can be provided. In addition, a method for manufacturing a small battery can be provided. In addition, according to one embodiment of the present invention, a small electrode can be provided. In addition, a method for manufacturing a small electrode can be provided.

[0026] In addition, according to one embodiment of the present invention, a battery structure that does not include metal foil as a current collector for at least one of the positive electrode and the negative electrode can be provided. In addition, a method for manufacturing a battery that does not include metal foil as a current collector for at least one of the positive electrode and the negative electrode can be provided.

[0027] In addition, according to one embodiment of the present invention, a battery structure that does not include copper foil as a current collector can be provided. In addition, a method for manufacturing a battery that does not include copper foil as a current collector can be provided. In addition, a battery that does not include copper foil as a current collector can prevent copper ions from dissolving out of an electrolyte in an overdischarge state.

[0028] In addition, according to one embodiment of the present invention, a novel electrode, a battery, or a method for producing the same can be provided.

[0029] Note that the description of these effects does not prevent the existence of other effects. In addition, one mode of the present invention does not necessarily have all of the above effects. Note that effects other than the above can be known and extracted from the description of the specification, drawings, claims, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figures 1A to 1D A diagram illustrating a method for manufacturing a separator-integrated electrode and its structure.

[0031] FIG. 2A to FIG. 2C It is a diagram for explaining the structure of a battery including a separator-integrated electrode.

[0032] FIG. 3A to FIG. 3C It is a diagram for explaining a modified example of the structure of the separator-integrated electrode.

[0033] Figure 4A An example of a cylindrical secondary battery is shown. Figure 4B An example of a cylindrical secondary battery is shown. Figure 4C A plurality of examples of cylindrical secondary batteries are shown. Figure 4D An example of a power storage system including a plurality of cylindrical secondary batteries is shown.

[0034] Figure 5A and Figure 5B is a diagram illustrating an example of a secondary battery, Figure 5C It is a diagram showing the interior of a secondary battery.

[0035] FIG. 6A to FIG. 6C It is a diagram for explaining an example of a secondary battery.

[0036] Fig. 7A and Figure 7B It is a diagram showing the appearance of a secondary battery.

[0037] FIG. 8A to FIG. 8C It is a diagram for explaining a method for manufacturing a secondary battery.

[0038] Fig. 9A An example of the structure of a battery pack is shown. Fig. 9B An example of the structure of a battery pack is shown. Fig. 9C A structural example of a battery pack is shown.

[0039] Fig. 10A is a perspective view showing a battery pack according to one embodiment of the present invention. Fig. 10B is the block diagram of the battery pack, Fig. 10C is a block diagram of a vehicle including a battery pack.

[0040] FIG. 11A to FIG. 11D It is a diagram illustrating an example of a transport vehicle. Fig.11E This is a diagram illustrating an example of an artificial satellite.

[0041] Fig. 12A and Fig. 12B It is a diagram for explaining a power storage device according to one embodiment of the present invention.

[0042] Fig.13A is a diagram showing an electric bicycle, Fig. 13Bis a diagram showing a secondary battery of an electric bicycle, Fig. 13C It is a figure explaining a small motorcycle.

[0043] FIG. 14A to FIG. 14D It is a diagram for explaining an example of an electronic device.

[0044] Fig.15A Showing an example of a wearable device, Fig. 15B showing a perspective view of a watch type device, Fig. 15C It is a diagram illustrating the side view of a wristwatch-type device.

[0045] FIG. 16A to FIG. 16D This is the SEM image described in Example 1.

[0046] 17A to 17C This is a graph of the charge and discharge characteristics described in Example 1. DETAILED DESCRIPTION

[0047] Hereinafter, examples of embodiments of the present invention will be described using drawings and the like. Note that the present invention should not be interpreted as being limited to the following examples of embodiments. The embodiments of the invention may be changed within the scope of the spirit of the present invention.

[0048] In addition, in this specification, etc., the particles are not limited to spherical (circular cross-sectional shape), and the cross-sectional shape of each particle can also be elliptical, rectangular, trapezoidal, triangular, a quadrilateral with curved corners, an asymmetric shape, etc., and each particle can also be amorphous.

[0049] In addition, in the drawings and the like of the present embodiment, each component may be exaggerated for clarity, and therefore, the present invention is not limited to the dimensions in the drawings.

[0050] (Implementation Method 1)

[0051] One embodiment of the present invention has a structure in which an insulator and an electrode are integrated. This structure may also be referred to as an electrode integrated with an insulator. In addition, the structure of an electrode integrated with an insulator and a method for manufacturing the same are described in this embodiment. In this specification, an electrode integrated with an insulator is referred to as an insulator-integrated electrode.

[0052] Furthermore, one embodiment of the present invention is characterized by an electrode structure that does not include a metal foil as a current collector.

[0053] Furthermore, one embodiment of the present invention is characterized by an electrode structure that does not include a copper foil as a current collector.

[0054] Note that the electrode described in this embodiment can be used as a positive electrode or a negative electrode of a battery. For example, in a battery in which the electrode is used as one of the positive electrode and the negative electrode, when the reaction potential of the electrode is higher than the reaction potential of the other electrode, the electrode is called a positive electrode. In addition, for example, in a battery in which the electrode is used as one of the positive electrode and the negative electrode, when the reaction potential of the electrode is lower than the reaction potential of the other electrode, the electrode is called a negative electrode.

[0055] use Figures 1A to 1D An electrode structure and a method for manufacturing the electrode structure according to one embodiment of the present invention will be described.

[0056] Figures 1A to 1C It is a cross-sectional view illustrating a method for manufacturing a separator-integrated electrode. Figure 1D yes Figure 1C An enlarged view of area A shown by a dotted line in FIG.

[0057] The manufacturing method of the separator integrated electrode is described. Figure 1A As shown, an insulator 11 is prepared.

[0058] As the separator 11, for example, the following materials can be used: paper or other cellulose-containing fibers, nonwoven fabrics, glass fibers, ceramics, or porous films containing nylon (polyamide), polyimide, vinylon (polyvinyl alcohol-based fibers), polyester, acrylic resin, polyolefin, or polyurethane. As a porous film containing polyolefin, for example, a polypropylene porous film can be used.

[0059] The separator may also have a multilayer structure. For example, a ceramic material, a fluorine material, a polyamide material, a polyimide material or a mixture thereof may be coated on a thin film of an organic material such as polypropylene or polyethylene. As a ceramic material, for example, aluminum oxide particles (alumina, boehmite, etc.), silicon oxide particles, etc. may be used. As a fluorine material, for example, PVDF, polytetrafluoroethylene, etc. may be used. As a polyamide material, for example, nylon, aromatic polyamide (meta-aramid, para-aramid), etc. may be used.

[0060] By applying ceramic materials, the oxidation resistance can be improved, thereby suppressing the degradation of the separator during high-voltage charging, thereby improving the reliability of the battery. By applying fluorine materials, it is easy to make the separator close to the electrode, thereby improving the output characteristics. By applying polyamide materials, especially aromatic polyamide, the heat resistance can be improved, thereby improving the safety of the battery.

[0061] Therefore, when the above-mentioned coating is performed on one surface of the separator and the other surface is integrated with the electrode, the electrode integrated with the separator is preferably a negative electrode.

[0062] By adopting a multi-layer structured separator, the safety of the battery can be ensured even if the total thickness of the separator is small, and thus the capacity per unit volume of the battery can be increased.

[0063] Then, if Figure 1B As shown, a silicon layer 31 is deposited on the separator 11. The silicon layer 31 can be deposited by sputtering. As a method for depositing silicon, a CVD method, a vacuum evaporation method, a PLD method, etc. can be used. The thickness of the silicon layer 31 is preferably 50 nm or more and 1000 nm or less, and more preferably 100 nm or more and 200 nm or less. When the thickness of the silicon layer 31 is less than 50 nm, the solvent of the slurry in the manufacture of the carbon particle layer 32 provided on the upper layer of the silicon layer 31 may penetrate the gap (pinhole, etc.) of the silicon layer 31, resulting in the separator 11 being dissolved by the solvent and the silicon layer 31 being likely to be peeled off. In addition, when the thickness of the silicon layer 31 is greater than 1000 nm, the resistance of the silicon layer 31 becomes large, and the battery performance may be reduced. By having such a silicon layer 31, the adhesion between the separator 11 and the coating electrode layer to be described later can be improved. Note that the thickness of the separator 11 is 5 μm or more, preferably 10 μm or more to prevent the separator 11 from being greatly deformed due to the film stress of the silicon layer 31.

[0064] Then, if Figure 1C As shown in FIG. 1 , a carbon particle layer 32 is formed on the silicon layer 31. The carbon particle layer 32 can be formed by, for example, applying a slurry containing graphite particles on the silicon layer 31 using a doctor blade coating device or the like, and drying a solvent contained in the slurry containing graphite particles using a drying furnace or the like. Therefore, the carbon particle layer 32 is sometimes referred to as a graphite layer, a graphite particle layer, or a coated electrode layer. In addition, as a method for applying the slurry, a slot film coater, a lip coater, a reverse coater, a gravure coater, or the like can be used.

[0065] Note that the thickness of the carbon particle layer 32 is preferably 5 μm or more and 200 μm, and more preferably 10 μm or more and 100 μm or less.

[0066] In this manner, a separator-integrated electrode 40 in which a separator and an electrode are integrated can be manufactured.

[0067] Reference Figure 1D The structure of the separator integrated electrode 40 is described. The separator integrated electrode 40 includes a separator 11 , a silicon layer 31 , and a carbon particle layer 32 .

[0068] The separator 11 has the function of separating the positive electrode and the negative electrode in the lithium-ion battery and the function of passing the electrolyte. Figure 1D As shown, the separator 11 has a plurality of pores.

[0069] like Figure 1DAs shown, silicon layer 31 is deposited on the top surface of separator 11. Note that a portion of silicon layer 31 may be formed inside a hole of separator 11, as shown in silicon layer 31a. In addition, silicon layer 31 may have silicon oxide on the surface.

[0070] The carbon particle layer 32 is formed so as to be in contact with the top surface of the silicon layer 31. The carbon particle layer 32 includes carbon particles 33 and a binder 13. Note that the carbon particle layer 32 may also include a conductive material 14.

[0071] As the carbon particles 33 , for example, graphite (natural graphite, artificial graphite), easily graphitizable carbon (soft carbon), hardly graphitizable carbon (hard carbon), etc. can be used.

[0072] As graphite, artificial graphite or natural graphite can be cited. As artificial graphite, for example, mesocarbon microbeads (MCMB), coke-based artificial graphite, asphalt-based artificial graphite, etc. can be cited. Here, spherical graphite with a spherical shape can be used as artificial graphite. For example, MCMB sometimes has a spherical shape, so it is preferred. In addition, MCMB is relatively easy to reduce its surface area, so it is sometimes preferred. As natural graphite, for example, flaky graphite, spheroidized natural graphite, etc. can be cited.

[0073] The non-graphitizable carbon can be obtained, for example, by calcining a synthetic resin such as a phenolic resin or an organic matter derived from a plant. The non-graphitizable carbon contained in the negative electrode active material of a lithium ion battery of one embodiment of the present invention has a plane spacing of (002) plane measured by X-ray diffraction (XRD) of preferably 0.34 nm or more and 0.50 nm or less, and more preferably 0.35 nm or more and 0.42 nm or less.

[0074] As the adhesive 13, for example, preferably used are rubber materials such as styrene-butadiene rubber (SBR), styrene-isoprene-styrene rubber, acrylonitrile-butadiene rubber, butadiene rubber, and ethylene-propylene-diene copolymer. In addition, fluororubber can also be used as the adhesive.

[0075] In addition, as a binder, for example, a water-soluble polymer is preferably used. As a water-soluble polymer, for example, polysaccharides etc. can also be used. As polysaccharides, cellulose derivatives such as carboxymethyl cellulose (CMC), methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, regenerated cellulose, starch etc. can be used. In addition, it is more preferred to use these water-soluble polymers and the above-mentioned rubber material in combination.

[0076] Alternatively, as an adhesive, it is preferred to use materials such as polystyrene, polymethyl acrylate, 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.

[0077] As the binder, a plurality of the above-mentioned materials may be used in combination.

[0078] For example, materials with particularly good viscosity regulating effects can also be used in combination with other materials. For example, although rubber materials and the like have high cohesive force and high elasticity, it is sometimes difficult to regulate viscosity when mixed in a solvent. In such a case, for example, it is preferably mixed with materials with particularly good viscosity regulating effects. As materials with particularly good viscosity regulating effects, for example, water-soluble polymers can be used. In addition, as water-soluble polymers with particularly good viscosity regulating effects, the above-mentioned polysaccharides can be used, for example, cellulose derivatives such as carboxymethyl cellulose (CMC), methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, and regenerated cellulose, or starch can be used.

[0079] Note that cellulose derivatives such as carboxymethyl cellulose, for example, can be easily used as viscosity modifiers by being converted into salts such as sodium salts and ammonium salts of carboxymethyl cellulose to improve their solubility. Due to the increased solubility, the dispersibility of active materials or other components can be improved when forming a slurry for an electrode. In this specification, etc., cellulose and cellulose derivatives used as binders for electrodes include their salts.

[0080] By dissolving a water-soluble polymer in water to stabilize its viscosity, the active material and other materials used as a binder combination, such as styrene-butadiene rubber, can be stably dispersed in an aqueous solution. Since the water-soluble polymer has a functional group, it is expected to be easily and stably attached to the surface of the active material. Most cellulose derivatives such as carboxymethyl cellulose have functional groups such as hydroxyl groups or carboxyl groups. Since they have functional groups, the polymer is expected to interact with each other and widely cover the surface of the active material.

[0081] When the binder covering or contacting the surface of the active material forms a film, it is also expected to be used as a passivation film to exert an effect of inhibiting the decomposition of the electrolyte. Here, a "passivation film" is a film that has no conductivity or very low conductivity. For example, when the passivation film is formed on the surface of the active material, it can inhibit the decomposition of the electrolyte at the battery reaction potential. More preferably, the passivation film can transmit lithium ions while inhibiting conductivity.

[0082] As the conductive material 14 , for example, any one or two or more of carbon black such as acetylene black and furnace black, graphite such as artificial graphite and natural graphite, carbon fiber such as carbon nanofiber and carbon nanotube, and graphene compound can be used.

[0083] As the carbon fiber, for example, mesophase pitch carbon fiber, isotropic pitch carbon fiber, etc. can be used. In addition, as the carbon fiber, carbon nanofiber or carbon nanotube can be used. For example, carbon nanotube can be produced by vapor phase growth method, etc.

[0084] The content of the conductive material in the total amount of the active material layer is preferably 0.5 wt % to 10 wt %, and more preferably 1 wt % to 5 wt %.

[0085] Unlike granular conductive materials such as carbon black that form point contact with the active material, the graphene compound can form a surface contact with low contact resistance, so the conductivity of the granular active material and the graphene compound can be improved with a smaller amount than that of a general conductive material. Therefore, the ratio of the active material in the active material layer can be increased. As a result, the discharge capacity of the battery can be increased.

[0086] Carbon compounds in the form of particles such as carbon black and graphite or fibrous carbon compounds such as carbon nanotubes can easily enter the microspace. For example, the microspace refers to the region between multiple active materials. By combining carbon compounds that can easily enter the microspace and sheet-like carbon compounds such as graphene that can impart conductivity to multiple particles, the density of the electrode can be increased and a good conductive path can be formed.

[0087] like Figure 1D As shown, the separator-integrated electrode 40 includes a separator 11 and a carbon particle layer 32 which are integrated via a silicon layer 31 .

[0088] As described above, the separator integrated electrode 40 does not include a metal foil. In addition, the separator integrated electrode 40 can be manufactured without using a metal foil. That is, a battery using the separator integrated electrode 40 can be lightweight. In addition, a battery using the separator integrated electrode 40 can be miniaturized. In addition, when the separator integrated electrode 40 is used as a negative electrode, since it does not include a metal foil, especially a copper foil, copper ions will not dissolve from the copper foil into the electrolyte in an over-discharge state, so a safe battery can be achieved.

[0089] FIG. 2A to FIG. 2C This is a diagram for explaining a coin-type battery, and explains an example in which a separator-integrated electrode 40 is used as a negative electrode.

[0090] Figure 2A This is a three-dimensional diagram of a coin-type battery. Figure 2B It is along Figure 2A The cross-sectional view of the dotted line A-A' in FIG. Figure 2C yes Figure 2B Deformation example.

[0091] like Figure 2A and Figure 2B As shown, the coin-type battery 10 includes a positive electrode can 51, a negative electrode can 52, and a gasket 53, and the positive electrode can 51 and the negative electrode can 52 are overlapped with the gasket 53. Note that the positive electrode can 51, the negative electrode can 52, and the gasket 53 are sometimes referred to as an outer package.

[0092] like Figure 2B As shown, the positive electrode 20 and the separator-integrated electrode 40 in the coin-type battery 10 are located inside the outer package. Although not shown, the inner side of the outer package contains an electrolyte.

[0093] The positive electrode 20 includes a positive electrode current collector 21 and a positive electrode active material layer 22 disposed on the positive electrode current collector. The separator integrated electrode 40 is as described above. The positive electrode 20 and the separator integrated electrode 40 can overlap in such a way that the positive electrode active material layer 22 contacts the separator 11 included in the separator integrated electrode 40.

[0094] The separator-integrated electrode 40 of one embodiment of the present invention does not include a current collector. Therefore, the carbon particle layer 32 included in the separator-integrated electrode 40 and the negative electrode can 52 of the outer package may have a region in contact with each other.

[0095] As Figure 2B The structural examples shown are different from the structural examples, such as Figure 2C As shown in FIG. 1 , a separator 12 may be included between the positive electrode 20 and the separator-integrated electrode 40. Figure 2C As shown, the area of ​​the separator-integrated electrode 40 may be larger than the area of ​​the positive electrode 20 .

[0096] As described above, the separator-integrated electrode 40 of one embodiment of the present invention may be an electrode having a structure that does not include a current collector. Therefore, a battery including the separator-integrated electrode 40 can realize a battery structure in which at least one of the positive electrode and the negative electrode does not include a current collector. Therefore, a battery including the separator-integrated electrode 40 can realize a lightweight battery structure. Alternatively, a battery including the separator-integrated electrode 40 can realize a small battery structure.

[0097] The separator-integrated electrode 40 of one embodiment of the present invention is not limited to the structure shown in FIG. 1 and FIG. 2 , and may have a structure as shown in FIG. Figure 3A As shown in FIG. 1 , the metal layer 34 is provided on the carbon particle layer 32. The metal layer 34 may be provided so as to cover the entire surface of the carbon particle layer 32, or may be provided as shown in FIG. Figure 3B As shown, it is provided so as to cover a part of the carbon particle layer 32 .

[0098] In addition, when a battery having a shape other than a coin-shaped battery, such as a laminated battery, a cylindrical battery, or a square battery, is used as the battery including the separator-integrated electrode 40, Figure 3C As shown, the metal layer 34 can also be connected to the conductor line 35 .

[0099] The metal layer 34 is preferably manufactured by a vapor phase method such as sputtering, vapor deposition, or CVD. By manufacturing the metal layer 34 by a vapor phase method, the thickness of the metal layer 34 does not become too large, so that the battery can be easily reduced in weight.

[0100] As the metal layer 34, for example, one or more of Ti, Pb, Zn, Sn, Mg, Zr, In, Cu, Ni and Li can be used. In addition, the thickness of the metal layer 34 is greater than or equal to 10 nm and less than or equal to 20 μm, preferably greater than or equal to 10 nm and less than or equal to 10 μm, and more preferably greater than or equal to 10 nm and less than or equal to 5 μm.

[0101] As described above, the separator-integrated electrode 40 of one embodiment of the present invention may be an electrode that does not include a metal foil as a current collector when the metal layer 34 is provided. Therefore, a battery including the separator-integrated electrode 40 can realize a battery structure that does not include a metal foil as a current collector for at least one of the positive electrode and the negative electrode. Therefore, a battery including the separator-integrated electrode 40 can realize a lightweight battery structure. Alternatively, a battery including the separator-integrated electrode 40 can realize a small battery structure.

[0102] The structure, method, and the like described in this embodiment mode can be used in combination with the structure, method, and the like described in other embodiment modes as appropriate.

[0103] (Implementation Method 2)

[0104] In this embodiment, an example of the shape of a secondary battery using the separator-integrated electrode manufactured by the manufacturing method described in the above embodiment as a negative electrode will be described.

[0105] [Cylindrical secondary battery]

[0106] Next, refer to Figure 4A An example of a cylindrical secondary battery will be described. Figure 4AAs shown, the top surface of the cylindrical secondary battery 616 includes a positive electrode cover (battery cover) 601, and the side and bottom surfaces thereof include a battery can (outer can) 602. The positive electrode cover 601 and the battery can (outer can) 602 are insulated by a gasket (insulating gasket) 610.

[0107] Figure 4B It is a diagram schematically showing a cross section of a cylindrical secondary battery. Figure 4B The cylindrical secondary battery shown includes a positive electrode cover (battery cover) 601 on the top surface and a battery can (outer can) 602 on the side and bottom surfaces. The positive electrode cover and the battery can (outer can) 602 are insulated by a gasket (insulating gasket) 610.

[0108] A battery element is provided inside the hollow cylindrical battery can 602, in which a strip-shaped positive electrode 604 and a strip-shaped negative electrode 606 are wound with a separator 605. In this way, in addition to the separator of the separator-integrated electrode (negative electrode 606), other separators may also be provided. Although not shown, the battery element is wound around the central axis. One end of the battery can 602 is closed and the other end is open. As the battery can 602, metals such as nickel, aluminum, titanium, their alloys, and alloys of them and other metals (such as stainless steel, etc.) that are resistant to corrosion by the electrolyte can be used. In addition, in order to prevent corrosion caused by the electrolyte, the battery can 602 is preferably covered with nickel and aluminum. Inside the battery can 602, the battery element in which the positive electrode, the negative electrode, and the separator are wound is sandwiched by a pair of opposing insulating plates 608 and insulating plates 609. In addition, a non-aqueous electrolyte (not shown) is injected into the interior of the battery can 602 in which the battery element is provided. As the nonaqueous electrolyte, the same electrolyte as that used in the coin-type secondary battery can be used.

[0109] Since the positive electrode and the negative electrode used for the cylindrical storage battery are wound, it is preferable that the active material is formed on both surfaces of the current collector.

[0110] By using the separator-integrated electrode described in Embodiment 1 for the negative electrode 606, a cylindrical secondary battery 616 with high capacity, high discharge capacity, and good cycle characteristics can be realized.

[0111] The positive electrode 604 is connected to the positive terminal (positive electrode current collecting wire) 603, and the negative electrode 606 is connected to the negative terminal (negative electrode current collecting wire) 607. Metal materials such as aluminum can be used for both the positive terminal 603 and the negative terminal 607. The positive terminal 603 is resistance welded to the safety valve mechanism 613, and the negative terminal 607 is resistance welded to the bottom of the battery can 602. The safety valve mechanism 613 is electrically connected to the positive electrode cover 601 through a PTC element (Positive Temperature Coefficient) 611. When the internal pressure of the battery rises to exceed a specified threshold, the safety valve mechanism 613 cuts off the electrical connection between the positive electrode cover 601 and the positive electrode 604. In addition, the PTC element 611 is a thermally sensitive resistance element whose resistance increases when the temperature rises, and limits the current by increasing the resistance to prevent abnormal heating. As a PTC element, barium titanate (BaTiO3)-based semiconductor ceramics, etc. can be used.

[0112] Figure 4C An example of a power storage system 615 is shown. The power storage system 615 includes a plurality of secondary batteries 616. The positive electrode of each secondary battery contacts a conductor 624 separated by an insulator 625, and the positive electrodes are electrically connected to each other. The conductor 624 is electrically connected to a control circuit 620 via a wiring 623. In addition, the negative electrode of each secondary battery is electrically connected to the control circuit 620 via a wiring 626. As the control circuit 620, a charge and discharge control circuit for performing charge and discharge or a protection circuit for preventing overcharge and / or overdischarge can be used.

[0113] Figure 4D An example of a power storage system 615 is shown. The power storage system 615 includes a plurality of secondary batteries 616, and the plurality of secondary batteries 616 are sandwiched between a conductive plate 628 and a conductive plate 614. The plurality of secondary batteries 616 are electrically connected to the conductive plate 628 and the conductive plate 614 through a wiring 627. The plurality of secondary batteries 616 may be connected in parallel or in series, or may be connected in parallel and then in series. By configuring the power storage system 615 including the plurality of secondary batteries 616, a large amount of electric power can be obtained.

[0114] Alternatively, a plurality of secondary batteries 616 may be connected in parallel and then connected in series.

[0115] In addition, a temperature control device may be included between the plurality of secondary batteries 616. When the secondary battery 616 is overheated, it can be cooled by the temperature control device, and when the secondary battery 616 is overcooled, it can be heated by the temperature control device. Therefore, the performance of the power storage system 615 is not easily affected by the external temperature.

[0116] In addition, Figure 4DIn FIG. 6 , the power storage system 615 is electrically connected to the control circuit 620 via wiring 621 and wiring 622. The wiring 621 is electrically connected to the positive electrodes of the plurality of secondary batteries 616 via the conductive plate 628, and the wiring 622 is electrically connected to the negative electrodes of the plurality of secondary batteries 616 via the conductive plate 614.

[0117] [Other structural examples of secondary batteries]

[0118] Another structural example of a secondary battery using a separator-integrated electrode as a negative electrode will be described with reference to FIGS. 5 and 6 .

[0119] Figure 5A The secondary battery 913 shown includes a winding body 950 provided with a terminal 951 and a terminal 952 inside a frame 930. The winding body 950 is impregnated with an electrolyte inside the frame 930. The terminal 952 is in contact with the frame 930, and the terminal 951 is prevented from contacting the frame 930 by an insulating material. Note that for convenience, although Figure 5A Frame 930 is shown separately in the figure, but in reality, winding body 950 is covered by frame 930, and terminals 951 and 952 extend outside frame 930. Frame 930 can be made of a metal material (such as aluminum) or a resin material.

[0120] In addition, if Figure 5B As shown, multiple materials can also be used to form Figure 5A For example, in the frame 930 shown in FIG. Figure 5B In the secondary battery 913 shown, a frame body 930 a and a frame body 930 b are bonded together, and a wound body 950 is provided in a region surrounded by the frame bodies 930 a and 930 b.

[0121] As the frame 930a, an insulating material such as an organic resin can be used. In particular, by using a material such as an organic resin to form the surface of the antenna, it is possible to suppress the shielding of the electric field by the secondary battery 913. In addition, if the electric field shielding caused by the frame 930a is small, the antenna can also be provided inside the frame 930a. As the frame 930b, for example, a metal material can be used.

[0122] Furthermore, Figure 5C The structure of the wound body 950 is shown. The wound body 950 includes a negative electrode 931, a positive electrode 932, and a separator 933. In this way, a separator different from the separator of the separator-integrated electrode (negative electrode 931) can be included. The wound body 950 is formed by overlapping the negative electrode 931 and the positive electrode 932 with the separator 933 sandwiched therebetween to form a laminated sheet, and the laminated sheet is wound. In addition, a plurality of layers of negative electrodes 931, positive electrodes 932, and separators 933 may also be stacked.

[0123] Alternatively, a secondary battery 913 including a wound body 950 a as shown in FIG. 6 may be used. Fig. 6A The wound body 950a shown includes a negative electrode 931, a positive electrode 932, and a separator 933. The negative electrode 931 includes a negative electrode active material layer 931a. The positive electrode 932 includes a positive electrode active material layer 932a.

[0124] By using the separator-integrated electrode described in Embodiment 1, a lightweight secondary battery 913 can be realized. In addition, a flexible secondary battery can also be realized.

[0125] The separator 933 is 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. In addition, from the viewpoint of safety, the width of the negative electrode active material layer 931a is preferably wider than the positive electrode active material layer 932a. In addition, the winding body 950a of the above shape is preferred because of its good safety and productivity.

[0126] like Figure 6B As shown, the negative electrode 931 is electrically connected to the terminal 951 by ultrasonic bonding, welding or pressing. The terminal 951 is electrically connected to the terminal 911a. In addition, the positive electrode 932 is electrically connected to the terminal 952 by ultrasonic bonding, welding or pressing. The terminal 952 is electrically connected to the terminal 911b.

[0127] like Figure 6C As shown, the wound body 950a and the electrolyte are covered by the frame 930 to form a secondary battery 913. The frame 930 is preferably provided with a safety valve, an overcurrent protection element, etc. The safety valve is a valve that is opened at a specified internal pressure in the frame 930 to prevent battery rupture.

[0128] like Figure 6B As shown, the secondary battery 913 may also include a plurality of winding bodies 950a. By using a plurality of winding bodies 950a, a secondary battery 913 with a larger discharge capacity can be realized. Fig. 6A and Figure 6B The other components of the secondary battery 913 shown can be referred to FIG. 5A to FIG. 5C The secondary battery 913 is shown.

[0129] <Laminated secondary battery>

[0130] then, Fig. 7A and Figure 7B An example of an external view of a laminated secondary battery using a separator-integrated electrode as a negative electrode is shown. Fig. 7A and Figure 7BIt includes 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. In this way, a separator different from the separator included in the separator-integrated electrode (negative electrode 506) may be included.

[0131] Fig. 8A It is an appearance diagram of the positive electrode 503 and the negative electrode 506. The positive electrode 503 includes a positive electrode current collector 501, and a positive electrode active material layer 502 is formed on the surface of the positive electrode current collector 501. In addition, the positive electrode 503 has an area where the positive electrode current collector 501 is partially exposed (hereinafter referred to as the tab area). The negative electrode 506 includes a negative electrode current collector 504, and a negative electrode active material layer 505 is formed on the surface of the negative electrode current collector 504. In addition, the negative electrode 506 has an area where the negative electrode current collector 504 is partially exposed, namely the tab area. Note that the area or shape of the tab area of ​​the positive electrode and the negative electrode is not limited to Fig. 8A Example shown.

[0132] <Method for manufacturing laminated secondary battery>

[0133] Reference Figure 8B and Figure 8C Yes Fig. 7A An example of a method for producing a laminated secondary battery whose appearance is shown in FIG. 1 is described below.

[0134] First, the negative electrode 506, the separator 507, and the positive electrode 503 are stacked. Figure 8B The stacked negative electrode 506, separator 507 and positive electrode 503 are shown. Here, an example using 5 sets of negative electrodes and 4 sets of positive electrodes is shown. In addition, it can also be said that it is a stacked body composed of negative electrodes, separators, and positive electrodes. Next, the tab regions of the positive electrode 503 are joined to each other, and the positive electrode lead electrode 510 is joined to the tab region of the outermost positive electrode. As the joining, ultrasonic welding or the like can be used, for example. Similarly, the tab regions of the negative electrode 506 are joined to each other, and the negative electrode lead electrode 511 is joined to the tab region of the outermost negative electrode.

[0135] Next, the negative electrode 506 , the separator 507 , and the positive electrode 503 are arranged on the outer packaging body 509 .

[0136] Below, as Figure 8C As shown, the outer package 509 is folded along the portion indicated by the dotted line. Then, the outer periphery of the outer package 509 is joined. As the joining method, for example, heat pressing or the like can be used. At this time, in order to inject the electrolyte later, a non-joined area (hereinafter referred to as the introduction port) is provided on a part (or one side) of the outer package 509.

[0137] Next, the electrolyte is introduced into the inner side of the outer packaging body 509 from the introduction port provided in the outer packaging body 509. The electrolyte is preferably introduced under a reduced pressure atmosphere or an inert gas atmosphere. Finally, the introduction port is joined. In this way, the laminated secondary battery 500 can be manufactured.

[0138] By using the separator-integrated electrode described in Embodiment 1 as a negative electrode, a lightweight secondary battery 500 can be realized.

[0139] [Battery pack example]

[0140] An example of a secondary battery pack according to one embodiment of the present invention that can be wirelessly charged using an antenna will be described with reference to FIG. 9 .

[0141] Fig. 9A 1 is a diagram showing the appearance of a secondary battery pack 531 , which has a thin rectangular parallelepiped shape (or a relatively thick flat plate shape). Fig. 9B 5 is a diagram for explaining the structure of a secondary battery pack 531. The secondary battery pack 531 includes a circuit board 540 and a secondary battery 513. A label 529 is attached to the secondary battery 513. The circuit board 540 is fixed by a sealing tape 515. The secondary battery pack 531 also includes an antenna 517.

[0142] The interior of the secondary battery 513 may have a structure including a wound body or a structure including a stacked body.

[0143] like Fig. 9B As shown, in the secondary battery pack 531, for example, a control circuit 590 is provided on a circuit board 540. In addition, the circuit board 540 is electrically connected to the terminal 514. In addition, the circuit board 540 is electrically connected to the antenna 517, one of the positive and negative wires 551 of the secondary battery 513, and the other of the positive and negative wires 552.

[0144] In addition, if Fig. 9C As shown, the circuit board 540 may further include a circuit system 590 a disposed on the circuit board 540 and a circuit system 590 b electrically connected to the circuit board 540 via the terminal 514 .

[0145] In addition, the shape of antenna 517 is not limited to a coil shape, for example, it can be a linear or plate shape. In addition, antennas such as a planar antenna, an aperture antenna, a traveling wave antenna, an EH antenna, a magnetic field antenna, or a dielectric antenna can also be used. Alternatively, antenna 517 can also be a flat conductor. The flat conductor can also be used as one of the conductors for electric field coupling. In other words, antenna 517 can also be used as one of the two conductors possessed by a capacitor. Thus, not only electromagnetic and magnetic fields are utilized, but also electric fields can be utilized to exchange electric power.

[0146] The secondary battery pack 531 includes a layer 519 between the antenna 517 and the secondary battery 513. The layer 519 has a function of shielding the electromagnetic field from the secondary battery 513, for example. As the layer 519, a magnetic body can be used, for example.

[0147] The structure, method, and the like described in this embodiment mode can be used in combination with the structure, method, and the like described in other embodiment modes as appropriate.

[0148] (Implementation 3)

[0149] In this embodiment, an example of a vehicle equipped with a secondary battery according to one embodiment of the present invention is described.

[0150] As a vehicle, a secondary battery can typically be used in a car. As a car, a new generation of clean energy vehicles such as a hybrid electric vehicle (HV), an electric vehicle (EV) or a plug-in hybrid electric vehicle (also referred to as PHEV or PHV) can be cited, and a secondary battery can be used as one of the power sources installed in the car. Vehicles are not limited to cars. For example, as a vehicle, a tram, a monorail, a ship, a submarine (submersible, unmanned submarine), a flying object (helicopter, unmanned aircraft (drone), airplane, rocket, satellite), an electric bicycle, an electric motorcycle, etc. can be cited, and a secondary battery including one embodiment of the present invention can be applied to these vehicles.

[0151] like Fig. 10C As shown, in an electric vehicle, as secondary batteries for main driving, first batteries 1301a and 1301b and a second battery 1311 for supplying power to an inverter 1312 for starting an engine 1304 are provided. The second battery 1311 is also called a cranking battery (also called a starter battery). The second battery 1311 only needs to have a high output and does not need to have a high capacity. In addition, the capacity of the second battery 1311 is smaller than that of the first batteries 1301a and 1301b.

[0152] The internal structure of the first battery 1301a can be Figure 5C or Fig. 6A The winding type shown can also be used Fig. 7A or Figure 7B The stacked type shown. In addition, the first battery 1301a may also use the all-solid battery of Embodiment 6. By using the all-solid battery of Embodiment 6 as the first battery 1301a, a high capacity can be achieved, safety is improved, and miniaturization and weight reduction can be achieved.

[0153] In this embodiment, an example of connecting the first battery 1301a and 1301b in parallel is shown, but more than three batteries may be connected in parallel. In addition, as long as sufficient power can be stored in the first battery 1301a, the first battery 1301b may not be provided. By forming a battery pack with multiple secondary batteries, a larger amount of power can be taken out. Multiple secondary batteries may be connected in parallel, in series, or in series after being connected in parallel. Sometimes multiple secondary batteries are referred to as battery packs.

[0154] In order to cut off the power from the plurality of secondary batteries, the vehicle-mounted secondary battery includes a charging plug or a circuit breaker that can cut off the high voltage without using a tool, which is provided in the first battery 1301a.

[0155] In addition, the power of the first battery 1301a, 1301b is mainly used to rotate the engine 1304, and the power is also supplied to the 42V series vehicle-mounted components (electric power steering system 1307, heater 1308, defogger 1309, etc.) through the DCDC circuit 1306. In the case where the rear wheel includes a rear engine 1317, the first battery 1301a is used to rotate the rear engine 1317.

[0156] Furthermore, the second battery 1311 supplies power to 14V series vehicle-mounted components (audio 1313 , power windows 1314 , lights 1315 , etc.) via the DCDC circuit 1310 .

[0157] Next, refer to Fig. 10A The first battery 1301a is described.

[0158] Fig. 10A An example of using nine rectangular secondary batteries 1300 as a battery pack 1415 is shown. In addition, the nine rectangular secondary batteries 1300 are connected in series and one electrode is fixed using a fixing portion 1413 formed of an insulator and the other electrode is fixed using a fixing portion 1414 formed of an insulator. In this embodiment, an example of fixing using fixing portions 1413 and 1414 is shown, but it can also be stored in a battery storage box (also referred to as a frame). Assuming that the vehicle is vibrated or shaken from the outside (road surface, etc.), it is preferable to fix multiple secondary batteries using fixing portions 1413, 1414 or a battery storage box. In addition, one electrode is electrically connected to the control circuit unit 1320 via wiring 1421. In addition, the other electrode is electrically connected to the control circuit unit 1320 via wiring 1422.

[0159] Alternatively, a memory circuit including a transistor using an oxide semiconductor may be used as the control circuit portion 1320. A charge control circuit or a battery control system including a memory circuit including a transistor using an oxide semiconductor is sometimes referred to as a BTOS (Battery operating system or Battery oxide semiconductor).

[0160] It is preferred to use a metal oxide used as an oxide semiconductor. For example, as a metal oxide, it is preferred to use an In-M-Zn oxide (the element M is selected from one or more of aluminum, gallium, yttrium, copper, vanadium, beryllium, boron, titanium, iron, nickel, germanium, zirconium, molybdenum, lanthanum, cerium, neodymium, hafnium, tantalum, tungsten and magnesium). In particular, the In-M-Zn oxide that can be applied to the metal oxide is preferably CAAC-OS (C-Axis Aligned Crystal Oxide Semiconductor) or CAC-OS (Cloud-Aligned Composite Oxide Semiconductor). In addition, In-Ga oxide and In-Zn oxide can also be used as metal oxides. CAAC-OS is an oxide semiconductor including a plurality of crystalline regions, and the c-axis of the plurality of crystalline regions is oriented in a specific direction. In addition, the specific direction refers to the thickness direction of the CAAC-OS film, the normal direction of the formed surface of the CAAC-OS film, or the normal direction of the surface of the CAAC-OS film. In addition, the crystalline region is a region having a periodicity of atomic arrangement. Note that when the atomic arrangement is viewed as a lattice arrangement, the crystalline region is also a region where the lattice arrangement is consistent.

[0161] In addition, "CAC-OS" refers to a structure in which the material is separated into a first region and a second region to form a mosaic shape, and the first region is distributed in the film (hereinafter also referred to as a cloud shape). That is, CAC-OS refers to a composite metal oxide having a structure in which the first region and the second region are mixed. Note that it is sometimes difficult to observe a clear boundary between the first region and the second region.

[0162] For example, in the CAC-OS of In-Ga-Zn oxide, based on the EDX mapping image obtained by energy dispersive X-ray spectroscopy (EDX), it can be confirmed that the structure has a region with In as the main component (first region) and a region with Ga as the main component (second region) that are unevenly distributed and mixed.

[0163] When CAC-OS is used for transistors, the complementary effect of the conductivity of the first region and the insulation of the second region can give CAC-OS a switch function (a function of controlling on / off). In other words, a portion of the CAC-OS material has a conductive function and another portion has an insulating function, and the entire material has a semiconductor function. By separating the conductive function and the insulating function, each function can be maximized. Therefore, by using CAC-OS for transistors, a large on-state current (I on ), high field effect mobility (μ) and good switching performance.

[0164] Oxide semiconductors have various structures and various characteristics. The oxide semiconductor of one embodiment of the present invention may include two or more of an amorphous oxide semiconductor, a polycrystalline oxide semiconductor, a-like OS, CAC-OS, nc-OS, and CAAC-OS.

[0165] In addition, the control circuit unit 1320 preferably uses a transistor containing an oxide semiconductor because the transistor can be used in a high temperature environment. In order to simplify the process, the control circuit unit 1320 can also be formed using a unipolar transistor. The operating ambient temperature range of the transistor containing an oxide semiconductor in the semiconductor layer is larger than that of the single-crystal Si transistor, that is, above -40°C and below 150°C, and the characteristic change when the secondary battery is overheated is smaller than that of the single-crystal Si transistor. The off-state current of the transistor containing an oxide semiconductor is also below the lower limit of the measurement at 150°C, but the temperature dependence of the off-state current characteristics of the single-crystal Si transistor is large. For example, at 150°C, the off-state current of the single-crystal Si transistor increases, and the current switching ratio does not become sufficiently large. The control circuit unit 1320 can improve safety.

[0166] The control circuit unit 1320 using a storage circuit including a transistor using an oxide semiconductor can also be used as an automatic control device for a secondary battery that causes instability such as a micro short circuit. As functions for solving the causes of instability of a secondary battery, there can be cited prevention of overcharging, prevention of overcurrent, control of overheating during charging, cell balancing in a battery pack, prevention of overdischarge, a capacity meter, automatic control of charging voltage and current according to temperature, control of charging current according to the degree of degradation, detection of abnormal behavior of a micro short circuit, prediction of abnormalities regarding a micro short circuit, etc. The control circuit unit 1320 has at least one of the above functions. In addition, ultra-miniaturization of the automatic control device for a secondary battery can be achieved.

[0167] In addition, "micro short circuit" refers to a very small short circuit inside the secondary battery. It is not a state where the positive and negative electrodes of the secondary battery cannot be charged or discharged due to a short circuit, but a phenomenon in which a short circuit current flows slightly in a very small short circuit part. Since a large voltage change occurs even in a short time and in a very small part, this abnormal voltage value will affect subsequent speculation.

[0168] One of the reasons for micro short circuits is believed to be that due to repeated charging and discharging, uneven distribution of positive electrode active materials occurs, local current concentration occurs in part of the positive electrode and part of the negative electrode, and part of the separator becomes inoperative, or side reactions produce side reactants, leading to micro short circuits.

[0169] In addition to micro short circuits, the control circuit unit 1320 detects the terminal voltage of the secondary battery and manages the charge and discharge state of the secondary battery. For example, to prevent overcharging, both the output transistor of the charging circuit and the blocking switch can be turned off at almost the same time.

[0170] then, Fig. 10B Show Fig. 10A An example of a block diagram of a battery pack 1415 is shown.

[0171] 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 measuring unit for the first battery 1301a. In the control circuit unit 1320, the upper limit voltage and the lower limit voltage of the secondary battery used are set to control the upper limit of the current flowing from the outside, the upper limit of the output current flowing to the outside, etc. The range above the lower limit voltage and below the upper limit voltage of the secondary battery is the recommended voltage range, and when the voltage is outside this range, the switch unit 1324 functions and serves as a protection circuit. In addition, the control circuit unit 1320 controls the switch unit 1324 to prevent overdischarge and / or overcharge, so it can also be called a protection circuit. For example, when the control circuit 1322 detects a voltage that will become overcharge, the current is shielded by making the switch of the switch unit 1324 in a closed state. In addition, the function of shielding the current according to the increase in temperature can also be set by setting a PTC element in the charge and discharge path. In addition, the control circuit unit 1320 includes an external terminal 1325 (+IN) and an external terminal 1326 (−IN).

[0172] The switch portion 1324 may be formed by combining n-channel transistors and p-channel transistors. In addition to switches including Si transistors using single crystal silicon, for example, Ge (germanium), SiGe (silicon germanium), GaAs (gallium arsenide), GaAlAs (gallium aluminum arsenic), InP (indium phosphide), SiC (silicon carbide), ZnSe (zinc selenide), GaN (gallium nitride), GaO x (gallium oxide; x is a real number greater than 0) constitute the switch section 1324. In addition, the storage element using the OS transistor can be freely configured by stacking it on a circuit using the Si transistor, so it is easy to achieve integration. In addition, the OS transistor can be manufactured by using the same manufacturing equipment as the Si transistor, thereby enabling low-cost manufacturing. That is, by stacking the control circuit section 1320 using the OS transistor on the switch section 1324 for integration, the switch section 1324 and the control circuit section 1320 can be integrated into one chip. The volume occupied by the control circuit section 1320 can be reduced, so miniaturization can be achieved.

[0173] The first battery 1301a and 1301b mainly supply power to the 42V series (high voltage series HV) vehicle-mounted equipment, while the second battery 1311 supplies power to the 14V series (low voltage series LV) vehicle-mounted equipment. In many cases, the second battery 1311 adopts a lead-acid battery because of cost advantages. However, the lead-acid battery has the disadvantages of large self-discharge compared with the lithium-ion battery and easy deterioration due to a phenomenon called sulfation. Although there is an advantage of no need for maintenance when a lithium-ion battery is used as the second battery 1311, an abnormality that is difficult to distinguish during manufacturing may occur when it is used for a long period of time, such as more than three years. In particular, in order to prevent the situation that the second battery 1311 of the starter inverter cannot work, even if the first battery 1301a and 1301b have residual capacity, the second battery 1311 is charged in a manner that is always kept fully charged by supplying power from the first battery to the second battery.

[0174] This embodiment shows an example in which lithium-ion secondary batteries are used for both the first battery 1301a and the second battery 1311. A lead-acid battery, an all-solid-state battery, or an electric double layer capacitor may also be used for the second battery 1311. For example, an all-solid-state battery of embodiment 6 may also be used. By using an all-solid-state battery of embodiment 6 as the second battery 1311, a large capacity can be achieved, thereby achieving miniaturization and lightness.

[0175] In addition, the regenerative energy caused by the rotation of the tire 1316 is transmitted to the engine 1304 through the transmission 1305, and is charged to the second battery 1311 from the engine controller 1303 and the battery controller 1302 through the control circuit unit 1321. In addition, the first battery 1301a is charged from the battery controller 1302 through the control circuit unit 1320. In addition, the first battery 1301b is charged from the battery controller 1302 through the control circuit unit 1320. In order to efficiently charge the regenerative energy, it is preferred that the first batteries 1301a and 1301b can be charged at a high speed.

[0176] The battery controller 1302 can set the charging voltage and charging current of the first batteries 1301a and 1301b, etc. The battery controller 1302 sets the charging conditions according to the charging characteristics of the secondary battery to be used and performs high-speed charging.

[0177] In addition, although not shown in the figure, when the electric vehicle is connected to an external charger, the socket of the charger or the connecting cable of the charger is electrically connected to the battery controller 1302. The power supplied from the external charger is charged to the first battery 1301a, 1301b through the battery controller 1302. In addition, some chargers are provided with a control circuit without using the function of the battery controller 1302, but in order to prevent overcharging, it is preferred to charge the first battery 1301a, 1301b through the control circuit unit 1320. In addition, sometimes the socket of the charger or the connecting cable of the charger is provided with a control circuit. The control circuit unit 1320 is sometimes referred to as 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. In addition, the ECU includes a microcomputer. In addition, the ECU uses a CPU or a GPU.

[0178] As an external charger installed in a charging station, there are 100V outlet-200V outlet or three-phase 200V and 50kW outlet, etc. In addition, it is also possible to charge by supplying power from an external charging device through a contactless power supply method.

[0179] In order to charge the battery in a short time during high-speed charging, a secondary battery that can withstand charging at a high voltage is desired.

[0180] In addition, when graphene is used as a conductive material and the capacity can be suppressed from decreasing and maintained at a high capacity even if the thickness of the electrode layer is increased and the load is increased, a synergistic effect can be achieved to realize a secondary battery with greatly improved electrical characteristics. In particular, it is very effective for secondary batteries used in vehicles, and a longer driving distance can be achieved without increasing the weight ratio of the secondary battery relative to the total weight of the vehicle, specifically, a vehicle that can travel a distance of more than 500 km per charge.

[0181] In particular, the secondary battery of the present embodiment described above uses the separator-integrated electrode described in Embodiment 1 as a negative electrode, and thus can provide a lightweight secondary battery as a secondary battery for vehicles.

[0182] Next, an example in which a secondary battery as one embodiment of the present invention is mounted on a vehicle, typically a transportation vehicle, will be described.

[0183] When the general Figure 4D , Figure 6C and Fig. 10A When any of the secondary batteries shown in is installed in a vehicle, a new generation of clean energy vehicles such as hybrid electric vehicles (HV), electric vehicles (EV) or plug-in hybrid electric vehicles (PHV) can be realized. In addition, the secondary battery can also be installed in agricultural machinery, electric bicycles including electric-assisted bicycles, motorcycles, electric wheelchairs, electric karts, ships, submarines, airplanes, rockets, artificial satellites, space probes, planetary probes or spacecraft. The secondary battery of one embodiment of the present invention can be a high-capacity secondary battery. Therefore, the secondary battery of one embodiment of the present invention is suitable for miniaturization and lightweight, and can be applied to transportation vehicles.

[0184] FIG. 11A to FIG. 11D A transport vehicle using one embodiment of the present invention is shown. Fig.11A The car 2001 shown is an electric car using an electric motor as a power source for running. Alternatively, the car 2001 is a hybrid car that can use an electric motor and an engine as a power source for running. When the secondary battery is installed in the vehicle, the example of the secondary battery shown in the embodiment 4 can be set in one or more parts. Fig.11A The illustrated automobile 2001 includes a battery pack 2200 including a secondary battery module in which a plurality of secondary batteries are connected, and preferably also includes a charge control device electrically connected to the secondary battery module.

[0185] In addition, in the automobile 2001, the secondary battery of the automobile 2001 can be charged by supplying power from an external charging device using a plug-in method or a contactless power supply method. When charging, the charging method or the specifications of the connector can be appropriately performed in accordance with the methods specified by CHAdeMO (registered trademark) or the combined charging system "Combined Charging System". As a charging device, a charging station set up in a commercial facility or a home power supply can also be used. For example, by supplying power from the outside using plug-in technology, the power storage device installed in the automobile 2001 can be charged. Charging can be performed by converting AC power into DC power using a conversion device such as an AC / DC converter.

[0186] In addition, although not shown in the figure, the power receiving device can also be installed in the vehicle and the power can be supplied non-contactly from the power transmission device on the ground for charging. When the non-contact power supply method is used, by assembling the power transmission device in the road or the outer wall, charging can be performed not only when the vehicle is parked but also when it is driving. In addition, the non-contact power supply method can also be used to send and receive power between two vehicles. Furthermore, a solar cell can be set on the outside of the vehicle to charge the secondary battery when it is parked or driving. Such non-contact power supply can be achieved using electromagnetic induction and magnetic field resonance.

[0187] Fig. 11B In the diagram, a large transport vehicle 2002 including an electrically controlled engine is shown as an example of a transport vehicle. The secondary battery module of the transport vehicle 2002 is, for example, a secondary battery module having a maximum voltage of 170V, in which four secondary batteries with a nominal voltage of 3.0V or more and 5.0V or less are connected in series and 48 cells are connected. The battery pack 2201 has the same characteristics as the battery pack 2201 except for the difference in the number of secondary batteries constituting the secondary battery module. Fig.11A The functions are the same, so the description is omitted.

[0188] exist Fig. 11C In the embodiment, a large transport vehicle 2003 including an engine controlled by electricity is shown as an example. The secondary battery module of the transport vehicle 2003 is, for example, a secondary battery module having a maximum voltage of 600V by connecting more than 100 secondary batteries having a nominal voltage of 3.0V or more and 5.0V or less in series. Therefore, a secondary battery with less uneven characteristics is required. By using a secondary battery using the separator-integrated electrode described in Embodiment 1 as a negative electrode, a lightweight secondary battery can be provided as a secondary battery for a vehicle.

[0189] exist Fig.11D , an aircraft 2004 equipped with an engine burning fuel is shown as an example. Fig.11DThe aircraft 2004 shown includes wheels for taking off and landing, so it can be said that the aircraft 2004 is a type of transportation vehicle. In the aircraft 2004, multiple secondary batteries are connected to form a secondary battery module and include a battery pack 2203 having a secondary battery module and a charging control device.

[0190] The secondary battery module of the aircraft 2004 is, for example, eight 4V secondary batteries connected in series and having a maximum voltage of 32 V. In addition to the number of secondary batteries constituting the secondary battery module of the battery pack 2203, the battery pack 2203 has the same Fig.11A The functions are the same, so the description is omitted.

[0191] Fig.11E As an example, an artificial satellite 2005 using a secondary battery 2204 is shown. Since the artificial satellite 2005 is used in the extremely low temperature space, it is preferable to include a secondary battery 2204 of one embodiment of the present invention having good low temperature resistance. In addition, the secondary battery 2204 is preferably installed inside the artificial satellite 2005 in a state covered with a heat-insulating member.

[0192] This embodiment mode can be used in combination with other embodiment modes.

[0193] (Implementation 4)

[0194] In this embodiment, using Fig. 12A and Fig. 12B An example in which the secondary battery of one embodiment of the present invention is installed in a building will be described.

[0195] Fig. 12A The house shown includes a storage device 2612 having a secondary battery of one embodiment of the present invention and a solar panel 2610. The storage device 2612 is electrically connected to the solar panel 2610 through wiring 2611 or the like. In addition, the storage device 2612 can be electrically connected to a charging device 2604 set on the ground. The power obtained by the solar panel 2610 can be charged into the storage device 2612. In addition, the power stored in the storage device 2612 can be charged into the secondary battery included in the vehicle 2603 through the charging device 2604. The storage device 2612 is preferably arranged in the underfloor space portion. By being arranged in the underfloor space portion, the space on the floor can be effectively utilized. Alternatively, the storage device 2612 can also be arranged on the floor.

[0196] The power stored in the power storage device 2612 can also 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 electronic devices can be used by using the power storage device 2612 of one embodiment of the present invention as an uninterruptible power supply.

[0197] Fig. 12B An example of a power storage device according to one embodiment of the present invention is shown below. Fig. 12B As shown, a power storage device 791 according to one embodiment of the present invention is installed in an underfloor space 796 of a building 799 .

[0198] The power storage device 791 is provided with a control device 790 , and the control device 790 is electrically connected to the switchboard 703 , the power storage controller 705 (also referred to as a control device), the display 706 , and the router 709 through wiring.

[0199] Electric power is supplied from the commercial power supply 701 to the switchboard 703 through the lead-in installation portion 710. In addition, both the electric power from the power storage device 791 and the electric power from the commercial power supply 701 are supplied to the switchboard 703, and the switchboard 703 supplies the supplied electric power to the general load 707 and the storage load 708 through the socket (not shown).

[0200] Examples of the general load 707 include electronic devices such as a television and a personal computer, and examples of the power storage load 708 include electronic devices such as a microwave oven, a refrigerator, and an air conditioner.

[0201] The power storage controller 705 has a measuring unit 711, a predicting unit 712, and a planning unit 713. The measuring unit 711 has a function of measuring the power consumption of the general load 707 and the power storage load 708 in a day (e.g., from 0:00 to 24:00). In addition, the measuring unit 711 may also have a function of measuring the power of the power storage device 791 and the power supplied from the commercial power supply 701. In addition, the predicting unit 712 has a function of predicting the required power consumed by the general load 707 and the power storage load 708 in the next day based on the power consumption of the general load 707 and the power storage load 708 in a day. In addition, the planning unit 713 has a function of determining the charging and discharging plan of the power storage device 791 based on the required power predicted by the predicting unit 712.

[0202] The amount of power consumed by the general load 707 and the power storage load 708 measured by the measuring unit 711 can be confirmed using the display 706. In addition, it can also be confirmed using electronic devices such as a television and a personal computer through the router 709. Furthermore, it can also be confirmed using a portable electronic terminal such as a smart phone or a tablet terminal through the router 709. In addition, the required power for each time period (or each hour) predicted by the prediction unit 712 can also be confirmed using the display 706, an electronic device or a portable electronic terminal.

[0203] This embodiment mode can be used in combination with other embodiment modes.

[0204] (Implementation 5)

[0205] In the present embodiment, as an example of a vehicle equipped with a secondary battery, an example in which a lithium ion battery according to one embodiment of the present invention is installed in a motorcycle or a bicycle is described.

[0206] Fig.13A An example of an electric bicycle using the power storage device according to one embodiment of the present invention will be described. Fig.13A The electric bicycle 8700 shown can use the power storage device of one embodiment of the present invention. For example, the power storage device of one embodiment of the present invention includes a plurality of storage batteries and a protection circuit.

[0207] The electric bicycle 8700 includes a power storage device 8702. The power storage device 8702 supplies power to a motor that assists the rider. In addition, the power storage device 8702 is portable. Fig. 13B The power storage device 8702 taken out of the bicycle is shown. The power storage device 8702 has a plurality of storage batteries 8701 included in the power storage device of one embodiment of the present invention built in, and the remaining power, etc. can be displayed by the display unit 8703. In addition, the power storage device 8702 includes the control circuit 8704 shown in Embodiment 7 that can perform charging control or abnormality detection of the secondary battery. The control circuit 8704 is electrically connected to the positive electrode and the negative electrode of the storage battery 8701. In addition, by combining with a secondary battery using the separator integrated electrode described in Embodiment 1 as a negative electrode, a lightweight secondary battery can be provided as a secondary battery for a vehicle.

[0208] Fig. 13C This is an example of a two-wheeled vehicle using the power storage device of one embodiment of the present invention. Fig. 13C The scooter 8600 shown includes a power storage device 8602, a rearview mirror 8601, and a turn signal lamp 8603. The power storage device 8602 can supply power to the turn signal lamp 8603. In addition, a lightweight secondary battery using the separator-integrated electrode described in Embodiment 1 as a negative electrode can be provided as a secondary battery for a vehicle.

[0209] In addition, Fig. 13C In the illustrated scooter 8600, the power storage device 8602 can be stored in the under-seat storage portion 8604. Even if the under-seat storage portion 8604 is small, the power storage device 8602 can be stored in the under-seat storage portion 8604.

[0210] This embodiment mode can be used in combination with other embodiment modes.

[0211] (Implementation method 6)

[0212] In this embodiment, an example of installing a secondary battery of one embodiment of the present invention in an electronic device is described. As an electronic device equipped with a secondary battery, for example, a television device (also referred to as a television or a television receiver), a display for a computer, a digital camera, a digital video camera, a digital photo frame, a mobile phone (also referred to as a mobile phone, a mobile phone device), a portable game console, a portable information terminal, a sound reproduction device, a large game console such as a pinball machine, etc. can be cited. As a portable information terminal, a notebook personal computer, a tablet terminal, an e-book terminal, a mobile phone, etc. can be cited.

[0213] Fig.14A An example of a mobile phone is shown. The mobile phone 2100 includes an operation button 2103, an external connection port 2104, a speaker 2105, a microphone 2106, and the like in addition to a display portion 2102 mounted on a housing 2101. In addition, the mobile phone 2100 includes a secondary battery 2107. By including the secondary battery 2107 using the separator-integrated electrode described in Embodiment 1 as a negative electrode, a lightweight secondary battery can be provided as a secondary battery in a small electronic device.

[0214] The mobile phone 2100 can execute various application programs such as mobile phone, e-mail, article reading and writing, music playing, Internet communication, computer games, etc.

[0215] The operation button 2103 may have various functions in addition to time setting, such as power switch, wireless communication switch, silent mode setting and cancellation, power saving mode setting and cancellation, etc. For example, by using the operating system incorporated in the mobile phone 2100, the function of the operation button 2103 can be freely set.

[0216] In addition, the mobile phone 2100 can perform short-range wireless communication standardized by the communication. For example, by communicating with a headset capable of wireless communication, a hands-free call can be made.

[0217] In addition, the mobile phone 2100 has an external connection port 2104, and data can be directly sent to or received from other information terminals through a connector. In addition, charging can also be performed through the external connection port 2104. In addition, the charging operation can also be performed using wireless power supply without using the external connection port 2104.

[0218] The mobile phone 2100 preferably includes a sensor. For example, a fingerprint sensor, a pulse sensor, a human body sensor such as a temperature sensor, a touch sensor, a pressure sensor, an acceleration sensor, etc. are preferably installed as the sensor.

[0219] Fig. 14BAn unmanned aerial vehicle 2300 including a plurality of rotors 2302 is shown. The unmanned aerial vehicle 2300 is also referred to as a drone. The unmanned aerial vehicle 2300 includes a secondary battery 2301 of one embodiment of the present invention, a camera 2303, and an antenna (not shown). The unmanned aerial vehicle 2300 can be remotely operated via the antenna. The secondary battery using the separator-integrated electrode described in Embodiment 1 as a negative electrode has a high energy density and can be used for a long period of time, so it is suitable as a secondary battery mounted on the unmanned aerial vehicle 2300.

[0220] Fig. 14C An example of a robot is shown. Fig. 14C The robot 6400 shown includes a secondary battery 6409, an illumination sensor 6401, a microphone 6402, an upper camera 6403, a speaker 6404, a display unit 6405, a lower camera 6406, an obstacle sensor 6407, a moving mechanism 6408, a computing device, and the like.

[0221] The microphone 6402 has a function of sensing the user's voice and surrounding sounds, etc. In addition, the speaker 6404 has a function of emitting sound. The robot 6400 can communicate with the user through the microphone 6402 and the speaker 6404.

[0222] The display unit 6405 has the function of displaying various information. The robot 6400 can display the information required by the user on the display unit 6405. The display unit 6405 can also be equipped with a touch panel. In addition, the display unit 6405 can be a detachable information terminal, and by setting it at a fixed position of the robot 6400, it can be charged and send and receive data.

[0223] The upper camera 6403 and the lower camera 6406 have the function of photographing the surrounding environment of the robot 6400. In addition, the obstacle sensor 6407 can detect whether there is an obstacle in the direction of the robot 6400 when it moves forward using the moving mechanism 6408. The robot 6400 can confirm the surrounding environment using the upper camera 6403, the lower camera 6406, and the obstacle sensor 6407 and move safely.

[0224] A secondary battery 6409 according to one embodiment of the present invention and a semiconductor device or an electronic component are provided inside the robot 6400. The secondary battery using the separator-integrated electrode described in Embodiments 1 and 2 as a negative electrode has a high energy density and can be used for a long period of time, so it is suitable as the secondary battery 6409 installed in the robot 6400.

[0225] Fig.14DAn example of a sweeping robot is shown. The sweeping robot 6300 includes a display unit 6302 disposed on the surface of a frame 6301, a plurality of cameras 6303 disposed on the side, a brush 6304, an operation button 6305, a secondary battery 6306, various sensors, etc. Although not shown in the figure, the sweeping robot 6300 also has wheels, a suction port, etc. The sweeping robot 6300 can walk automatically, detect garbage 6310, and can suck up garbage from the suction port set below.

[0226] The sweeping robot 6300 can determine whether there are obstacles such as walls, furniture, or steps by analyzing the image taken by the camera 6303. In addition, when an object such as a wire that may be entangled with the brush 6304 is found through image analysis, the rotation of the brush 6304 can be stopped. The internal area of ​​the sweeping robot 6300 is equipped with a secondary battery 6306 and a semiconductor device or an electronic component according to one embodiment of the present invention. The secondary battery using the separator-integrated electrode described in embodiments 1 and 2 as a negative electrode has a high energy density and can be used for a long time over a long period of time, so it is suitable as a secondary battery 6306 installed in the sweeping robot 6300.

[0227] Fig.15A An example of a wearable device is shown. A secondary battery is used as a power source of the wearable device. In addition, in order to improve the splash-proof, waterproof or dust-proof performance when the user uses the wearable device in daily life or outdoors, the user not only wants the wearable device to be able to be charged by wire with the connector part exposed for connection, but also wants to be able to be charged wirelessly.

[0228] For example, the secondary battery of one embodiment of the present invention can be installed in Fig.15A The eyeglass-type device 4000 is shown. The eyeglass-type device 4000 includes a frame 4000a and a display unit 4000b. By installing a secondary battery in the temple portion of the curved frame 4000a, the eyeglass-type device 4000 can be lightweight, well-balanced, and have a long continuous use time. The secondary battery using the separator-integrated electrode described in Embodiments 1 and 2 as a negative electrode has a high energy density, and a space-saving structure that can cope with the miniaturization of the frame can be realized.

[0229] In addition, the secondary battery of one embodiment of the present invention can be mounted on the earphone type device 4001. The earphone type device 4001 includes at least a microphone part 4001a, a flexible tube 4001b, and an earphone part 4001c. In addition, the secondary battery can be provided in the flexible tube 4001b or in the earphone part 4001c. The secondary battery using the separator integrated electrode described in Embodiments 1 and 2 as a negative electrode has a high energy density and can realize a structure capable of coping with the space saving required for miniaturization of the frame.

[0230] In addition, the secondary battery of one embodiment of the present invention can be mounted on a device 4002 that can be directly mounted on the body. In addition, the secondary battery 4002b can be provided in the thin housing 4002a of the device 4002. The secondary battery using the separator-integrated electrode described in Embodiments 1 and 2 as the negative electrode has a high energy density, and a space-saving structure that can cope with the miniaturization of the housing can be realized.

[0231] In addition, the secondary battery of one embodiment of the present invention can be mounted on the device 4003 that can be mounted on clothes. In addition, the secondary battery 4003b can be set in the thin frame 4003a of the device 4003. The secondary battery using the separator-integrated electrode described in Embodiments 1 and 2 as the negative electrode has a high energy density and can realize a structure that can cope with the space saving required for miniaturization of the frame.

[0232] In addition, the secondary battery of one embodiment of the present invention can be mounted on a belt-type device 4006. The belt-type device 4006 includes a belt portion 4006a and a wireless power supply and receiving portion 4006b, and the secondary battery can be mounted in the inner area of ​​the belt portion 4006a. The secondary battery using the separator-integrated electrode described in Embodiments 1 and 2 as a negative electrode has a high energy density, and a space-saving structure that can cope with the miniaturization of the frame can be realized.

[0233] In addition, the secondary battery of one embodiment of the present invention can be mounted on a watch-type device 4005. The watch-type device 4005 includes a display portion 4005a and a strap portion 4005b, and the secondary battery can be set in the display portion 4005a or the strap portion 4005b. The secondary battery using the separator-integrated electrode described in Embodiments 1 and 2 as a negative electrode has a high energy density, and a space-saving structure that can cope with the miniaturization of the frame can be realized.

[0234] The display unit 4005a can display various information such as e-mails and incoming phone calls in addition to the time.

[0235] In addition, since the watch-type device 4005 is a wearable device that is directly wrapped around the wrist, it can also be equipped with sensors for measuring the user's pulse, blood pressure, etc. Thus, the user's exercise volume and health-related data can be stored for health management.

[0236] Fig. 15B is a perspective view showing the watch-type device 4005 taken off from the wrist.

[0237] in addition, Fig. 15C A side view is shown. Fig. 15CThe internal region includes a secondary battery 913. The secondary battery 913 is the secondary battery described in Embodiment Mode 4. The secondary battery 913 is provided at a position overlapping the display portion 4005, so that the wristwatch type device 4005 can be compact and lightweight while having high density and high capacity.

[0238] The wristwatch-type device 4005 needs to be small and lightweight, so by using the separator-integrated electrode described in Embodiments 1 and 2 as the negative electrode, a high-energy-density and lightweight secondary battery 913 can be realized.

[0239] This embodiment mode can be used in combination with other embodiment modes.

[0240] [Example]

[0241] In this example, a separator-integrated electrode according to one embodiment of the present invention was manufactured, and the strength and charge-discharge characteristics of the electrode were evaluated.

[0242] <Manufacturing of Electrodes>

[0243] Electrodes 1 , 2 , and 3 of separator-integrated electrodes according to one embodiment of the present invention were manufactured with reference to the manufacturing method described in Embodiment 1. Comparative electrodes 1 and 2 were manufactured by the same manufacturing method.

[0244] [Preparation of Isolate]

[0245] First, separators were prepared for manufacturing the electrode 1, the electrode 2, the electrode 3, the comparative electrode 1, and the comparative electrode 2. As the separator, a PP (polypropylene) separator having a thickness of 25 μm was used.

[0246] [Manufacturing of Silicon Layer]

[0247] Next, the above-mentioned insulator was fixed on the substrate and then placed in a sputtering deposition device to deposit a silicon film. A 5N silicon (boron-doped) target with a diameter of 101.6 mm was used for the deposition of the silicon film, and the deposition was performed under the conditions of 40 sccm of argon, 0.4 Pa of pressure, and 500 W (DC). The sample in which the silicon film on the above-mentioned insulator was deposited until the thickness reached about 50 nm was recorded as sample 1.

[0248] In addition, sample 2, sample 3, comparative sample 1, and comparative sample 2 were manufactured, each having a different silicon film thickness from sample 1. The sample in which the silicon film on the insulator was deposited until the thickness reached about 100 nm was recorded as sample 2. In addition, the sample in which the silicon film on the insulator was deposited until the thickness reached about 200 nm was recorded as sample 3. In addition, as comparative sample 1, a sample in which the silicon film on the insulator was deposited until the thickness reached about 10 nm was prepared. In addition, as comparative sample 2, a sample in which the silicon film on the insulator was deposited until the thickness reached about 20 nm was prepared.

[0249] [Manufacturing of Carbon Particle Layer]

[0250] Next, a carbon particle layer (graphite layer) was produced on the silicon layer in each of Sample 1, Sample 2, Sample 3, Comparative Sample 1, and Comparative Sample 2. The carbon particle layer was produced by a doctor blade coating method.

[0251] The slurry for coating the carbon particle layer was prepared by mixing graphite: AB (acetylene black): PVdF (polyvinylidene fluoride) = 95:2:3 (weight ratio) as a dispersion medium using NMP (N-methyl-pyrrolidone). The loading of the carbon particle layer was about 10 mg / cm 2 The coating was performed by adjusting the blade gap in a manner of . The dispersion medium after coating was dried at 50° C. for 3 hours using a ventilation dryer. The manufacturing conditions of the carbon particle layer were the same for all samples.

[0252] By the method shown above, a carbon particle layer is provided in each of Sample 1, Sample 2, Sample 3, Comparative Sample 1, and Comparative Sample 2. Sample 1 after the carbon particle layer is provided is referred to as Electrode 1, Sample 2 after the carbon particle layer is provided is referred to as Electrode 2, Sample 3 after the carbon particle layer is provided is referred to as Electrode 3, Comparative Sample 1 after the carbon particle layer is provided is referred to as Comparative Electrode 1, and Comparative Sample 2 after the carbon particle layer is provided is referred to as Comparative Electrode 2.

[0253] [Strength of separator-integrated electrode]

[0254] Next, the punching strength of electrode 1, electrode 2, electrode 3, comparative electrode 1, and comparative electrode 2 was investigated. Table 1 shows the results of punching each of electrode 1, electrode 2, electrode 3, comparative electrode 1, and comparative electrode 2 into a circle with a diameter of 12 mm. Note that the carbon particle layer of comparative electrode 1 was completely peeled off before punching, and punching was not performed.

[0255] [Table 1]

[0256]

[0257]

[0258] Fig.16A , Fig. 16B , Fig. 16C and Fig.16D The photograph shows the shape after being punched into a round shape. Fig.16A The photo shows the comparison electrode 2 (silicon layer 20 nm) after punching. Fig. 16B The photo shows the electrode 1 (silicon layer 50nm) after punching. Fig. 16C The photo shows the electrode 2 (silicon layer 100 nm) after punching. Fig.16D The photograph after punching out the electrode 3 (silicon layer 200 nm) is shown.

[0259] As shown in Table 1 and FIG. 16 , when the thickness of the silicon layer is 20 nm or more, an insulator-integrated electrode in which the insulator and the carbon particle layer are integrated can be obtained. Furthermore, when the thickness of the silicon layer is 50 nm or more, the peeling of the carbon particle layer is greatly reduced. Furthermore, when the thickness of the silicon layer is 100 nm or more, a good insulator-integrated electrode with almost no peeling of the carbon particle layer can be obtained.

[0260] Here, the separator integrated electrode punched out from the electrode 1 is referred to as the electrode 1A. In addition, the separator integrated electrode punched out from the electrode 2 is referred to as the electrode 2A. In addition, the separator integrated electrode punched out from the electrode 3 is referred to as the electrode 3A. In addition, the separator integrated electrode punched out from the comparison electrode 2 is referred to as the comparison electrode 2A.

[0261] [Manufacturing of half-cell]

[0262] Next, CR2032 type (20 mm in diameter and 3.2 mm in height) coin-shaped batteries were manufactured using the electrode 1A, the electrode 2A, the electrode 3A, and the comparative electrode 2A as positive electrodes.

[0263] A lithium metal foil was used as a counter electrode (negative electrode of the coin-type battery) and a glass fiber sheet (thickness 260 μm, pore size 1.2 μm) was provided between the counter electrode and the above electrodes (electrode 1A, electrode 2A, electrode 3A and comparative electrode 2A).

[0264] As an electrolyte contained in the electrolytic solution, 1 mol / L lithium hexafluorophosphate (LiPF6) was used, and as the electrolytic solution, ethylene carbonate (EC) and diethyl carbonate (DEC) mixed at a ratio of EC:DEC=3:7 (volume ratio) were used.

[0265] The positive electrode can and the negative electrode can are formed of stainless steel (SUS).

[0266] Here, the coin-shaped battery manufactured using electrode 1A is referred to as battery 1. In addition, the coin-shaped battery manufactured using electrode 2A is referred to as battery 2. In addition, the coin-shaped battery manufactured using electrode 3A is referred to as battery 3. In addition, the coin-shaped battery manufactured using comparison electrode 2A is referred to as comparison battery 2.

[0267] [Charge and discharge characteristics]

[0268] The charge and discharge characteristics of the battery 1, battery 2, battery 3 and comparison battery 2 manufactured above were investigated. The measurement of the charge and discharge characteristics started with discharge. Discharge was performed at CCCV (constant current constant voltage), 0.2C, 0.01V, and a load stop current of 0.02C. Next, charge was performed at CC (constant current), 0.2C, and a load stop voltage of 1.0V. Note that here, 1C represents a current value of 0.035mA / g as a unit weight of graphite. The measurement temperature was set to 25°C.

[0269] 17A to 17C The results of measuring the charge and discharge characteristics of Battery 1, Battery 2, and Battery 3 are shown. Note that Comparative Battery 2 was hardly chargeable or dischargeable under the above-described charge and discharge conditions, and the results are not shown.

[0270] Fig.17A is a graph showing the charge and discharge results of battery 1 (silicon layer 50nm), in which charging and discharging can be performed. In addition, Fig. 17B is a graph showing the charge and discharge results of battery 2 (silicon layer 100 nm), in which charging and discharging can be performed. In addition, Fig. 17C 3 is a graph showing the charge and discharge results of battery 3 (silicon layer 200 nm), in which both charge and discharge are possible.

[0271] When comparing the charge and discharge characteristics of battery 1, battery 2, and battery 3, the discharge curve of battery 1 is on the lower voltage side compared to the discharge curves of battery 2 and battery 3. In addition, the charge curve of battery 1 is on the higher voltage side compared to the charge curves of battery 2 and battery 3. In other words, it can be estimated that the internal resistance (also called reaction resistance) of battery 1 is higher than that of battery 2 and battery 3.

[0272] As shown in the above examples, it can be seen that in a battery including a separator-integrated electrode manufactured by the manufacturing method described in Embodiment 1, charging and discharging can be performed when the thickness of the silicon layer is 50 nm or more. That is, by using the separator-integrated electrode described in Embodiment 1 that does not include a metal foil as a current collector, a battery that can be charged and discharged and is lightweight can be manufactured.

[0273] In addition, it can be seen that the internal resistance of battery 2 with a silicon layer thickness of 100nm and battery 3 with a silicon layer thickness of 200nm is low, and good charging and discharging operations can be performed. Therefore, it can be said that in an insulator-integrated electrode of one embodiment of the present invention, the thickness of the silicon layer is preferably greater than 100nm and less than 200nm.

[0274] [Explanation of symbols]

[0275] 10: coin-shaped battery, 11: separator, 12: separator, 13: binder, 14: conductive material, 20: positive electrode, 21: positive electrode current collector, 22: positive electrode active material layer, 31a: silicon layer, 31: silicon layer, 32: carbon particle layer, 33: carbon particles, 34: metal layer, 35: wire, 40: separator integrated electrode, 51: positive electrode can, 52: negative electrode can, 53: gasket

Claims

1. A battery comprising: Isolator integrated electrode, The insulator-integrated electrode includes an insulator, a carbon particle layer, and a silicon layer located between the insulator and the carbon particle layer.

2. A battery comprising: Isolator integrated electrode; as well as Outer packaging, The insulator-integrated electrode comprises an insulator, a carbon particle layer, and a silicon layer located between the insulator and the carbon particle layer. Furthermore, the carbon particle layer and the outer packaging body have a region in contact with each other.

3. The battery according to claim 1 or 2, The thickness of the silicon layer is greater than or equal to 100 nm and less than or equal to 200 nm.

4. The battery according to claim 1 or 2, wherein the separator comprises polypropylene.

5. A method for manufacturing a battery comprising a separator-integrated electrode, The separator integrated electrode comprises a separator, a carbon particle layer and a silicon layer located between the separator and the carbon particle layer. The manufacturing method comprises the following steps: A first step of manufacturing the silicon layer on the insulator by sputtering; and a second step of manufacturing the carbon particle layer by coating a slurry containing carbon particles on the silicon layer, in, The silicon layer has a thickness of not less than 100 nm and not more than 200 nm.

6. The method for manufacturing a battery according to claim 5, Wherein the slurry comprises N-methyl-pyrrolidone.

7. The method for manufacturing a battery according to claim 5 or 6, wherein the separator comprises polypropylene.

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