electronic machinery

Abstract

To provide an energy storage device that can be repeatedly bent. Or, a highly reliable energy storage device. To provide a place. Or to provide a long-life energy storage device. Or to prevent repeated bending. To provide an electronic device that can do so. Or, to provide an electronic device that is flexible. [Solution] The film has a positive electrode and a negative electrode, and the film has a plurality of protrusions, The difference between the maximum and minimum heights of the surface of the material is 0.15 mm or more and less than 0.8 mm. The rigidity ratio of the material is 6.5 × 10 9 The film is smaller than N and has a metal layer, and the thickness of the metal layer is The thickness is between 5 μm and 200 μm, and the positive and negative electrodes are wrapped in film in the energy storage device. It is placed there.

Description

[Technical Field]

[0001] The present invention relates to a product, method, or method of manufacture. Or, the present invention relates to a process, machine Relating to a manufacturer or composition of matter. In one aspect of the present invention, semiconductor devices, display devices, light-emitting devices, energy storage devices, memory devices, and the The present invention relates to a method for driving such devices, a method for manufacturing them, or a method for evaluating them. In particular, one aspect of the present invention The present invention relates to an energy storage device, a method for manufacturing the same, or a method for evaluating the same.

[0002] In this specification, the term "energy storage device" refers to all elements and devices that have an energy storage function. That is the case. [Background technology]

[0003] In recent years, secondary batteries such as lithium-ion secondary batteries, lithium-ion capacitors, air batteries, etc. The development of various energy storage devices is actively underway. In particular, high output and high energy density are being pursued. Lithium-ion rechargeable batteries are used in mobile phones, smartphones, and notebook personal computers. Electronic devices such as portable information terminals, portable music players, digital cameras, or medical devices. , hybrid electric vehicle (HEV), electric vehicle (EV), or plug-in hybrid vehicle (P With the development of the semiconductor industry, next-generation clean energy vehicles such as HEVs are rapidly increasing. Demand is expanding, and it is becoming indispensable to modern information society as a source of rechargeable energy. This is the case. Patent Document 1 shows an example of mounting an energy storage device on an electronic device.

[0004] In recent years, electronic devices worn on the human body have been proposed, and wearable displays have emerged. They are called such things. For the sake of convenience, such electronic devices are, for example, not worn on the human body. The ability to repeatedly perform detachment and re-detachment is required. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2015-38868 [Overview of the project] [Problems that the invention aims to solve]

[0006] When impurities enter the inside of an energy storage device, it can lead to a decrease in the device's performance. For example... If impurities such as water are mixed into the non-aqueous electrolyte, the discharge capacity may decrease. For example, in energy storage... Due to the poor airtightness of the device's exterior, components from the atmosphere enter the interior of the exterior, and as a result, Impurities may be introduced into the energy storage device.

[0007] Furthermore, energy storage devices installed in electronic devices worn on the human body are used in the same way as the electronic device itself. When the battery is repeatedly detached, the battery itself may also be repeatedly bent. When bending, deterioration may occur in the outer casing, and impurities such as moisture may enter the inside of the outer casing. Knowing the amount of moisture that gets inside the outer casing is important for improving the reliability of energy storage devices. It is important.

[0008] One aspect of the present invention aims to provide an energy storage device that can be repeatedly bent. Alternatively, one aspect of the present invention aims to provide a highly reliable energy storage device. Alternatively, one aspect of the present invention aims to provide an energy storage device with a long lifespan. Alternatively, one aspect of the present invention aims to provide an electronic device that can be repeatedly bent. This is one aspect of the present invention. Alternatively, one aspect of the present invention aims to provide a flexible electronic device. It shall be one of them.

[0009] Alternatively, one aspect of the present invention aims to provide a flexible film. Alternatively, one aspect of the present invention is to provide a film that can be repeatedly bent. This will be the first topic.

[0010] Alternatively, one aspect of the present invention aims to provide a method for evaluating the reliability of an energy storage device. Alternatively, one aspect of the present invention provides a method for evaluating the amount of impurities inside an energy storage device. One of the challenges is to provide a method for evaluating the amount of moisture inside an energy storage device. One of the objectives is to provide a solution. Alternatively, one aspect of the present invention relates to the inner casing of an energy storage device. One of the objectives is to provide a method for evaluating the moisture content of a part.

[0011] Alternatively, one aspect of the present invention aims to provide a power storage device with a novel structure. Alternatively, one aspect of the present invention relates to a novel energy storage device, an electronic device equipped with a novel energy storage device, etc. One of the challenges is to provide it.

[0012] Furthermore, the description of these problems does not preclude the existence of other problems. One approach does not necessarily need to solve all of these problems. The title will become clear from the description in the specification, drawings, claims, etc. It is possible to extract other issues from the descriptions in the drawings, claims, etc. [Means for solving the problem]

[0013] One aspect of the present invention comprises a film, a positive electrode and a negative electrode, wherein the maximum surface height of the film The difference between the height and the minimum height is between 0.15 mm and 0.8 mm, and the film's rigidity ratio is 6. 5 x 10 9 The film is smaller than N, has a metal layer, and the thickness of the metal layer is 5 μm or more. The device has a thickness of 0 μm or less, and the positive and negative electrodes are encased in film. The film, for example, has multiple protrusions.

[0014] Alternatively, one aspect of the present invention comprises a film, a positive electrode and a negative electrode, and the film, from the upper surface The ratio of surface area to observed area is between 1.005 and 10, and the film has a metal layer. Furthermore, the thickness of the metal layer is 5 μm or more and 200 μm or less, and the positive and negative electrodes are made of film. It is a more enclosed energy storage device.

[0015] Furthermore, in the above configuration, the distortion at the film's breaking point is greater than 0.6 and less than or equal to 2. It is preferable that the metal layer has aluminum. preferable.

[0016] Alternatively, one aspect of the present invention is an energy storage device having an outer casing, a positive electrode and a negative electrode, and the outer casing It has a first region and a second region, and the stiffness of the first region is 1 / 2 of the stiffness of the second region. It is an energy storage device with a capacity of 0.2 times or more and 0.4 times or less.

[0017] Alternatively, one aspect of the present invention is an energy storage device having an outer casing, a positive electrode and a negative electrode, and the outer casing It has a first region and a second region, and in the first region and the second region, one Let H be the difference between the maximum and minimum heights of the surface as viewed from the direction, and the value of H in the first region is the second This is an energy storage device whose H value in the specified region is between 2 and 5 times the value of H.

[0018] Furthermore, in the above configuration, the energy storage device is repeatedly bent, and the second region is different from the first region. It is preferable to have a region that is closer to the end of the outer casing. Also, in the above configuration, The curve is repeatedly bent, and the radius of curvature of the first region is smaller than the radius of curvature of the second region. It is preferable that it has a region. [Effects of the Invention]

[0019] According to one aspect of the present invention, a power storage device that can be repeatedly bent can be provided. Furthermore, according to one aspect of the present invention, a highly reliable energy storage device can be provided. According to one aspect of the present invention, a long-life energy storage device can be provided. Depending on the embodiment, it is possible to provide electronic devices that can be repeatedly bent. In one embodiment, a flexible electronic device can be provided.

[0020] Furthermore, according to one aspect of the present invention, a flexible film can be provided. According to one aspect of the present invention, a film that can be repeatedly bent can be provided. .

[0021] Furthermore, according to one aspect of the present invention, a method for evaluating the reliability of an energy storage device can be provided. Furthermore, according to one aspect of the present invention, a method for evaluating the amount of impurities inside an energy storage device can be provided. To be able to. Furthermore, according to one aspect of the present invention, a method for evaluating the amount of moisture inside an energy storage device is provided. This is possible. Furthermore, according to one aspect of the present invention, the amount of moisture inside the outer casing of a power storage device can be evaluated. We can provide a method.

[0022] Furthermore, according to one aspect of the present invention, a novel energy storage device with a new structure can be provided. According to one aspect of the present invention, a novel energy storage device, an electronic device equipped with the novel energy storage device, and the like are provided. It is possible.

[0023] Furthermore, the description of these effects does not preclude the existence of other effects. One embodiment does not necessarily have to possess all of these effects. Furthermore, other effects may be considered. This will become clear from the description in the specification, drawings, claims, etc., and the specification, drawings It is possible to extract effects other than those mentioned above from the descriptions in the surfaces, claims, etc. [Brief explanation of the drawing]

[0024] [Figure 1] A diagram illustrating the cross-section of the film. [Figure 2] A diagram illustrating the cross-section of the film. [Figure 3] A diagram illustrating the cross-section of the film. [Figure 4] A diagram illustrating the top surface of the film. [Figure 5] A diagram illustrating the top surface of the film. [Figure 6] A diagram illustrating the top surface of the film. [Figure 7] A diagram illustrating the top surface of the film. [Figure 8] Film test results. [Figure 9] Film test results. [Figure 10] A diagram illustrating an energy storage device. [Figure 11] A diagram illustrating a cross-section of an energy storage device. [Figure 12] A diagram illustrating the method for manufacturing an energy storage device. [Figure 13] A diagram illustrating the method for manufacturing an energy storage device. [Figure 14] A diagram illustrating an energy storage device. [Figure 15] A diagram illustrating the radius of curvature of a surface. [Figure 16] A diagram illustrating the radius of curvature of film. [Figure 17] A diagram illustrating a cross-section of an energy storage device. [Figure 18] A diagram illustrating a cross-section of an energy storage device. [Figure 19] A diagram illustrating a cross-section of an energy storage device. [Figure 20] A diagram illustrating the top view and cross-section of an energy storage device. [Figure 21] A diagram illustrating the top view and cross-section of an energy storage device. [Figure 22] A diagram illustrating the top view and cross-section of an energy storage device. [Figure 23] A diagram illustrating the top view and cross-section of an energy storage device. [Figure 24] A diagram illustrating a cross-section of an energy storage device. [Figure 25] A diagram illustrating a cross-section of an energy storage device. [Figure 26] A diagram illustrating a cross-section of an energy storage device. [Figure 27] A diagram illustrating a cross-section of an energy storage device. [Figure 28] Diagram illustrating the cross-section of an electronic device and a film. [Figure 29] A cross-sectional view showing one embodiment of the manufacturing method of the present invention. [Figure 30] A cross-sectional view showing one embodiment of the manufacturing method of the present invention. [Figure 31] A cross-sectional view showing one embodiment of the manufacturing method of the present invention. [Figure 32] A diagram illustrating the cross-section of a particle. [Figure 33] A diagram illustrating the cross-section of an electrode. [Figure 34] A diagram illustrating an example of an energy storage device. [Figure 35] A diagram illustrating an example of an energy storage device. [Figure 36] A diagram illustrating an example of an energy storage device. [Figure 37] A diagram illustrating an example of an energy storage device. [Figure 38] A diagram illustrating an example of an energy storage device. [Figure 39]A diagram illustrating an example of an electronic device. [Figure 40] A diagram illustrating an example of an electronic device. [Figure 41] A diagram illustrating an example of an electronic device. [Figure 42] A diagram illustrating an example of an electronic device. [Figure 43] A block diagram illustrating one aspect of the present invention. [Figure 44] A conceptual diagram illustrating one aspect of the present invention. [Figure 45] A circuit diagram illustrating one aspect of the present invention. [Figure 46] A circuit diagram illustrating one aspect of the present invention. [Figure 47] A conceptual diagram illustrating one aspect of the present invention. [Figure 48] A block diagram illustrating one aspect of the present invention. [Figure 49] A flowchart illustrating one aspect of the present invention. [Figure 50] A diagram showing the results of moisture content measurement. [Modes for carrying out the invention]

[0025] Embodiments of the present invention will be described in detail below with reference to the drawings. However, the present invention Not limited to these descriptions, the form and details can be varied in various ways, as any person skilled in the art would know. This is easily understood. Therefore, the present invention is interpreted to be limited to the contents of the embodiments described below. It is not something that should be done.

[0026] In addition, in each figure described herein, the size of each element such as film, layer, substrate, and region is not shown. Thickness and other specifications may be exaggerated for the sake of clarity in individual descriptions. Therefore, they may not necessarily reflect the actual quantities. The size of the constituent elements is not limited to their own size, nor is it limited to the relative size between each constituent element. stomach.

[0027] In this specification, the ordinal numbers such as "1st," "2nd," etc., are used for convenience. This does not indicate the order of processes or the order of layering. For example, "1 The word "no" can be replaced with "the second" or "the third" as appropriate in the explanation. Ordinal numbers described in the specification, etc., and ordinal numbers used to specify one aspect of the present invention They may not match.

[0028] Furthermore, in the configuration of the present invention described herein, etc., the same part or similar function The same reference numerals are used consistently across different drawings for certain parts, and explanations of their repetition are omitted. Furthermore, when referring to parts with similar functions, the hatch pattern is the same, and a special designation is given. There are cases where this does not happen.

[0029] In this specification, both the positive and negative electrodes for an energy storage device are collectively referred to as electrodes. However, in this case, the electrodes shall indicate at least one of the positive and negative electrodes. ru.

[0030] Here, we will explain the charging and discharging rates of an energy storage device. For example, capacity X[ When charging a secondary battery with a constant current, a charging rate of 1C means that charging will be completed in exactly one hour. This refers to the current value I[A] at which charging is complete, and a charging rate of 0.2C is I / 5[A] (that is, This refers to the current value at which charging is completed in exactly 5 hours. Similarly, the discharge rate is 1C and This refers to the current value I[A] at which discharge ends in exactly one hour, and the discharge rate is 0.2C. This refers to I / 5[A] (i.e., the current value at which discharge ends in exactly 5 hours). .

[0031] (Embodiment 1) This embodiment describes an energy storage device according to one aspect of the present invention and the exterior body of the energy storage device. I will reveal it.

[0032] One example of an energy storage device is a secondary battery that uses electrochemical reactions, such as a lithium-ion battery. Examples of energy storage devices include electric double-layer capacitors and redox capacitors. Examples include electrochemical capacitors, air batteries, and fuel cells.

[0033] In one embodiment of the present invention, it is preferable that the energy storage device can be repeatedly charged and discharged.

[0034] When charging and discharging an energy storage device, the electrolyte may decompose at the reaction potential of the electrodes. Yes. The decomposition reaction of the electrolyte is often an irreversible reaction. Therefore, the charging and discharging efficiency of the energy storage device This can reduce the efficiency. A decrease in charge / discharge efficiency can reduce the discharge capacity of the energy storage device. I'll have diarrhea.

[0035] Furthermore, due to the decomposition reaction of the electrolyte, the discharge capacity gradually decreases with repeated charging and discharging. There is a match.

[0036] By using a non-aqueous electrolyte as the electrolyte for the energy storage device, the range of potential in which the energy storage device operates can be increased. In some cases, the range can be widened. For example, over a wider range of potentials, the electrolyte Decomposition can be suppressed. Therefore, the discharge capacity of the energy storage device can be increased.

[0037] An energy storage device according to one aspect of the present invention comprises an outer casing, electrodes located inside the outer casing, and a non-aqueous electrolyte. It is preferable that it has the following:

[0038] <Exterior> An exterior body according to one aspect of the present invention will be described below.

[0039] When impurities enter the interior of the outer casing of the energy storage device, the characteristics of the energy storage device deteriorate. This can occur. For example, if impurities such as water are mixed into a non-aqueous electrolyte, the discharge capacity may decrease. For example, if the airtightness of the casing of the energy storage device is poor, components from the atmosphere may mix into the casing. As a result, impurities may be introduced into the energy storage device.

[0040] Here, in the energy storage device, the concentration of moisture inside the outer casing is determined by the energy storage device and the outer casing. The electrolyte concentration is preferably 300 ppm or less per unit weight, and 100 ppm is preferable. Less than pm is more preferable, 50 ppm or less is even more preferable, and 20 ppm or less is even more preferable. It seems so.

[0041] In an energy storage device, the amount of moisture inside the outer casing is, for example, Karl Fischer moisture. It can be measured using a measuring instrument or similar device.

[0042] The exterior material is preferably made of a material with low impurity permeability. In particular, a material with low moisture permeability is preferable. It is preferable that it contains a material. For example, it is preferable that it contains a metal.

[0043] An outer casing of an energy storage device according to one aspect of the present invention is a film (referred to as a sheet or foil). It is preferable to use (in some cases).

[0044] An exterior body according to one aspect of the present invention is made of aluminum, copper, tin, niobium, titanium, nickel, and monoxide. At least one of the metals selected from gunmetal, iron, molybdenum, tungsten, tantalum, chromium, etc. It is preferable to have one of these. Furthermore, alloys of these metals may be present. For example, ste It may have stainless steel. Furthermore, the exterior may have a metal layer containing these metals or alloys. It is preferable that aluminum, copper, tin, niobium, titanium, etc. have a small Young's modulus. Furthermore, it can be easy to process. Also, aluminum is inexpensive and easy to process, and externally This is a particularly preferred metal for the mounting.

[0045] Here, the thickness of the metal layer is, for example, 5 μm to 200 μm, or 10 μm to 100 μm. The size is less than or equal to μm, or between 15 μm and 50 μm.

[0046] Alternatively, the exterior body according to one embodiment of the present invention may have a carbon sheet. For example, a film having graphite, carbon fiber, activated carbon, graphene, graphene compounds, etc. It can be listed.

[0047] Furthermore, the exterior body of one embodiment of the present invention preferably has a resin. It may be in a lumpy form. For example, the resin can be polyethylene, polypropylene, or polycarbonate. Materials such as ionomers, polyamides, etc., can be used.

[0048] Furthermore, in order to prevent short circuits between the electrodes of the energy storage device and the outer casing, the electrical conductivity of the outer casing surface Low conductivity is preferable. Therefore, it is preferable that the outer casing has a resin layer or the like on its surface. For example, a film having resin layers on both sides of a metal layer can be used as the outer casing. Cut.

[0049] For example, an exterior body according to one aspect of the present invention is a film having the metal or the alloy, A resin layer may be provided on at least one of the front and back surfaces.

[0050] For example, as an exterior material, metal film (aluminum, stainless steel, copper, etc.), organic material Plastic film made of organic materials (organic resins and fibers, etc.) and inorganic materials (ceramics) Hybrid material films containing (such as) carbon-containing inorganic films (carbon films) A single-layer film selected from, for example, graphite film, or a combination of these. A laminated film is used.

[0051] Furthermore, when using a metal film, the inner surface should be insulated with, for example, polypropylene. Materials such as pyrene, polyethylene, polycarbonate, ionomer, and polyamide are used for coating. Furthermore, an insulating synthetic resin film, such as a polyamide resin or polyester resin, is provided on the outer surface. A three-layer film structure is preferable. Alternatively, polyethylene terephthalate can be used as the resin film. (PET) resin or the like may be used. A metal film may be coated with two or more laminated films. For example, the inner surface is coated with a material such as polypropylene, and the outer surface is coated with a polyamide resin and polyethylene It may also be coated with a film made of laminated ethylene terephthalate (PET) or the like. Here, for example, resin The film thickness is 10 μm to 200 μm, or 15 μm to 100 μm.

[0052] An energy storage device according to one aspect of the present invention deforms in accordance with the deformation of the equipment on which the energy storage device is mounted. It is possible.

[0053] A power storage device according to one aspect of the present invention is bendable. A bendable power storage device is It can be mounted on deformable devices, such as electronic devices like wearable devices. When attaching it to or while wearing it, the wearable device may deform, causing... This can improve the wearability of wearable devices.

[0054] Wearable devices and other electronic devices are repeatedly attached to and removed from the human body. Preferably, the energy storage device according to one aspect of the present invention can be repeatedly bent. This is preferable.

[0055] By bending the energy storage device, the outer casing deforms. The deformation of the outer casing is caused by a turtle shell in part of the outer casing. This can cause phenomena such as cracks forming or parts of the exterior being stretched and thinned. This occurs. As a result of this phenomenon, the permeability of impurities in the outer casing increases. Therefore, impurities from the atmosphere, such as moisture, can easily enter the interior of the outer casing.

[0056] The outer casing of a power storage device according to one aspect of the present invention is impure when the power storage device is repeatedly bent. It can suppress the increase in the permeability of materials.

[0057] Here, repeated bending means, for example, repeatedly switching between a state with a large radius of curvature and a state with a small radius of curvature. The point is that when bending an energy storage device, the smaller the radius of curvature, the greater the deformation of the outer casing, and turtle Cracks and other damage are more likely to occur.

[0058] When bending an energy storage device, the deformation of the outer casing may be large in localized areas. For example, localized deflection may occur in the exterior body. Localized deflection is This is a cause of wrinkle formation. Wrinkles can also be thought of as regions with an extremely small radius of curvature. When the device is repeatedly bent, cracks and other damage may be more likely to occur in the wrinkled areas. .

[0059] Therefore, it is preferable that the outer casing of the energy storage device according to one aspect of the present invention is less prone to bending. It's nice.

[0060] Examples of films that can be used as exterior components are described below.

[0061] To suppress film warping, for example, one can increase the thickness of the film.

[0062] Alternatively, bending can be suppressed by processing the film. For example, To achieve this, you can create a raised section on the film. An example of creating a raised section on a film is to emboss the film. Examples include applying a special coating or making the film accordion-shaped.

[0063] Metal films are easy to emboss. Furthermore, embossing can create raised areas. This increases the ratio of the surface area to the surface area of ​​the outer casing exposed to the outside air, for example, the area viewed from the top. Therefore, it has excellent heat dissipation properties. Embossing creates a shape on the surface (or back) of the film. The resulting protrusions form a closed space with a variable volume, where the film is part of the wall of the sealing structure. This can be described as the convex portion of the film forming a bellows-like structure. Furthermore, not only is embossing, a type of press processing, possible for raising the edges of a part of the film (relief Any method that can form (F) is acceptable.

[0064] Next, the cross-sectional shape of the convex portion will be explained using Figures 1 and 2.

[0065] As shown in Figure 1, the film 10 has a convex portion 10a having a vertex in a first direction, Convex portions 10b having their apex in the second direction are arranged alternately. The first direction is on one side of the surface, and the second direction is on the other side of the surface.

[0066] The cross-sectional shapes of the protrusions 10a and 10b are hollow semicircular, hollow semielliptical, hollow polygonal, Alternatively, it can be a hollow, irregular shape. Note that in the case of a hollow polygon, it will have more angles than a hexagon. Having this feature makes it possible to reduce stress concentration at the corners, which is preferable.

[0067] Figure 1 shows the depth of the protrusion 10a 351, the pitch of the protrusion 10a 352, and the depth of the protrusion 10b 3 53, distance between protrusions 10a and 10b 354, film thickness of film 10 355, protrusion The bottom thickness of 10a is 356. Here, the height 357 is the maximum height of the film surface. This is the difference between that and the minimum height.

[0068] Next, various examples of the film 10 having the protrusion 10a are shown in Figures 2(A) to (F).

[0069] Furthermore, various examples of the film 10 having the protrusions 10a and 10b are shown in Figure 3(A) to (D) is shown.

[0070] Next, the shape of the upper surface of the protrusion will be explained using Figures 4 to 7.

[0071] The film shown in Figure 4(A) has regularly arranged convex portions 10a, each having a vertex on one side. Here, the dashed line e1, which indicates the direction in which the convex portions 10a are aligned, is oblique to the edge of the film. It is.

[0072] The film shown in Figure 4(B) has regularly arranged convex portions 10a, each having a vertex on one side. Here, the dashed line e1, which indicates the direction in which the convex portions 10a are aligned, is relative to the long side of the film. They are parallel.

[0073] The film shown in Figure 5(A) has a convex portion 10a with a top on one side and on the other side The convex portions 10b, each having a vertex, are arranged in a regular pattern. Here, the direction in which the convex portions 10a are aligned. The dashed line e1, which indicates the direction in which the convex portions 10b are aligned, and the dashed line e2, which indicates the direction in which the convex portions 10b are aligned, are oblique to the edge of the film. Yes, and dashed lines e1 and e2 intersect.

[0074] The film shown in Figure 5(B) has a convex portion 10a with a top on one side and on the other side The convex portions 10b, each having a vertex, are arranged in a regular pattern. Here, the direction in which the convex portions 10a are aligned. The dashed line e1, which indicates the direction in which the convex portion 10b is aligned, and the dashed line e2, which indicates the direction in which the convex portion 10b is aligned, are parallel to the long side of the film. It is a row.

[0075] The film shown in Figure 5(C) has a convex portion 10a with a top on one side and on the other side The convex portions 10b, each having a vertex, are arranged in a regular pattern. Here, the direction in which the convex portions 10a are aligned. The dashed line e1, which indicates the direction in which the convex portion 10b is aligned, and the dashed line e2, which indicates the direction in which the convex portion 10b is aligned, are parallel to the short side of the film. It is a row.

[0076] The film shown in Figure 5(D) has a convex portion 10a with a top on one side and on the other side The protrusions 10b, each having a vertex, are arranged irregularly.

[0077] Note that while the top surface shape of each convex portion shown in Figure 5 is circular, it does not have to be circular. For example, it can be a polygon or an irregular shape.

[0078] Furthermore, as shown in the film in Figure 5, there is a convex portion 10a with a top on one side and the other side The convex portion 10b, which has its apex on the surface side, may have the same upper surface shape. Alternatively, as shown in Figure 6 ( As shown in A), a convex portion 10a having a vertex on one side and a portion having a vertex on the other side The upper surface shapes of the protrusions 10b may be different from each other.

[0079] In the film shown in Figure 6(A), the upper surface shape of the protrusion 10a is linear, and the protrusion 10 The upper surface shape of b is circular. The upper surface shape of the convex portion 10a can be linear, curved, wavy, It may be zigzag or irregular in shape. Also, the upper surface shape of the convex portion 10b may be polygonal or irregular. It's okay to have it.

[0080] Alternatively, as shown in Figure 6(B), the upper surface shape of the protrusions 10a and 10b is cross-shaped. That's good too.

[0081] The top surface shape shown in Figures 5 and 6 provides stress to bending in at least two directions. This can alleviate the problem.

[0082] Furthermore, Figure 7 shows an example where the upper surface shape of the convex portion is linear. Note that the shape shown in Figure 7 is called a bellows structure. It may be called as follows. As a cross-section along the dashed line e3 shown in Figures 7(A) to (D), see Figures 1 to Figure Option 3 can be applied.

[0083] The film shown in Figure 7(A) has linear protrusions 10a arranged on one side, with the top portion on one side. Here, the dashed line e1 indicating the direction of the linear protrusion 10a is relative to the edge of the film. They are parallel. Also, the film shown in Figure 7(B) has a linear convex portion with its apex on one side. 10a and linear protrusions 10b having their apex on the other side are arranged alternately. Next, there is the dashed line e1 indicating the direction of the linear protrusion 10a, and the dashed line e indicating the direction of the linear protrusion 10b. 2 is parallel to the edge of the film.

[0084] The film shown in Figure 7(C) has linear protrusions 10a arranged on one side, with the top portion on one side. Here, the dashed line e1 indicating the direction of the linear protrusion 10a is relative to the edge of the film. It is slanted. Also, the film shown in Figure 7(D) has a linear convex portion with its apex on one side. 10a and linear protrusions 10b having their apex on the other side are arranged alternately. Next, there is the dashed line e1 indicating the direction of the linear protrusion 10a, and the dashed line e indicating the direction of the linear protrusion 10b. 2 is oblique to the edge of the film.

[0085] An exterior body according to one aspect of the present invention has a plurality of protrusions, the depth of which is preferably 1 mm or less. More preferably 0.15 mm or more and less than 0.8 mm, even more preferably 0.3 mm or more It is 0.7 mm or less.

[0086] Furthermore, the density of protrusions per unit area is, for example, 0.02 pieces / mm². 2 More than 2 pieces / mm 2 The following is good Mashiku, 0.05 pieces / mm 2 More than 1 piece / mm 2 The following is more preferable: 0.1 pieces / mm 2 Below Upper 0.5 pieces / mm 2 The following are even more preferable.

[0087] Here, let R be the ratio of the surface area to the area viewed from above. Let R be shown in the diagram. Let me explain. In the region 11 enclosed by the dashed line in Figure 5(A), the area viewed from above is: This is the area in the top view of Figure 5(A). Here, the top view shows the film 10 in an approximately vertical direction. A view from the top is preferred. If the area viewed from the top is J1 and the surface area is J2, then R This can be expressed as =J2 / J1.

[0088] Here, R is preferably between 1.005 and 10, and between 1.015 and 5. Preferably, it is greater than 1.05 and more preferably 3 or less, and even more preferably 1.1 or more and 2 or less. It is preferable that it is greater than 1.08 and less than 1.7, and greater than 1.1. A value less than 1.4 is even more preferable.

[0089] Here, the surface area of ​​the film is, for example, measured by a scanning probe microscope (SPM), more specifically, For example, evaluation can be performed using AFM, DFM, etc. Alternatively, for example, a confocal laser microscope, etc. Use and evaluate.

[0090] <Buckling load> Here, the load at which buckling occurs is called the buckling load. By increasing the buckling load, the film This makes it less likely to bend or sag. It also makes it less likely for wrinkles to form in the film.

[0091] On the other hand, if the buckling load is too high, the film becomes difficult to deform, and when bending stress is applied, The film becomes more prone to cracks and other damage.

[0092] When bending a film, the presence of convex portions in the film results in a difference compared to a flat film. This allows for a higher buckling load. Also, the R=J2 / J1 of the film can be increased. This can sometimes result in a higher buckling load compared to a flat film.

[0093] <rigidity> Furthermore, when the energy storage device is repeatedly bent, for example, tensile and compressive stresses can be applied to the outer casing. This force is applied. When such a force is applied, a crack may form in a part of the exterior, or the exterior may... This may cause phenomena such as parts of the device being pulled and becoming thinner.

[0094] Therefore, it is preferable that the exterior body of one aspect of the present invention is easily expandable and contractible. This reduces the force applied to the exterior and suppresses cracks and other damage to the exterior.

[0095] By lowering the rigidity of an object, it becomes easier to stretch and contract. Using materials with a low Young's modulus... This allows for a reduction in rigidity.

[0096] Furthermore, the rigidity can be reduced by processing the film. For example, the convex part It is sufficient to provide this. Also, if the rigidity can be reduced by providing slits or the like in the film, There is a protrusion on the film, which allows the exterior body to be formed per unit area when viewed from above. The ratio of surface areas increases.

[0097] The rigidity of the film is determined by the film's resistance to the applied force while it is being pulled. This is obtained by measuring the elongation. This type of measurement is sometimes called a tensile test. Let k be the stiffness of the film, P be the force in the tensile test, and δ be the displacement. k, P, and δ are given by a number. The relationship is expressed in equation (1). Therefore, P and δ are measured by a tensile test of the film. By doing so, the stiffness k of the film can be determined.

[0098]

number

[0099] Let L be the length, W the width, and A the cross-sectional area of ​​the sample. The strain ε is expressed by equation (2). Stress σ is expressed by equation (3).

[0100]

number

[0101]

number

[0102] The value G defined in equation (4) is sometimes called the stiffness modulus.

[0103]

number

[0104] Also, the value obtained by multiplying the stiffness modulus G by the thickness of the sample (or multiplying the stiffness k by the length of the sample and dividing by the width of the sample) Let the value obtained be the parameter G'. Here, G' is expressed by equation (5).

[0105]

number

[0106] Here, let E be the ratio of stress σ to strain ε. E can be expressed by equation (6).

[0107]

number

[0108] Substituting equations (1) through (3) into equation (6), E can be expressed by equation (7). Therefore, in this case, E is equal to the shear modulus G.

[0109]

number

[0110] Since E and G are equal, and from equation (6), G, σ, and ε satisfy equation (8).

[0111]

number

[0112] <Tensile Test> The following is an example of determining k from a tensile test of a film.

[0113] Samples A1 to A3 and comparative sample C1 were prepared. In all samples, the metal layer The front and back surfaces are coated with a resin layer.

[0114] Samples A1 to A3 have been embossed. Here, the area viewed from the top surface is The ratio of surface area is larger for sample A2 than for sample A1, and larger for sample A3 than for sample A2. It's been processed to achieve that.

[0115] Each sample was cut into roughly rectangular pieces with a width W of 15 mm and a length L of 100 mm. Here, the length L For example, in a rectangle, this refers to the length of a side that is roughly parallel to the direction of tension.

[0116] Of the 100mm length, the first jig is used to fix the first 25mm from one end to the other. Then, the other end is fixed with the second jig up to 25 mm. Between the first jig and the second jig The distance was set to 50mm.

[0117] The first jig was pulled at a speed of 10 mm / min, applying a tensile stress. The applied force was 5 N. The point where this occurred was designated as the starting position for measurement. The strain in response to the applied force was measured.

[0118] The measurement results for comparative sample C1 and sample A1 are shown in Figure 8(A), and the measurement results for sample A2 and A3 are shown in Figure 8(A). The results are shown in Figure 8(B). In Figures 8(A) and (B), the horizontal axis represents strain ε and the vertical axis represents force P. This shows that the displacement (change) δ is the change in length due to the tensile test. The strain ε is given by equation (2). It is expressed as follows: Here, L is the length before tension.

[0119]

number

[0120] When Equation (8) is transformed here, Equation (9) is obtained. Also, when both sides of Equation (9) are multiplied by the cross-sectional area A, Equation (10) is obtained from the relationship with Equation (3). Therefore, the shear modulus G can be obtained as the slope when the horizontal axis is ε and the vertical axis is the stress σ (that is, the value obtained by dividing the slope of the straight line when the horizontal axis is ε and the vertical axis is the force P by the cross-sectional area). Also, from the relationships of Equation (1) and Equation (2), Equation (11) is obtained. Therefore, the value obtained by dividing the slope of the straight line when the horizontal axis is ε and the vertical axis is the force P by L is the stiffness k. Also, from the relationships of Equation (1) and Equation (2), Equation (11) is obtained. Therefore, the value obtained by dividing the slope of the straight line when the horizontal axis is ε and the vertical axis is the force P by L is the stiffness k.

[0121]

Number

[0122]

Number

[0123]

Number

[0124] An enlarged view of the range where the strain ε is 0.002 or less is shown in FIG. 9. In the range where the strain ε is 0 or more and 0.002 or less, an approximation was performed using a linear equation to obtain the slope. The determination coefficient R obtained in the approximation was 0.96 to 0.97. For each sample, G’ and k obtained from the slope values are shown in Table 1. determination coefficient R 2 was 0.96 to 0.97. For each sample, G’ and k obtained from the slope values are shown in Table 1. G’ and k are shown in Table 1.

[0125]

Table 1

[0126] As shown in Table 1, the greater the ratio of the surface area to the area seen from the top surface, the higher the stiffness and the stiffness The rate is low. Here, the sample thicknesses of Samples A1 to A3 are the thickness before embossing, or the thickness of the embossed convex part after processing, or the thickness of the region between the convex parts. Here as an example, the thickness was calculated as the thickness of the film before processing. The cross-sectional area was calculated as the product of the sample width and the sample thickness.

[0127] The exterior body of the power storage device according to one aspect of the present invention is, for example, compared to the reference sample C1 without processing such as providing convex parts, preferably the rigidity, the elastic modulus, and the parameter G' are less than 0.9 times, more preferably not less than 0.5 times and less than 0.9 times, still more preferably not less than 0.6 times and less than 0.8 times is.

[0128] Also, the elastic modulus of the exterior body of the power storage device is, for example, preferably 6.5×10 9 N / m 2 or smaller, more preferably 6.3×10 9 N or less, still more preferably 4.0×10 9 N or more and 5.7×10 9 N or less. The parameter G' of the exterior body of the power storage device is, for example, preferably 9.9×10 5 N / m 2 smaller, more preferably 9.6×10 5 N or less, still more preferably 6.1×10 5 N or more and 8.7×10 5 N or less.

[0129] <Breaking point> Here, in the results of the tensile test shown in FIG. 8, a state where the force rapidly decreases in the tensile test is observed.

[0130] From the results of the tensile test shown in FIG. 8, the approximate values of the strain ε and the force P at the point where the force rapidly decreases are shown in Table 2. <000­0960>

[0131]

Table 2

[0132] In the case where the force rapidly decreases in this way, cracks or other breaks may occur in the film. In such a case, this point is called a break point. Here, by providing convex portions or the like on the film, for example, in the plane of the film, there may be a region where force is likely to concentrate locally. The ease of this concentration may depend on, for example, the depth and interval of the convex portion. Also, by providing convex portions or the like, there may be a region where the film becomes thinner. In these regions, cracks or the like are particularly likely to occur, so they tend to be factors causing breakage. That is, by providing convex portions or the like on the film, breakage of the film may become more likely to occur.

[0133] From Table 2, in Samples A1 and A2, the force at the break point was 0.139 or more, and the strain ε was 0.7 or more, and values almost equivalent to those of Comparative Sample 1 (without embossing) were obtained. However, in Sample A3, the force at the break point was 0.133 and the strain was 0.43, resulting in values lower than those of Comparative Sample 1.

[0134] In Sample A3, the ratio of the surface area to the area seen from the top surface is large, and for example, there may be a location where tensile stress on the film tends to concentrate.

[0135] The exterior body of the power storage device according to one aspect of the present invention has, for example, a strain ε at the break point of 0.6 or more, or greater than 0.6 and 2 or less.

[0136] <Graphene compound> A graphene compound according to one embodiment of the present invention will be described below.

[0137] Graphene is a material in which carbon atoms are arranged in a single atomic layer and have π bonds between the carbon atoms. A material in which two to 100 layers of graphene are stacked is sometimes called multigraphene. Graphene and multigraphene, for example, along the longitudinal direction or the long axis in a plane. The length is 50 nm to 100 μm or 800 nm to 50 μm.

[0138] In this specification, etc., compounds having graphene or multigraphene as a basic framework The substance is called "graphene compound". It is also called "nd"). Graphene compounds include graphene and multigraphene. nothing.

[0139] The following provides a detailed explanation of graphene compounds.

[0140] Graphene compounds, for example, include graphene or multigraphene, which contain atoms other than carbon. Alternatively, it is a compound modified with an atomic group containing atoms other than carbon. Also, graphene or Multigraphene is modified with carbon-based atomic groups such as alkyl groups and alkylenes. It may also be a compound. Furthermore, the atomic group that modifies graphene or multigraphene is These may be referred to as substituents, functional groups, or characteristic groups. Hereinafter, modifications are defined as follows: Graphene, multigraphene, and Graphene are produced by substitution, addition, or other reactions. Graphene compounds, or graphene oxide (described later), containing atoms other than carbon, or other atoms other than carbon. This refers to the introduction of an atomic group containing atoms, or an atomic group mainly composed of carbon.

[0141] Furthermore, the front and back surfaces of graphene are modified by different atoms or groups of atoms. It is acceptable. Also, in multigraphene, each layer contains different atoms or groups of atoms. It may be modified.

[0142] As an example of graphene modified with the above-mentioned atoms or groups of atoms, oxygen or oxygen Examples include graphene or multigraphene modified with functional groups containing oxygen. Examples of functional groups it contains include epoxy groups, carbonyl groups such as carboxyl groups, or hydroxyl groups. Examples include groups such as oxygen or functional groups containing oxygen. It is sometimes called graphene oxide. In this specification, graphene oxide is multilayer This also includes graphene oxide.

[0143] By introducing specific atomic groups into graphene compounds, the physical properties of the graphene compounds can be altered. Therefore, it is possible to perform the desired modifications on the graphene compound according to its intended use. This allows for the intentional expression of desired properties in graphene compounds.

[0144] Next, an example of a method for producing graphene oxide will be described. Graphene oxide is produced by the above graph It can be obtained by oxidizing graphene or multigraphene. Alternatively, graphene oxide can be obtained by acid Graphite oxide can be obtained by separating graphite. Graphite oxide is obtained by oxidizing graphite. This can be obtained by further adding the aforementioned atoms or groups of atoms to graphene oxide. You can display it.

[0145] The compound obtained by reducing graphene oxide is called "RGO (Reduced Graph)". It is sometimes called "graphene Oxide". Note that RGO contains graphene oxide. Not all of the oxygen is eliminated; some oxygen or oxygen-containing atomic groups remain bonded together. In some cases, RGO may be an epoxy group, a carboxyl group or other carbonyl group, It may have functional groups such as hydroxyl groups.

[0146] Graphene compounds are formed in the form of a single sheet, with multiple graphene compounds partially overlapping. It may be as follows. Such graphene compounds are sometimes called graphene compound sheets. There is a compatibility. For example, graphene compound sheets have a thickness of 0.33 nm to 10 mm. Preferably, the region is greater than 0.34 nm and less than or equal to 10 μm. Graphene compound A group of atoms other than carbon, a group of atoms containing atoms other than carbon, or a group of atoms such as alkyl groups containing carbon It may be modified with a main group of atoms, etc. Also, the graphene compound sheet has Each of the multiple layers may be modified with different atoms or groups of atoms.

[0147] Graphene compounds include not only six-membered rings composed of carbon, but also five-membered rings composed of carbon, and carbon It may have multi-membered rings of seven or more members composed of elements. Here, the neighborhood of multi-membered rings of seven or more members In this case, a region may be created through which lithium ions can pass.

[0148] Alternatively, for example, multiple graphene compounds may be aggregated to form a sheet-like structure. Graphene compounds have a planar shape, which allows for surface contact.

[0149] Graphene compounds can have high conductivity even when thin, and graphene formation occurs through surface contact. This can increase the contact area between the compounds, or between the graphene compound and the active material. Therefore, a conductive path can be efficiently formed even with a small amount per unit volume.

[0150] On the other hand, graphene compounds can also be used as insulators. For example, graphene compounds A sheet of material can be used as a sheet-shaped insulator. For example, graphene oxide. It may have higher insulating properties compared to unoxidized graphene compounds. Also, atomic groups Graphene compounds modified in this way can have their insulating properties enhanced depending on the type of atomic group used for modification. It is sometimes possible.

[0151] Herein, the graphene compound may have a graphene precursor. Graphene precursors are substances used to manufacture graphene. The fen precursor may include, for example, the aforementioned graphene oxide or graphite oxide. stomach.

[0152] Furthermore, graphene containing alkali metals, and graphene containing elements other than carbon such as oxygen In some cases, graphene analogs are used to refer to graphene compounds. In this specification, graphene compounds include: This also includes graphene analogs.

[0153] Furthermore, the graphene compounds described herein contain atoms, groups of atoms, and their interlayers. It may contain ions. Furthermore, the graphene compound may contain atoms, atomic groups, and their interlayers. The presence of ions alters the physical properties of graphene compounds, such as electrical conductivity and ionic conductivity. This may change. Also, the interlayer distance may increase.

[0154] Graphene compounds possess excellent electrical properties, including high conductivity, and high flexibility. It may possess excellent physical properties such as high mechanical strength. Depending on the type of modification, the compound can be made to have extremely low conductivity and act as an insulator. There is also a planar shape. Graphene compounds have a contact resistance. Enables low-resistance surface contact.

[0155] This embodiment can be implemented in appropriate combination with other embodiments.

[0156] (Embodiment 2) This embodiment describes an energy storage device according to one aspect of the present invention.

[0157] <Example of an energy storage device: a slim battery> The following is an example of an energy storage device using an exterior body according to one aspect of the present invention.

[0158] Figure 10 shows a thin battery as an example of an energy storage device. The thin battery is flexible. If the configuration is such that it has flexibility, it can be mounted on electronic devices that have at least a portion of a flexible part. If possible, the battery can also be bent to match the deformation of the electronic device.

[0159] Figure 10 shows an external view of the energy storage device 500, which is a thin battery. Also, Figure 11(A) Figure 11(B) shows the A1-A2 and B1-B2 sections, which are indicated by dashed lines in Figure 10. The energy storage device 500 has a positive electrode 503 having a positive electrode current collector 501 and a positive electrode active material layer 502. a negative electrode 506 having a negative electrode current collector 504 and a negative electrode active material layer 505, and a separator 507 It comprises an electrolyte 508 and an outer casing 509. A positive electrode 50 is provided inside the outer casing 509. A separator 507 is installed between 3 and the negative electrode 506. Also, inside the outer casing 509, It is filled with electrolyte solution 508.

[0160] In the example shown in Figure 10, the outer casing 509 has region 509a and region 509b. This is preferable. In the example shown in Figure 10, region 509b is the sealing region of the outer casing 509. It functions. Region 509b seals three sides on the upper surface of the outer casing 509. Outer casing 5 09 can be sealed using, for example, heat.

[0161] The exterior body shown in Embodiment 1 can be used as the exterior body 509.

[0162] Furthermore, as region 509a, one can refer to the description of the exterior body shown in Embodiment 1. Alternatively, as region 509b, one can refer to the description of the exterior body shown in Embodiment 1. ru.

[0163] Furthermore, the sealing structure of the energy storage device is made by folding a single rectangular film in the middle and then folding the two ends... The structure involves overlapping two films and fixing the three sides with an adhesive layer to seal them, or overlapping two films and the film The structure is designed to close off the four edges by fixing them with an adhesive layer.

[0164] The adhesive layer can be a thermoplastic film material, a thermosetting adhesive, an anaerobic adhesive, or an UV-curing adhesive. The materials of these adhesives include light-curing adhesives and reaction-curing adhesives. In terms of materials, epoxy resin, acrylic resin, silicone resin, and phenolic resin are used. It is possible.

[0165] As the solvent for electrolyte 508, an aprotic organic solvent is preferred, for example, ethylene carbonate Carbonate (EC), propylene carbonate (PC), butylene carbonate, chloro Ethylene carbonate, vinylene carbonate, γ-butyrolactone, γ-valerolactone Dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl Carbonate (EMC), methyl formate, methyl acetate, methyl butyrate, 1,3-dioxane, 1,4-Dioxane, dimethoxyethane (DME), dimethyl sulfoxide, diethyl ester methyl diglyme, acetonitrile, benzonitrile, tetrahydrofuran, One of the following, such as ruhoran or sultone, or any combination and ratio of two or more of these. It can be used as a percentage.

[0166] Furthermore, by using a polymer material that gels as the solvent for the electrolyte, leakage properties can be addressed. Safety is enhanced. Furthermore, it becomes possible to make secondary batteries thinner and lighter. The high-molecular-weight components that are gelled... Typical examples of these materials include silicone gel, acrylic gel, acrylonitrile gel, and poly Ethylene oxide gels, polypropylene oxide gels, fluorine polymer gels These include:

[0167] Furthermore, as the solvent for the electrolyte, an ionic liquid (a room-temperature molten salt) that is flame-retardant and non-volatile is used. By using one or more of these devices, the internal temperature of the energy storage device may rise due to internal short circuits or overcharging. However, this can prevent the rupture or ignition of the energy storage device. Ionic liquids are composed of cations and anions. It consists of and contains organic cations and anions. As organic cations used in the electrolyte, four quaternary ammonium cations, tertiary sulfonium cations, and quaternary phosphonium cations Aliphatic onium cations such as imidazolium cations and pyridinium cations, etc. Aromatic cations are an example. In addition, monovalent amides are used as anions in the electrolyte. Anions, monovalent methide anions, fluorosulfonate anions, perfluoroalkyl Anions of tetrafluoroborate, perfluoroalkyl volate Toanions, hexafluorophosphate anions, or perfluoroalkyl phosphates Examples include ether anions.

[0168] Furthermore, when using lithium ions as the carrier, the electrolyte to be dissolved in the above solvent... For example, LiPF6, LiClO4, LiAsF6, LiBF4, LiAlCl4, L iSCN, LiBr, LiI, Li2SO4, Li2B 10 Cl 10 Li2B 12 Cl 12 , LiCF3SO3, LiC4F9SO3, LiC(CF3SO2)3, LiC(C 2F5SO2)3, LiN(CF3SO2)2, LiN(C4F9SO2)(CF3SO 2) One type of lithium salt such as LiN(C2F5SO2)2, or two or more of these. These can be used in any combination and ratio.

[0169] Furthermore, the electrolyte used in the energy storage device may contain particulate debris and elements other than the constituent elements of the electrolyte (hereinafter, It is preferable to use a highly purified electrolyte with a low content of impurities (also simply called "impurities"). Specifically, the weight ratio of impurities to the electrolyte should be 1% or less, preferably 0.1% or less. More preferably, it is 0.01% or less.

[0170] Furthermore, the electrolyte contains vinylene carbonate, propanesultone (PS), and tert-butyl. Addition of benzene (TBB), fluoroethylene carbonate (FEC), LiBOB, etc. Additives may be added. The concentration of the additive should be, for example, 0.1 weight% or less of the total solvent. The upper 5 weight percentage should be less than or equal to 5.

[0171] Alternatively, a gel electrolyte obtained by swelling a polymer with an electrolyte solution may be used.

[0172] Examples of polymers include polyalkylene oxides such as polyethylene oxide (PEO). Polymers having a side structure, PVDF, polyacrylonitrile, etc., and those Copolymers containing the above can be used. For example, PVDF and hexafluoropropylene ( PVDF-HFP, a copolymer of HFP, can be used. The rimer may have a porous structure.

[0173] Furthermore, instead of an electrolyte, a solid electrolyte containing inorganic materials such as sulfide-based or oxide-based materials may be used. Solid electrolytes containing polymer materials such as PEO (polyethylene oxide) can be used. It is possible. When using a solid electrolyte, the installation of separators and spacers becomes unnecessary. Also, Because the entire battery can be made solid, the risk of leakage is eliminated, dramatically improving safety.

[0174] For example, the separator 507 may be paper, nonwoven fabric, glass fiber, ceramics, or Nylon (polyamide), Vinylon (polyvinyl alcohol-based fiber), polyester, A This product uses synthetic fibers made from acrylic, polyolefin, polyurethane, etc. It is possible.

[0175] The separator 507 is processed into a bag shape and encloses either the positive electrode 503 or the negative electrode 506. It is preferable to arrange them in such a way. For example, as shown in Figure 12(A), the positive electrode 503 is sandwiched between them. The separator 507 is folded in half, and the sealing portion 5 is formed outside the area that overlaps with the positive electrode 503. By sealing with 14, the positive electrode 503 can be securely supported within the separator 507. And, as shown in Figure 12(B), the positive electrode 503 enclosed in the separator 507 and the negative electrode By alternately stacking poles 506 and 509 and arranging them inside the outer casing 509, a thin storage battery is created. It is preferable to form a power storage device 500.

[0176] The positive electrode 503 and the negative electrode 506 will be described in detail in the embodiments described later.

[0177] Next, we will explain the aging process after the battery has been manufactured. It is preferable to perform aging. An example of aging conditions is described below. First, Charge at a rate of 0.001C to 0.2C. The temperature should be, for example, above room temperature, 50°C. The temperature should be below °C. Here, the reaction potential of the positive or negative electrode exceeds the range of the potential window of electrolyte 508. In some cases, the electrolyte may decompose due to the charging and discharging of the battery. If more gas is generated, and that gas accumulates inside the cell, the electrolyte will come into contact with the electrode surface. This results in areas where this cannot be done. In other words, the effective reaction area of ​​the electrode decreases, and the effective reaction area This corresponds to an increase in resistance.

[0178] Furthermore, if the resistance becomes excessively high, the potential of the negative electrode decreases, which leads to lithium ionization of the graphite. Simultaneously with the insertion, lithium deposition occurs on the graphite surface. This lithium deposition is This can lead to a decrease in capacity. For example, after lithium is deposited, a film or other substance may grow on the surface. If left untreated, the lithium deposited on the surface cannot be re-dissolved, and lithium that does not contribute to the capacity remains. The amount increases. Also, if the deposited lithium physically collapses and loses conductivity with the electrode... However, lithium that does not contribute to capacity is still produced. Therefore, the negative electrode potential increases, and the charging voltage rises. It is preferable to release the gas before reaching the lithium potential.

[0179] Furthermore, after degassing, the temperature should be higher than room temperature, preferably between 30°C and 60°C. More preferably, at a temperature of 35°C to 50°C, for example, for 1 hour to 100 hours. It may be held in an electrically charged state. During the initial charging, the electrolyte that decomposes on the surface is released onto the graphite surface. A coating is formed. Therefore, for example, by holding it at a temperature higher than room temperature after degassing, It is also possible that the formed coating may become denser.

[0180] Figure 13 shows an example of welding a current collector to a lead electrode. As shown in Figure 13(A), The positive electrode 503 and negative electrode 506, encased in the Parator 507, are stacked alternately. Next, the positive electrode assembly... The current collector 501 is connected to the positive lead electrode 510, and the negative current collector 504 is connected to the negative lead electrode 511, Each component is welded. Figure 13(B) shows an example of welding the positive electrode current collector 501 to the positive electrode lead electrode 510. As shown, the positive electrode current collector 501 is welded in the welding area 512 using ultrasonic welding or the like to form the positive electrode lead electrode. It is welded to 510. The positive electrode current collector 501 also has a curved portion 513 as shown in Figure 13(B). This reduces the stress caused by external forces applied to the energy storage device 500 after its manufacture. This can be done, and the reliability of the energy storage device 500 can be improved. Here, the positive electrode current collector and the negative electrode In current collectors, the area where welding is performed is sometimes called the tab area.

[0181] In the energy storage device 500 shown in Figures 10 and 11, the positive lead electrode 510 and the negative electrode Using the lead electrode 511, the positive electrode current collector 501 or the negative electrode current collector 504 is ultrasonically welded. The positive lead electrode 510 and the negative lead electrode 511 are exposed to the outside. The positive electrode current collector 501 and the negative electrode current collector 504 serve the dual role of terminals that provide electrical contact. It is also possible to do this without using lead electrodes, with a positive electrode current collector 501 and a negative electrode current collector 5 A portion of 04 may be positioned so as to be exposed to the outside from the outer casing 509.

[0182] Also, in Figure 10, the positive lead electrode 510 and the negative lead electrode 511 are arranged on the same side. However, as shown in Figure 14, the positive lead electrode 510 and the negative lead electrode 511 are on different sides. They may be arranged as follows. Thus, in one aspect of the present invention, the storage battery allows the lead electrodes to be freely arranged. Because it allows for a high degree of design freedom, products using a storage battery according to one embodiment of the present invention This increases the design flexibility. Furthermore, it allows for the production of products using a battery according to one aspect of the present invention. It can enhance sexual performance.

[0183] Furthermore, in Figure 11, as an example, the number of pairs of opposing positive electrode active material layers and negative electrode active material layers is set to 5. However, of course, the number of electrode active material layers is not limited to five; there can be more or fewer. This is also good. When there are many electrode active material layers, it is possible to create a storage battery with a larger capacity. It is possible. Also, when the number of electrode active material layers is small, it is possible to make it thinner and create a rechargeable battery with excellent flexibility. It is possible.

[0184] In the above configuration, the battery casing 509 has a minimum radius of curvature of, for example, 3 mm or more. It can be deformed to be 0 mm or less, more preferably 3 mm to 10 mm or less. The film that forms the outer casing of the battery consists of one or two layers, forming a laminated structure. In the case of a pond, the curved cross-sectional structure of the battery is sandwiched between two curves of the outer film. This results in a structure.

[0185] The radius of curvature of a surface will be explained using Figure 15. In Figure 15(A), the curved surface 170 In the plane 1701 that cuts through 0, a portion of the curve 1702 contained in the curved surface 1700 is a circle Approximating it as an arc, let the radius of the circle be the radius of curvature 1703, and the center of the circle be the center of curvature 1704. Figure 15(B) shows a top view of the curved surface 1700. Figure 15(C) shows the curved surface on plane 1701. The cross-sectional view of 1700 is shown. When a curved surface is cut by a plane, the angle of the plane relative to the curved surface... The radius of curvature of the curve appearing in the cross-section will differ depending on the cutting position, but in this specification, etc. The smallest radius of curvature is defined as the radius of curvature of the surface.

[0186] A curved secondary battery was constructed using two films as an outer casing, sandwiching the electrodes, electrolyte, and other components of the 1805 battery. In this case, the radius of curvature 1802 of the film 1801 on the side closer to the center of curvature 1800 of the secondary battery. This is smaller than the radius of curvature 1804 of film 1803 on the side farther from the center of curvature 1800. Figure 16(A)). When the secondary battery is curved to make the cross-section arc-shaped, the center of curvature is close to 1800. Compressive stress is applied to the surface of the film, and tension is present on the surface of the film far from the center of curvature of 1800. Tension stress is applied (Figure 16(B)). When a pattern is formed on the exterior body with protrusions, this Even when compressive or tensile stress is applied, the effects of strain are kept within acceptable limits. Therefore, the secondary battery has the smallest radius of curvature of the outer casing on the side closer to the center of curvature. For example, the dimensions are 3 mm to 30 mm, more preferably 3 mm to 10 mm. It can be transformed into this.

[0187] Furthermore, the cross-sectional shape of a secondary battery is not limited to a simple arc shape, but can also have a shape in which part of it is an arc. It is possible to create shapes such as the one shown in Figure 16(C), or wavy (Figure 16(D)), or S-shaped. It is also possible to do so. If the curved surface of the secondary battery has a shape with multiple centers of curvature, Among the radii of curvature at each of the number of curvature centers, in the surface with the smallest radius of curvature, 2 For example, the smallest radius of curvature of the outer casing closest to the center of curvature of the individual casings is between 3 mm and 30 mm. The material can be deformed to be more preferably 3 mm or more and 10 mm or less.

[0188] Next, various examples of stacking of positive, negative, and separator electrodes are shown.

[0189] Figure 17(A) shows an example in which six layers each of the positive electrode 111 and the negative electrode 115 are stacked. A positive electrode active material layer 122 is provided on one side of the positive electrode current collector 121 of electrode 111. A negative electrode active material layer 126 is provided on one side of the negative electrode current collector 125 of the negative electrode 115.

[0190] Furthermore, in the configuration shown in Figure 17(A), the positive electrode 111 does not have a positive electrode active material layer 122. The positive electrode 11 is in contact with the negative electrode 115, so that the surfaces of the negative electrode 115 that do not have the negative electrode active material layer 126 are in contact with each other. 1 and the negative electrode 115 are stacked. By stacking them in this order, the positive electrode active material of the positive electrode 111 The surfaces that do not have the material layer 122, and the surfaces that do not have the negative electrode active material layer 126 of the negative electrode 115 This allows for the creation of metal-to-metal contact surfaces. These metal-to-metal contact surfaces are formed between the active material and the separator. The coefficient of friction can be reduced compared to the contact surface.

[0191] Therefore, when the energy storage device is bent, the positive electrode 111 does not have a positive electrode active material layer 122 on its surface. As the surfaces of the negative electrode 115 that do not have the negative electrode active material layer 126 slide against each other, the inner and outer diameters of the curve The stress caused by the difference can be relieved. Here, the inner diameter of the curve is, for example, the energy storage device 5 When 00 is curved, the outer casing 509 of the energy storage device 500 is located inside the curved portion. This refers to the radius of curvature of the surface. Therefore, it is possible to suppress the deterioration of the energy storage device 500. Furthermore, it can be used to create a highly reliable energy storage device 500.

[0192] Furthermore, Figure 17(B) shows an example of stacking of positive electrode 111 and negative electrode 115 that differs from that shown in Figure 17(A). In the configuration shown in Figure 17(B), positive electrode active material layers 122 are provided on both sides of the positive electrode current collector 121. In this respect, it differs from the configuration shown in Figure 17(A). As shown in Figure 17(B), the positive electrode current collector By providing positive electrode active material layers 122 on both sides of 121, the energy storage device 500 has a unit volume of The capacity can be increased.

[0193] Furthermore, Figure 17(C) shows an example of stacking of positive electrode 111 and negative electrode 115 that differs from that shown in Figure 17(B). In the configuration shown in Figure 17(C), a negative electrode active material layer 126 is provided on both sides of the negative electrode current collector 125. In this respect, it differs from the configuration shown in Figure 17(B). As shown in Figure 17(C), the negative electrode current collector By providing a negative electrode active material layer 126 on both sides of 125, the energy storage device 500 has a unit volume of The capacity can be increased even further.

[0194] Furthermore, in the configurations shown in Figures 11 and 17, the separator 123 encloses the positive electrode 111 in a bag-like manner. Although the present invention has been configured in this way, it is not limited to this. Here, in Figure 18(A), An example is shown of a separator 123 with a different configuration from 17(A). The configuration is shown in Figure 18(A). Next, a sheet-like separator 123 is placed between the positive electrode active material layer 122 and the negative electrode active material layer 126. This differs from the configuration shown in Figure 17(A) in that each sheet is provided individually. In this configuration, six layers each of positive electrode 111 and negative electrode 115 are stacked, and six layers of separator 123 are stacked. It is established.

[0195] Figure 18(B) also shows an example in which a different separator 123 is provided compared to Figure 18(A). In the configuration shown in 18(B), one separator 123 separates the positive electrode active material layer 122 and the negative electrode active material In the point where it is folded multiple times so as to be sandwiched between layers 126, as shown in Figure 18(A) The configuration is different. Also, the configuration in Figure 18(B) is different from the configuration in Figure 18(A) in terms of the separation of each layer. It can also be described as a configuration where Ta 123 is extended and the layers are connected. This is shown in Figure 18(B). In this configuration, six layers each of positive electrode 111 and negative electrode 115 are stacked, and the separator 123 is an example. If folded five or more times, it is sufficient. Also, the separator 123 consists of the positive electrode active material layer 122 and the negative electrode active material In addition to being sandwiched between the layers 126, it is also extended to provide multiple positive electrodes 111 and negative electrodes 1 You can also bundle the 15s together.

[0196] Alternatively, the positive electrode, negative electrode, and separator may be stacked as shown in Figure 19. Figure 19(A) Figure 19(B) is a cross-sectional view of the first electrode assembly 130, and Figure 19(B) is a cross-sectional view of the second electrode assembly 131. Figure 19(C) is a cross-sectional view taken along the dashed line A1-A2 in Figure 10. To make the diagram clearer, the first electrode assembly 130, the second electrode assembly 131 and the separator An excerpt from Layer 123 is shown below.

[0197] As shown in Figure 19(C), the energy storage device 500 comprises a plurality of first electrode assemblies 130 and It has multiple second electrode assemblies 131.

[0198] As shown in Figure 19(A), in the first electrode assembly 130, both sides of the positive electrode current collector 121 Positive electrode 111a having positive electrode active material layer 122, separator 123, and both sides of negative electrode current collector 125 Both the negative electrode 115a having a negative electrode active material layer 126, the separator 123, and the positive electrode current collector 121 The positive electrode 111a, which has a positive electrode active material layer 122 on its surface, is stacked in this order. Also, Figure 19( As shown in B), in the second electrode assembly 131, negative electrode active material is present on both sides of the negative electrode current collector 125. The negative electrode 115a has a layer 126, the separator 123, and positive electrode active material is present on both sides of the positive electrode current collector 121. Positive electrode 111a having a solid layer 122, separator 123, negative electrode current collector 125, both sides of which have a negative electrode active The negative electrode 115a, which has a material layer 126, is stacked in this order.

[0199] Furthermore, as shown in Figure 19(C), there are multiple first electrode assemblies 130 and multiple second The electrode assembly 131 is covered by a wound separator 123.

[0200] <Example of exterior structure> Figure 20(A) shows an example where the shape of region 509b differs from that in Figure 10. Figure 20(A) is a storage The top surface of the electrical device 500 is shown. Figure 20(B) shows the same direction as the dashed line A1-A2 in Figure 20(A). The corresponding cross-section is shown. Here, in Figure 20(A) and subsequent drawings, to avoid complexity, the positive electrode 5 The descriptions for 03, negative electrode 506, and separator 507 may be omitted.

[0201] In Figure 20(A), the exterior body 509 has region 509a and region 509b. Region 5 At least a part or all of 09b is a sealing portion.

[0202] <Example 1> Figure 21(A) shows an example where the shape of region 509b differs from that in Figure 20(A).

[0203] Figure 21(A) shows the top surface of the energy storage device 500. Figure 21(B) shows a point on Figure 21(A). The cross-section corresponding to the dashed line A1-A2 is shown.

[0204] In Figure 21(A), the exterior body 509 has region 509a and region 509b. Region 5 At least a part or all of 09b is a sealing portion.

[0205] Here, in the upper surface shown in Figure 21(A), of the region 509b, the left and right sides of the outer casing 509 The area located on the side has an arched shape, or it can be described as having a depression. It's also possible.

[0206] The sealing region 509b has an arched shape that follows the side surface of the outer casing 509. As a result, when the energy storage device 500 is bent, the stress is relieved, and wrinkles are formed in the outer casing 509. It may be possible to suppress it.

[0207] Figure 22(A) shows the top surface of the energy storage device 500. Figure 22(B) shows the same point as in Figure 22(A). The cross-section corresponding to the dashed line A1-A2 is shown. The outer casing of the energy storage device 500 shown in Figure 22(A) Body 509 has regions 509a, 509b, and 509c. Figure 22(A) In this region, region 509a is located outside the left and right sides of region 509c, and region 509b is located outside region 509a. It is located on the outside.

[0208] Furthermore, region 509b is preferably, for example, a sealing portion of the outer casing 509. Figure 22( In the upper surface of the outer casing 509 shown in A), by making region 509b a sealing portion, the upper edge And two sides are sealed.

[0209] <Modification 2> Figure 23(A) shows the top surface of the energy storage device 500. Figure 23(B) shows the same point as in Figure 23(A). The cross-section corresponding to the dashed line B1-B2 is shown. The outer casing of the energy storage device 500 shown in Figure 23(A) Body 509 has regions 509a, 509b, and 509c. Figure 23(A) In this configuration, region 509a is located outside the upper and lower parts of region 509c.

[0210] Region 509b is preferably the sealing portion of the outer casing 509, as shown in Figure 23(A) On the upper surface of the body 509, region 509b is made a sealing portion, so the upper edge and the two sides The edges are sealed.

[0211] Furthermore, the energy storage device 500 shown in Figure 23(B) is located in region 500a, region 500c and region It has 500d. Here, region 500a has region 509a, and region 500c has region 5 Region 500d has region 509a, and region 500d has region 509a.

[0212] An example of bending the energy storage device 500 will be explained using Figure 24. Figure 24(A) shows the energy storage device The cross-section corresponding to the dashed line A1-A2 in Figure 10 of position 500, Figure 24(B1), is shown in Figure 1. This is a cross-section corresponding to the dashed line B1-B2 at 0. Figure 24(B2) shows the energy storage device 50 This is an example of a cross-section corresponding to the dashed line B1-B2 when 0 is bent along the B1-B2 direction. Structure 541 is a structure located inside the outer casing 509 in the energy storage device 500. For example, it consists of a stack of positive electrode, negative electrode, and separator.

[0213] When the energy storage device 500 is bent along the B1-B2 direction, the stress due to bending is applied to the outer casing 509 In the outer casing 509, the region 509b having a sealing portion is formed by bonding two sheets together. It is divided and is less deformable compared to region 509a. For example, region 509b is region 5 It is less prone to stretching compared to 09a. Therefore, the region of region 509a that is close to region 509b, for example For example, in the region 561 enclosed by the dashed line in Figure 24(A), the ratio with other regions of region 509a is In comparison, greater stress may be applied. Also, greater deformation may occur. For example, cracks are likely to occur in the outer casing 509 in areas such as region 561.

[0214] Here, for example, by making the shape of region 509b an arch shape as shown in Figure 21, storage When the electrical device 500 is bent along the B1-B2 direction, the stress in region 561 is relieved, and cracks are prevented. It may be possible to suppress these and other factors.

[0215] In one embodiment of the present invention, a power storage device is provided with a protrusion on the outer casing to reduce rigidity, for example. This is preferable because it allows for the reduction of the stiffness modulus of region 509a. As a result, region 509a becomes more flexible and can easily expand and contract, thus relieving stress. On the other hand, the exterior The thickness of the energy storage device may increase by adding a protrusion to the body. Thickness refers, for example, to the thickness of the thickest region in an energy storage device. For example, region 50 If the protrusion of 9a is made deeper, the maximum height and minimum height of the film surface in region 509a The difference (for example, the height 357 shown in Figure 1) becomes large. Therefore, the energy storage device 500 is an electronic device. When installed in electronic devices, etc., the volume occupied by the energy storage device 500 increases. This results in increased dead space inside.

[0216] Therefore, as shown in Figure 22, the vicinity of region 509b is designated as region 509a, and the area inside it is designated as region 509a. A region 509c is provided, and in region 509c, for example, no protrusions, or no protrusions, etc. By making it shallower compared to region 509a, the energy storage device 500 can be mounted on electronic equipment, etc. In addition, the volume occupied by the energy storage device 500 can be reduced. Also, internal odors of electronic devices, etc. This reduces dead space.

[0217] When bonding the adhesive layer and the film and fixing them to form a sealing structure, pressure is applied, and the part that is pressed The size of the protrusion is made different in region 509b and region 509a. Region 509a By reducing the size of the convex portion in region 509b compared to the previous method, the effects of strain can be brought within an acceptable range. It can be suppressed.

[0218] If a protrusion is provided in region 509a and not in region 509b, then in region 509a Even if there is volume expansion inside the energy storage device, it can expand significantly. It has the effect of preventing the rupture of the structure. On the other hand, if there is no protrusion in region 509b, Compared to region 509a, region 509b exhibits reduced flexibility and stress relaxation. Therefore, Providing protrusions at the edges of the film helps to keep the effects of strain within an acceptable range. It encourages this.

[0219] Next, regarding an example in which the energy storage device 500 shown in Figure 23 is bent along the B1-B2 direction, see Figure 2 Let's explain using figure 5. Figure 25(A) shows an example of the energy storage device 500 in a nearly flat state. Figures 25(B) and 25(C) show examples of bending the energy storage device 500. In the example shown in Figure 25(C), regions 500a and 500d are relative to region 500c. In comparison, it is more curved, meaning it has a smaller radius of curvature.

[0220] Figure 26 shows an example of bending the energy storage device 500, illustrating the appearance of the outer casing 509. Figure 26 (A) shows an example of the energy storage device 500 in a nearly flat state. Figure 26(B) shows the energy storage device 5 An example of bending 00 is shown. In the example shown in Figure 26(B), regions 500a and 500d are Compared to region 500c, region 509 is more curved, meaning it has a smaller radius of curvature. Region a is deformed more than region 509c.

[0221] The stiffness ratio of region 509a is smaller than that of region 509c, making it more prone to stretching. Because the deformable region 509a is easily stretched, the distortion of the outer casing 509 of the energy storage device 500 and Therefore, the localized concentration of force on the outer casing 509 is mitigated. It can suppress cracks and other defects in 09.

[0222] Furthermore, in the energy storage device 500, for example, the maximum thickness of region 509a is compared with region 509c. By making it thinner, when the energy storage device 500 is mounted on electronic equipment, etc., the energy storage device 50 It can reduce the occupied volume of 0. Also, dead space inside electronic devices, etc. It can be reduced.

[0223] In Figures 10, 14, and 20 to 23, region 509b is flatter than region 509a. It is preferable that it be flat. Also, region 509b is flatter than region 509a when viewed from above. It is preferable that the value R, which is the ratio of surface area to product, is small. Also, in region 509b, The difference between the maximum and minimum heights of the film surface (for example, the height 357 shown in Figure 1) is in region 509a It is preferable that it be smaller than this.

[0224] Furthermore, in Figures 22 and 23, region 509c is flatter than region 509a. This is preferable. Furthermore, it is preferable that R in region 509a is larger than that in region 509c. Furthermore, it is preferable that the ratio be at least twice, and preferably between twice and five times. Furthermore, it is preferable that H in region 509a is greater than that in region 509c, for example, 2 It is preferable that it be more than double, and preferably between 2 and 5 times.

[0225] Furthermore, in Figures 22 and 23, region 509c is flatter than region 509b. This is also fine. Furthermore, region 509c may have a smaller R than region 509b. Also, region H in region 509c may be smaller than that in region 509a.

[0226] In Figures 22 and 23, for example, the stiffness or stiffness ratio of region 509a is preferably 1 .45×10 4 N or less, more preferably 0.90 × 10 3 N or more 1.30×10 4 N or less Furthermore, the stiffness or shear modulus of region 509a is equal to the stiffness or shear modulus of region 509c. Preferably, it should be between 1.2 and 4 times, and between 1.5 and 3 times the stiffness or rigidity modulus of region 509c. The following is more preferable, where the stiffness or rigidity modulus of region 509c is 1.7 times or more and 2.5 times or less. It is preferable.

[0227] Next, using Figure 27, one of the cross-sections of region 509a and region 509c of the exterior body 509. An example is shown. Figure 27(A) shows the region 571 enclosed by the dashed line in Figure 23(B). An enlarged view of the exterior body 509 is shown. Figure 27(B) shows the area enclosed by the dashed line in Figure 27(A). An enlarged view of region 572 is shown. Distance 531 is the surface of region 509c as viewed from one direction. This is the difference between the maximum and minimum heights in the region. Distance 533 is measured from one direction in region 509a. This is the difference between the maximum and minimum heights on the surface. In Figure 27(B), the distance from 531 is... The separation 533 is large. As an example of a different region 572 from Figure 27(B), see Figure 27(C) and Figure 27(D) is shown. In Figure 27(C), distance 533 is greater than distance 531, and territory The surface heights of region 509c and region 509a are approximately the same. Also, in Figure 27(D), Distance 531 and distance 533 are almost the same, and distance 532 is larger compared to Figure 27(B), etc.

[0228] Figure 28 shows an example in which the energy storage device 500 is installed inside the equipment 700. Figure 28(A) shows the equipment A cross-section of the device 700 is shown. The device 700 consists of a display unit 551, a housing 552, and the inside of the housing 552 It has a power storage device 500 located in the part, and the power storage device 500 is part of the outer casing 509. It has a region 509a and a structure 541.

[0229] The device 700 shown in Figure 28(B) differs in that the energy storage device 500 has region 509c. In the example shown in Figure 28(C), the maximum thickness of region 509c is thinner than that of region 509a. Therefore, a space 554 can be provided below region 509c. The device 700 is a circuit base If there is a board or the like, the circuit board or the like can be placed in the space 554, for example, the housing 55 The volume of 2 can be reduced. Or, for example, a more functional device 700 and This is possible. Also, the energy storage device 500 becomes thinner in the area below the display unit 551. Therefore, the thickness of the device 700 (553 mm) can be made even thinner.

[0230] Examples of devices 700 include electronic devices such as wearable devices. Further details will be provided later. Electronic devices and the like shown in the embodiment can be used.

[0231] <Manufacturing method>

[0232] The following is an explanation of embossing, a type of press work.

[0233] Figure 29 is a cross-sectional view showing an example of embossing. Embossing is a process that involves pressing It is a type of processing in which an embossed roll with an uneven surface is pressed onto a film, and the embossed roll This refers to the process of forming bumps and ridges on a film that correspond to the bumps and ridges of the surface. A sroll is a roll with a pattern engraved on its surface.

[0234] Figure 29 also shows an example of embossing on both sides of the film. This is a method for forming a film having a convex portion with a top.

[0235] Figure 29 shows an embossing roll 53 in contact with one side of the film and a roll in contact with the other side The film 50 is sandwiched between the embossing roll 55 and the film 50 in the direction of film travel. This shows the film being fed out at 60. A pattern is being created on the film surface by pressure or heat. The pattern is formed. Alternatively, the pattern may be formed on the film surface by both pressure and heat.

[0236] Embossing rolls include metal rolls, ceramic rolls, plastic rolls, and rubber rolls. Rolls, organic resin rolls, wood rolls, etc., can be used as appropriate.

[0237] Figure 29 shows the male embossed roll 53 and the female embossed roll 5 Embossing is performed using 5. The male embossing roll 53 has multiple protrusions 53a. The protrusion corresponds to the protrusion formed on the film to be processed. Female handle embossing throw The 55 has multiple protrusions 55a. The adjacent protrusions 55a form the embossed groove of the male handle. The protrusion 53a provided on the rod 53 forms a recess that fits into the protrusion formed on the film.

[0238] Embossing that raises a portion of film 50, and air that indents a portion of film 50 By continuously applying pressure, convex and flat sections can be formed in a continuous manner. As a result, A pattern can be formed on the film 50.

[0239] Furthermore, the height h3 of the protrusion 53a of the male pattern embossing roll 53 is the same as that of the female pattern embossing roll 5 It is preferable that the height of the protrusion 55a of 5 is smaller than h5. Also, the male embossing roll 53 The width of the protrusion 53a is formed by adjacent protrusions 55a in the female pattern embossing roll 55. It is preferable that the width is smaller than the width of the recess. As a result, the protrusions formed on the sheet Therefore, it is possible to form a region thicker than the bottom of the convex portion at the top of the convex portion.

[0240] Furthermore, the height of the protrusions on the embossing roll is such that the region having the protrusions on the embossing roll is... This is the difference between the distance from the top surface to the center and the radius of the embossing roll. For example, In the boss roll 55, the height h5 of the convex part of the emboss roll is the top of the convex part 55a This is the difference (d5-r5) between the distance d5 between the surface and the center and the radius r5 of the embossing roll 55. .

[0241] Furthermore, in embossing rolls, the width of the raised portion refers to the smallest length of the raised portion. Example For example, in the embossing roll 55, the smallest length g5 in the width of the protrusion 55a is the protrusion This refers to the width of section 55a.

[0242] Furthermore, in an embossed roll, the width of the recess formed by adjacent protrusions is the width of the adjacent protrusions This refers to the smallest length in the spacing between the sides. For example, in the embossing roll 55, adjacent The smallest length f5 between the sides of the interlocking protrusions 55a is called the width of the recess.

[0243] Next, Figure 30 shows a method for forming a film having multiple protrusions in a different way than in Figure 29. This will be explained using the following. Figure 30 shows an example of embossing on one side of a film. This is a method for forming a film having a convex portion with its apex on one side.

[0244] Figure 30(A) shows an embossing roll 55 in contact with one side of the film and a roll in contact with the other side The film 50 is sandwiched between the roll 54 and the film 50 in the direction of film travel 60. This shows the process of being fed out. Note that roll 54 may be fixed and not rotating. Therefore, in order to provide the embossing roll 55 on only one side of the film, the film has multiple A protrusion is provided, but the protrusion does not have space. That is, it protrudes on one surface, and on the other surface It is flat in that respect.

[0245] Next, as shown in Figure 30(B), a raised portion is formed on one surface by embossing. A portion of the film 51 is removed. Here, the convex portion is in contact with the flat surface, i.e., the roll 54. Remove a portion of the film from the surface that was previously covered. One method for removing a portion of the film is to use a laser. Thermal removal by irradiation with light, chemical removal by dropping etching solution, and physical removal by tools. This includes target removal, etc.

[0246] As a result, as shown in Figure 30(C), a space 10c can be formed in the convex portion 10a. Furthermore, a film 52 having a protrusion 10a can be formed.

[0247] In the film manufacturing method shown in Figure 30, the film 50 is a metal film. It is preferable to use the following. Next, after going through the steps in Figures 30(A) to 30(C), the metal It is preferable to provide a heat-seal layer on one or both sides of the film.

[0248] Next, a method for forming a film having multiple protrusions using a method different from that shown in Figures 29 and 30. This will be explained using Figure 31. Figure 31 shows how to use an embossing plate to create a film on both sides. This is an example of embossing. Also, if one side has a vertex, it becomes a convex part, and on the other side... This is a method for forming a film having a convex portion with a top.

[0249] As shown in Figure 31(A), an embossed plate 56 has a convex portion 56a and a concave portion 56b. Prepare an embossed plate 57 having a convex portion 57a ​​and a concave portion 57b.

[0250] Next, a film 50 is placed between the embossing plates 56 and 57.

[0251] Next, the embossing plate 56 is moved in the direction of arrow 61 shown in Figure 31(A), i.e., the film 50 Press the embossing plate 57 against one side of the film 50 as shown in Figure 31(A). Press in the direction of arrow 62, that is, towards the other side of film 50 (see Figure 31(C)). ). At this time, the convex portion 56a of the embossing plate 56 and the concave portion 57 of the embossing plate 57 b fits into the recess 56b of the embossed plate 56 and the protrusion 57 of the embossed plate 57 It is preferable to adjust the positions of the embossed plates 56 and 57 so that a fits into place.

[0252] Here, the height h6 of the protrusion 56a of the embossing plate 5 It is preferable that the depth of the recess 57b of 7 is smaller than h9. Also, the convexity of the embossed plate 56 The width f6 of part 56a is preferably smaller than the width f9 of the recess 57b of the embossing plate 57. (See Figure 31(B)).

[0253] Furthermore, the height h7 of the protrusion 57a ​​of the embossing plate 57 is equal to the height h7 of the recess of the embossing plate 56. It is preferable that the depth of 56b is less than h8. Also, the raised portion 57a ​​of the embossed plate 57 The width f7 is preferably smaller than the width f8 of the recess 56b of the embossed plate 56 (Figure 31(B)).

[0254] As a result of these factors, as shown in Figure 31(D), one side has a convex portion with a vertex, and the other side has a convex portion with a vertex, and the other side A film 52 can be formed having a convex portion with a top on the surface side. In this configuration, it is possible to form a region at the top of the convex portion that is thicker than the bottom of the convex portion.

[0255] Furthermore, the use of embossing rolls and embossing plates is not limited to the use of film. A relief may be formed on the part.

[0256] Here, we will explain the case where two or more types of embossing are applied to the surface of the film.

[0257] After applying the first type of embossing to the entire film, further embossing is applied on top of the embossed surface. A second type of embossing may be applied to it.

[0258] Alternatively, the strength of the press, heat, etc. during processing can be adjusted to create raised areas of embossing within the surface of the film. The height and other properties may be changed.

[0259] This embodiment can be implemented in appropriate combination with other embodiments.

[0260] (Embodiment 3) In this embodiment, the positive and negative electrodes of an energy storage device according to one aspect of the present invention will be described. ru.

[0261] In one aspect of the present invention, the positive electrode preferably has a positive electrode active material. The positive electrode may have a binder. Furthermore, the positive electrode of one aspect of the present invention may have a conductive additive. good.

[0262] In one embodiment of the present invention, the negative electrode preferably has a negative electrode active material. The negative electrode may have a binder. Furthermore, the negative electrode in one embodiment of the present invention may have a conductive additive. good.

[0263] <Negative electrode active material> For example, carbon-based materials or alloy-based materials can be used as the negative electrode active material.

[0264] Examples of carbon-based materials include graphite, easily graphitizable carbon (soft carbon), and poorly graphitizable carbon (hard carbon). Using carbon fiber, carbon nanotubes, graphene, carbon black, etc. stomach.

[0265] Examples of graphite include artificial graphite and natural graphite. For example, meso Examples include carbon microbeads (MCMB), coke-based artificial graphite, and pitch-based artificial graphite. Here, spheroidal graphite, which has a spherical shape, can be used as artificial graphite. For example, MCMB may have a spherical shape, which is preferable. Also, the surface of MCMB Reducing the product is relatively easy and sometimes preferable. Examples of natural graphite include Examples include flaky graphite and spheroidized natural graphite.

[0266] Graphite is formed when lithium ions are inserted into graphite (during the formation of lithium-graphite intercalation compounds). It exhibits a potential as low as lithium metal (0.1V to 0.3V vs. Li / Li + This allows lithium-ion secondary batteries to exhibit a high operating voltage. Furthermore, Graphite has a relatively high capacity per unit volume, relatively small volume expansion, and is inexpensive. It is preferable because it has advantages such as higher safety compared to lithium metal.

[0267] Here, when lithium ions are inserted into graphite, for example, the interlayer distance of the graphite becomes 0. It is known that the interlayer distance increases from 336 nm to 0.370 nm. It increases by 1%.

[0268] As a negative electrode active material, the charge-discharge reaction is carried out by alloying and dealloying reactions with lithium. Any possible element can be used. For example, silicon, tin, gallium, aluminum, Germanium, lead, antimony, bismuth, silver, zinc, cadmium, indium, etc. Materials containing at least one of these elements can be used. Such elements have a capacity compared to carbon. Larger, and especially silicon, has a high theoretical capacity of 4200 mAh / g. Therefore, the negative electrode active material Silicon is preferred. Compounds containing these elements may also be used. For example, SiO, Mg2Si, Mg2Ge, SnO, SnO2, Mg2Sn, SnS2, V2Sn3, FeSn2, CoSn2, Ni3Sn2, Cu6Sn5, Ag3Sn, Ag 3Sb, Ni2MnSb, CeSb3, LaSn3, La3Co2Sn7, CoSb3, Examples include InSb and SbSn. Here, charging and discharging occur through alloying and dealloying reactions with lithium. In some cases, elements capable of carrying out reactions, and compounds containing such elements, are referred to as alloying materials. be.

[0269] Furthermore, in this specification, SiO refers to, for example, silicon monoxide. Or SiO refers to, It can also be expressed as SiOx. Here, it is preferable that x has a value in one neighborhood. For example x Preferably, the value is between 0.2 and 1.5, and more preferably between 0.3 and 1.2.

[0270] Furthermore, the negative electrode active material according to one aspect of the present invention may also have silicon, lithium, and oxygen. Good. For example, silicon and lithium silicon oxide located on the outside of the silicon, You may have it.

[0271] Furthermore, titanium dioxide (TiO2) and lithium titanium oxide (Li4) are used as negative electrode active materials. Ti5O 12 ), lithium-graphite intercalation compound (Li x C6), niobium pentoxide (Nb2O5) ), use oxides such as tungsten oxide (WO2) and molybdenum oxide (MoO2). It is possible.

[0272] Furthermore, as the negative electrode active material, a Li3N type structure, which is a lithium and transition metal binitride, is also used. TsuLi 3-x M x N (M = Co, Ni, Cu) can be used. For example, Li 2. 6Co 0.4 The N3 has a large charge / discharge capacity (900mAh / g, 1890mAh / cm²).3 )of This is preferable.

[0273] When using a lithium-transition metal binitride, lithium ions are included in the negative electrode active material. In combination with materials such as V2O5 and Cr3O8 that do not contain lithium ions as the positive electrode active material. It is preferable that this be done. Furthermore, when using a material containing lithium ions as the positive electrode active material, Also, by pre-desorbing the lithium ions contained in the positive electrode active material, the negative electrode active material and Therefore, a lithium-transition metal composite can be used.

[0274] Furthermore, materials that undergo a conversion reaction can also be used as the negative electrode active material. For example For example, lithium, such as cobalt oxide (CoO), nickel oxide (NiO), and iron oxide (FeO). Transition metal oxides that do not form alloys with mu may be used as the negative electrode active material. Conversion reaction Materials that produce this include Fe2O3, CuO, Cu2O, RuO2, and Cr2O3. Oxides such as CoS 0.89 , sulfides such as NiS and CuS, Zn3N2, Cu3N, Ge Nitrides such as 3N4, phosphides such as NiP2, FeP2, CoP3, FeF3, BiF3, etc. This also occurs with fluorides.

[0275] The negative electrode active material is preferable because a lower reaction potential allows for a higher voltage in the energy storage device. On the other hand, when the potential is low, the reducing power of the electrolyte also increases, so for example, when used in the electrolyte... Organic solvents may be reduced and decomposed. A potential window is defined as the range of potentials within which the electrolyte does not undergo electrolysis. This is called the potential window. Originally, the negative electrode's electrode potential is the same as that of the electrolyte. It needs to be within the potential window, for example, lithium-ion secondary batteries and lithium-ion capacitors Many of the active materials used in the negative electrode of a device have a potential that exceeds the potential window of almost all electrolytes. In particular, materials with low reaction potentials, such as graphite and silicon, offer the advantage of being able to increase the voltage of energy storage devices. On the other hand, there is the problem that the electrolyte is more prone to reductive decomposition.

[0276] <Cathode active material> For example, the positive electrode active material may have an olivine-type crystal structure, a layered rock salt-type crystal structure, or a spi A composite oxide having a Nell-type crystal structure can be used.

[0277] As positive electrode active materials, LiFeO2, LiCoO2, LiNiO2, LiMn2O4, V Compounds such as 2O5, Cr2O5, and MnO2 can be used. In particular, LiCoO2 It has a large capacity, is more stable in the atmosphere than LiNiO2, and is more stable than LiNiO2. It is preferable because it has advantages such as being thermally stable. Also, LiMn2O4 and other materials A lithium-containing material having a spinel-type crystal structure containing cinnabar, with a small amount of lithium nickelate added. Um (LiNiO2 and LiNi 1-x M x When O2 (M=Co, Al, etc.) is mixed, This is preferable because it can improve the characteristics of secondary batteries using this method.

[0278] For example, the positive electrode active material has an average particle diameter of primary particles that is between 5 nm and 50 μm. Preferably, the specific surface area is 100 nm or more and more preferably 500 nm or less. m 2 / g or more 15m 2 It is preferable that it be less than or equal to / g. Also, the average particle size of the secondary particles is The particle size is preferably between 5 μm and 50 μm. The average particle size is measured using SEM (Scanning Electron Microscope). Observation by microscope or TEM, or by particle size distribution analyzer using laser diffraction / scattering, etc. It can be measured in this way. Furthermore, the specific surface area can be measured by the gas adsorption method.

[0279] Furthermore, as a positive electrode active material, the composition formula is Li a Mn b M c O d Lithium A manganese composite oxide can be used. Here, element M is other than lithium or manganese. It is preferable to use a selected metal element, or silicon, phosphorus, or nickel. This is even more preferable. Also, when measuring the entire particle of lithium manganese composite oxide, When the voltage <a / (b+c)<2、かつc>is 0, and 0.26≦(b+c) / d<0.5 It is preferable to satisfy this condition. Furthermore, in order to achieve high capacity, the crystal structure in the surface and the center is This involves using a lithium manganese composite oxide having regions with different crystal orientations or oxygen content. This is preferable. In order to obtain such a lithium manganese composite oxide, for example, 1.6 ≤ It is preferable to set a ≤ 1.848, 0.19 ≤ c / b ≤ 0.935, and 2.5 ≤ d ≤ 3. Furthermore, Li 1.68 Mn 0.8062 Ni 0.318 The chemical formula for O3 is It is particularly preferable to use thium manganese composite oxide. In this specification, Li 1. 68 Mn 0.8062 Ni 0.318 Lithium manganese composite represented by the chemical formula O3 Oxides are defined as a mixture where the ratio (molar ratio) of the raw materials is Li2CO3:MnCO3:NiO=0 Lithium manganese composite oxide formed by 0.84:0.8062:0.318 It refers to a substance. Therefore, the lithium manganese composite oxide has the compositional formula Li 1.68 Mn 0.80 ​ 62 Ni 0.318 It is represented as O3, but the composition may deviate from this.

[0280] The composition of the entire lithium manganese composite oxide particle, including metal, silicon, phosphorus, etc., is as follows: For example, it can be measured using ICP-MS (Inductively Coupled Plasma Mass Spectrometer). The oxygen composition of the entire particle of lithium manganese composite oxide is, for example, EDX (energy dispersion). It is possible to measure using (type X-ray spectroscopy). Furthermore, it can be used in combination with ICP-MS analysis. This can be determined by using valence evaluation from molten gas analysis and XAFS (X-ray absorption fine structure) analysis. This can be done. Furthermore, lithium manganese composite oxide is defined as at least lithium and manganese. This refers to oxides containing chromium, cobalt, aluminum, nickel, iron, magnesium, Molybdenum, zinc, indium, gallium, copper, titanium, niobium, silicon, and phosphorus It may contain at least one element selected from the group consisting of the following:

[0281] Lithium manganese composite oxide having regions with different crystal structure, crystal orientation, or oxygen content An example of a cross-sectional view of a particle is shown in Figure 32.

[0282] As shown in Figure 32(A), it has regions with different crystal structures, crystal orientations, or oxygen content. The lithium manganese composite oxide has region 331, region 332, and region 333. This is preferable. Region 332 is in contact with at least a portion of the outside of region 331. Here, outside The side indicates that it is closer to the surface of the particle. Also, region 333 is lithium manganese composite It is preferable that the particles having oxides have a region that coincides with the surface.

[0283] Furthermore, as shown in Figure 32(B), region 331 has an area that is not covered by region 332. This is also possible. Furthermore, region 332 may have regions not covered by region 333. Also, for example... For example, region 331 may have a region adjacent to region 333. Also, region 331 may have a region adjacent to region 3 There may be regions that are not covered by either region 32 or region 333.

[0284] Region 332 preferably has a different composition from region 331.

[0285] For example, the composition of region 331 and region 332 can be measured separately, and region 331 can be found to be lithium, man. Region 332 contains lithium, manganese, element M, and oxygen. The atomic ratio of lithium, manganese, element M, and oxygen in region 331 is a1:b1: Represented as c1:d1, this is the atomic ratio of lithium, manganese, element M, and oxygen in region 332. This section explains the case where the region is represented as a2:b2:c2:d2. Note that region 331 and region 3 Each of the 32 compositions was determined, for example, by EDX (energy) analysis using TEM (transmission electron microscope). - It can be measured by dispersive X-ray spectroscopy. In measurements using EDX, lithium compounds Measurement of composition can be difficult. Therefore, the difference in composition between region 331 and region 332 is described below. Next, we will discuss elements other than lithium. Here, d1 / (b1+c1) is 2.2 or greater. Preferably, it is 2.3 or higher, more preferably 2.35 or higher and 3 or lower. Furthermore, it is preferable that d2 / (b2+c2) is less than 2.2, and 2.1 It is more preferable that it be less than 1.1, and even more preferable that it be between 1.1 and 1.9. Even in this case, the entire lithium manganese composite oxide particle including regions 331 and 332 The composition is preferably such that the aforementioned 0.26 ≤ (b+c) / d < 0.5 is satisfied.

[0286] Furthermore, the manganese in region 332 has a different valency than the manganese in region 331. It is also possible to do so. Furthermore, the element M present in region 332 has a different value than the element M present in region 331. It may have a number.

[0287] More specifically, region 331 is a lithium manganese composite having a layered rock salt-type crystalline structure. It is preferable that it be an oxide. Also, region 332 is lithium having a spinel-type crystal structure It is preferable that it be a manganese composite oxide.

[0288] Here, if there is a spatial distribution of the composition of each region or the valence of elements, for example, multiple locations The composition and valency of each region are evaluated, their average values ​​are calculated, and the composition and valency of that region are also evaluated. good.

[0289] Furthermore, a transition layer may be present between region 332 and region 331. Here, the transition layer is: For example, a region in which the composition changes continuously or stepwise. Alternatively, a transition layer is a crystal A transition layer is a region in which the structure changes continuously or stepwise. This is a region where the constant changes continuously or stepwise. Alternatively, it refers to regions 332 and 331. A mixed layer may be present between them. Here, the mixed layer is, for example, two layers having different crystal orientations. This refers to the case where the above crystals are mixed. Alternatively, a mixed layer may be, for example, a layer having different crystal structures. This refers to a case where two or more crystals are mixed. Alternatively, a mixed layer is, for example, a layer having different compositions. This refers to a case where two or more crystals are mixed.

[0290] Region 333 can be made of carbon or a metallic compound. Here, as a metallic compound, For example, cobalt, aluminum, nickel, iron, manganese, titanium, zinc, lithium, etc. Examples of metal compounds include oxides and fluorides of these metals. It can be done.

[0291] Region 333 is particularly preferably composed of carbon, as carbon has high conductivity. Therefore, by using carbon-coated particles as electrodes in an energy storage device, for example, the resistance of the electrodes can be reduced. It can be made lower. Furthermore, region 333 preferably contains a graphene compound. By using a graphene compound in region 333, lithium manganese composite oxide particles It can be efficiently coated. Graphene compounds will be discussed later. Also, region 3 More specifically, 33 may have graphene, or it may have graphene oxide. Furthermore, graphene obtained by reducing graphene oxide is used as the graphene. This is preferable. Graphene has excellent electrical properties, such as high conductivity, and high flexibility. It also possesses excellent physical properties, including high mechanical strength. Region 333 contains oxide When reduction is performed using lafen, the region 332 adjacent to region 333 is oxidized. be.

[0292] Region 333 contains a graphene compound, which allows the lithium manganese composite oxide to be used as the cathode. The cycle characteristics of the secondary battery using this material can be improved.

[0293] The thickness of the carbon-containing layer is preferably between 0.4 nm and 40 nm.

[0294] Alternatively, the lithium manganese composite oxide, for example, has an average particle diameter of primary particles of 5 nm or more and preferably 50 μm or less, more preferably 100 nm or more and 500 nm or less. Also, the specific surface area is preferably 5 m 2 / g or more and 15 m 2 / g or less. Also, the average particle diameter of the secondary particles is preferably 5 μm or more and 50 μm or less.

[0295] Alternatively, as the positive electrode active material, a composite material (general formula LiMPO4 (M is one or more of Fe(II), M n(II), Co(II), Ni(II))) can be used. Representative examples of the general formula L iMPO4 include LiFePO4, LiNiPO4, LiCoPO4, Li MnPO4, LiFe a Ni b PO4, LiFe a Co b PO4, LiFe a Mn b PO 4, LiNi a Co b PO4, LiNi a Mn b PO4 (a + b is 1 or less, 0 < a < 1, 0 < b < 1), LiFe c Ni d Co e PO4, LiFe c Ni d Mn e PO4, LiN i c Co d Mn e PO4 (c + d + e is 1 or less, 0 < c < 1, 0 < d < 1, 0 < e < 1) , LiFe f Ni g Co h Mn i PO4 (f + g + h + i is 1 or less, 0 < f < 1, 0 < g < 1, 0 < h < 1, 0 < i < 1), etc. of lithium compounds can be used. <00

[0296] In particular, LiFePO4 satisfies well the requirements for a cathode active material, such as safety, stability, high capacity density, and the presence of lithium ions that can be extracted during initial oxidation (charging), etc., and thus is preferable. Therefore, it is preferable.

[0297] Alternatively, as the cathode active material, a composite material such as a general formula Li (2-j) MSiO4 (M is one or more of Fe(II), Mn(II), Co(II), Ni(II); 0 ≦ j ≦ 2) etc. can be used. As representative examples of the general formula Li (2-j) MSiO4, there are Li (2-j) F eSiO4, Li (2-j) NiSiO4, Li (2-j) CoSiO4, Li (2-j ) MnSiO4, Li (2-j) Fe k Ni l SiO4, Li (2-j) Fe k Co l S iO4, Li (2-j) Fe k Mn l SiO4, Li (2-j) Ni k Co l SiO4, Li (2-j) Ni k Mn l SiO4 (k + l is 1 or less, 0 < k < 1, 0 < l < 1), L i (2-j) Fe m Ni n Co q SiO4, Li (2-j) Fe m Ni n Mn q SiO4 、Li (2-j) Ni m Co n Mn q SiO4 (m + n + q is 1 or less, 0 < m < 1, 0 < n < 1, 0 < q < 1), Li (2-j) Fe r Ni s Co t Mn u SiO4(r + s + t + u is 1 or less, 0 < r < 1, 0 < s < 1, 0 < t < 1, 0 < u < 1), etc. lithium compounds can be used as materials.

[0298] Also, as the positive electrode active material, A x M2(XO4)3 (A = Li, Na, Mg, M = Fe, Mn, Ti, V, Nb, X = S, P, Mo, W, As, Si) represented by the general formula of NASICON type compounds can be used. NASICON type compounds include Fe2(MnO4)3, Fe2(SO4)3, Li3Fe2(PO4)3, etc. Also, as the positive electrode active material, L i2MPO4F, Li2MP2O7, Li5MO4 (M = Fe, Mn) represented by the general formula of compounds, perovskite type fluorides such as NaFeF3, FeF3, metal chalcogenides (sulfides, selenides, tellurides) such as TiS2, MoS2 , etc., oxides having an inverse spinel type crystal structure such as LiMVO4, vanadium oxide systems (V2O5, V6O , LiV 13 , 3O8, etc.), manganese oxides, organic sulfur compounds, etc. can be used as materials.

[0299] In addition, when the carrier ion is an alkali metal ion other than lithium ion or an alkaline earth metal ion, as the positive electrode active material, instead of lithium, an alkali metal (for example, sodium rium, potassium, etc.), an alkaline earth metal (for example, calcium, strontium, barium , beryllium, magnesium, etc.) may be used. For example, NaFeO2, or Na 2 / 3 [Fe 1 / 2 Mn1 / 2 Using sodium-containing layered oxides such as O2 as the positive electrode active material It can be used.

[0300] Furthermore, a material combining multiple of the above materials may be used as the positive electrode active material. For example, A solid solution formed by combining multiple of the above materials can be used as the positive electrode active material. For example, L iCo 1 / 3 Mn 1 / 3 Ni 1 / 3 A solid solution of O2 and Li2MnO3 is used as the positive electrode active material. It is possible to be there.

[0301] Although not shown in the diagram, a conductive material such as a carbon layer may be provided on the surface of the positive electrode active material. By providing conductive materials such as a base layer, the conductivity of the electrodes can be improved. The carbon layer coating on the positive electrode active material is achieved by mixing carbohydrates such as glucose during the firing of the positive electrode active material. It can be formed by doing so.

[0302] The average particle size of the primary particles of the granular positive electrode active material is between 50 nm and 100 μm. It would be good to do so.

[0303] <Binding agent> Binding agents include styrene-butadiene rubber (SBR) and styrene-isoprene-styrene. Lens rubber, acrylonitrile-butadiene rubber, butadiene rubber, ethylene-propylene It is preferable to use a diene-based rubber material such as a diene copolymer. Fluororubber can be used.

[0304] Furthermore, it is preferable to use a water-soluble polymer as the binder. For example, polysaccharides can be used as the derivative. Cellulose (CMC), methylcellulose, ethylcellulose, hydroxypropylcellulose Cellulose derivatives such as lurose, diacetylcellulose, and regenerated cellulose, as well as starch, etc. These can be used. Furthermore, these water-soluble polymers can be used in combination with the aforementioned rubber materials. It would be even better if they were there.

[0305] Alternatively, as a binder, polystyrene, polymethyl acrylate, polymethacrylate Chill (polymethyl methacrylate (PMMA)), sodium polyacrylate, polyvinyl Polyalcohol (PVA), polyethylene oxide (PEO), polypropylene oxide, Polyimide, polyvinyl chloride, polytetrafluoroethylene, polyethylene, polypropylene Polyethylene, isobutylene, polyethylene terephthalate, nylon, polyvinylidene fluoride ( PVdF), polyacrylonitrile (PAN), polyvinyl chloride, ethylene propyl It is preferable to use materials such as rangene polymers, polyvinyl acetate, and nitrocellulose. stomach.

[0306] You may use a combination of two or more of the above-mentioned binding agents.

[0307] The binder content relative to the total amount of the active material layer 102 is preferably between 1 wt% and 10 wt%. Furthermore, 2 wt% to 8 wt% is more preferable, and 3 wt% to 5 wt% is even preferable. Furthermore, the content of the conductive additive relative to the total amount of the active material layer 102 should be 1 wt% or more and 10 wt% or more. A value of t% or less is preferred, and a value of 1 wt% to 5 wt% is more preferred.

[0308] <Conductive additive>

[0309] Examples of conductive additives include carbon materials, metal materials, or conductive ceramic materials. It is possible to use a fibrous material as a conductive additive. The content of the conductive additive is preferably 1 wt% to 10 wt%, and preferably 1 wt% to 5 wt%. Less than t% is preferable.

[0310] Conductive additives can be used to form an electrical conduction network within electrodes. This allows the electrical conduction pathway between the positive electrode active materials to be maintained. By adding auxiliary agents, it is possible to create an active material layer with high electrical conductivity.

[0311] Examples of conductive additives include natural graphite, artificial graphite such as mesocarbon microbeads, and carbon. Fibers can be used. For example, mesophase pitch carbon fibers can be used. Carbon fibers such as fiber and isotropic pitch carbon fibers can be used. Carbon nanofibers and carbon nanotubes can be used. Notubes can be fabricated, for example, by vapor phase growth. Also, as a conductive additive, For example, carbon black (acetylene black (AB), etc.), graphite particles. Carbon materials such as ions, graphene, and fullerenes can be used. Also, for example, copper, Metal powders and fibers such as nickel, aluminum, silver, and gold, and conductive ceramic materials, etc. You can use it.

[0312] Graphene compounds may be used as conductive additives.

[0313] Graphene compounds possess excellent electrical properties, including high conductivity, and high flexibility. It may possess excellent physical properties such as high mechanical strength. The compound has a planar shape. The graphene compound enables surface contact with low contact resistance. Furthermore, even thin materials can have very high conductivity, allowing for efficient use within the active material layer in small quantities. A conductive path can be formed. Therefore, graphene compounds are used as conductive additives. This is preferable because it increases the contact area between the active material and the conductive additive. Furthermore, it is preferable because it can reduce electrical resistance. Here, as a graphene compound For example, it is particularly preferable to use graphene, multigraphene, or RGO.

[0314] When using active materials with small particle sizes, for example, active materials with a particle size of 1 μm or less, the specific surface area of ​​the active material The size is large, and more conductive paths are needed to connect the active materials. In such cases, fewer Using a graphene compound that can efficiently form conductive paths even in small quantities is particularly advantageous. It is preferable.

[0315] In the following example, a graphene compound is used as a conductive additive in the active material layer 102. An example of a cross-sectional configuration will be explained.

[0316] Figure 33(A) shows a longitudinal cross-sectional view of the active material layer 102. The active material layer 102 consists of granular active material. It contains 103, a graphene compound 321 as a conductive additive, and a binder 104. So, if graphene or multigraphene is used as graphene compound 321, Good. Here, it is preferable that the graphene compound 321 has a sheet-like shape. , graphene compound 321 is a multiple multigraphene, or / and multiple graphene The materials may partially overlap and form a sheet-like structure.

[0317] In the longitudinal section of the active material layer 102, as shown in Figure 33(A), within the active material layer 102 In the area, the sheet-like graphene compound 321 is dispersed in a generally uniform manner. (See Figure 33(A)) In the diagram, graphene compound 321 is schematically represented by a thick line, but in reality, it is a single layer of carbon molecules. Alternatively, it is a thin film with multiple layers and thickness. Multiple graphene compounds 321 are multiple granular active The material is to surround, cover, or spread on the surface of multiple granular active materials 103. Because they are formed to adhere to each other, they are in surface contact with one another.

[0318] Here, multiple graphene compounds bond together to form a network of graphene compounds. Forming a material sheet (hereinafter referred to as graphene compound net or graphene net) This is possible. When the active material is covered with a graphene net, the graphene net interacts with the active material. It can also function as a binder to hold them together. Therefore, the amount of binder can be reduced. Because it is possible or not to use, the active ingredients in the electrode volume and electrode weight The ratio of quality can be improved. In other words, the capacity of the energy storage device can be increased. ru.

[0319] Here, graphene oxide is used as graphene compound 321 and mixed with the active material to produce the active material It is preferable to reduce the layer after it forms the crystalline layer 102. Formation of graphene compound 321 Furthermore, by using graphene oxide, which has extremely high dispersibility in polar solvents, graphene Compound 321 can be dispersed approximately uniformly within the active material layer 102. The solvent is volatilized and removed from the dispersion medium containing dispersed graphene oxide, and the graphene oxide is returned. Therefore, the graphene compound 321 remaining in the active material layer 102 partially overlaps, By being dispersed to the extent that they are in surface contact with each other, a three-dimensional conductive path can be formed. Furthermore, the reduction of graphene oxide may be carried out, for example, by heat treatment, or by using a reducing agent. You may go.

[0320] Therefore, unlike granular conductive additives such as acetylene black that make point contact with the active material, the graph Since compound 321 enables surface contact with low contact resistance, it is not a typical conductive additive. This method improves the electrical conductivity between granular active material 103 and graphene compound 321 using a smaller amount. Therefore, it is possible to increase the ratio of the active material 103 in the active material layer 102. Yes, it is possible. This allows for an increase in the discharge capacity of the energy storage device.

[0321] Figure 33(B) shows a magnified view of the area enclosed by the dashed line in Figure 33(A). Binding agent 10 4 may be present in a layered manner on the surface of the active material 103. The graphene compound 321 is a binder. It is preferable that the binder 104 has a region in contact with the surface of 104. The binder 104 is, for example, the active material 10 It is located between 3 and the graphene compound 321. Preferably, it is bonded on the active material 103. A binder 104 is provided, and a graphene compound 321 is further provided on the binder 104.

[0322] <Current collector> The current collector 101 is made of metals such as stainless steel, gold, platinum, aluminum, titanium, and this Highly conductive materials such as alloys can be used. Also, the current collector 101 can be used as the positive electrode. If present, it is preferable that it does not dissolve at the positive electrode potential. Also, if the current collector 101 is used as the negative electrode, In such cases, it is preferable that it does not form an alloy with carrier ions such as lithium. Elements that improve heat resistance, such as titanium, neodymium, scandium, and molybdenum, are added. Aluminum alloys can be used. Furthermore, they react with silicon to form silicides. It may be formed with a metallic element that reacts with silicon to form a silicide. These include zirconium, titanium, hafnium, vanadium, niobium, tantalum, and chromium. These include molybdenum, tungsten, cobalt, nickel, etc. The current collector 101 is foil-shaped, plate-shaped, etc. Appropriate shapes such as sheet, mesh, perforated metal, and expanded metal are used. This is possible. The current collector 101 should preferably have a thickness of 5 μm or more and 30 μm or less. .

[0323] This embodiment can be implemented in appropriate combination with other embodiments.

[0324] (Embodiment 4) In this embodiment, the configuration example of the thin battery described in Embodiment 2 and the energy storage system This section describes an example of a system configuration.

[0325] <Example configuration of a slim battery storage system> Figures 34 and 35 show examples of the configuration of a thin storage battery. The wound body 99 shown in Figure 34(A) 3 has a negative electrode 994, a positive electrode 995, and a separator 996.

[0326] The wound body 993 has the negative electrode 994 and the positive electrode 995 overlapping with the separator 996 in between. The laminated sheets are stacked and then wound up. This wound body 993 is placed in a rectangular sealed container. By covering it with a material, a rectangular secondary battery is created.

[0327] The number of layers in the stack consisting of the negative electrode 994, positive electrode 995, and separator 996 is required. The design should be appropriate depending on the capacitance and element volume. The negative electrode 994 is connected to the lead electrode 997 and the lead electrode. One end of electrode 998 is connected to a negative electrode current collector (not shown), and positive electrode 995 is connected to a lead The electrode 997 and the other lead electrode 998 are connected to a positive electrode current collector (not shown). .

[0328] The storage battery 980 shown in Figures 34(B) and 34(C) is enclosed by a film 981. The space formed by bonding the film 982 having a recess to the above by heat-pressing or the like This houses the wound body 993 described above. The wound body 993 contains the lead electrode 997 and It has a hard electrode 998 and electrolysis occurs inside the film 981 and the film 982 which has a recess. It is impregnated with liquid.

[0329] Film 981 and film 982 having a recess are made of a metal material such as aluminum. Materials and resins can be used. Film 981 and film 982 having recesses If a resin material is used as the material, when an external force is applied, the film 981 and the recess will be affected. The film 982 having the property can be deformed, and a flexible storage battery can be manufactured. It is possible.

[0330] Furthermore, Figures 34(B) and 34(C) show examples where two films are used. By folding a single film, a space is formed, and the aforementioned wound body 9 is placed in that space. You may store 93.

[0331] Furthermore, by making the outer casing and sealing container of the energy storage device from resin material, flexibility is achieved. It is possible to manufacture an energy storage device. However, if the outer casing or sealing container is made of resin material, The parts that connect to the outside will be made of conductive material.

[0332] For example, Figure 35 shows an example of another thin, flexible battery. Figure 35(A) shows the wound body 9 Since 93 is identical to the one shown in Figure 34(A), a detailed explanation will be omitted. .

[0333] The storage battery 990 shown in Figures 35(B) and 35(C) is located inside the outer casing 991 as described above. This houses the wound body 993. The wound body 993 contains the lead electrode 997 and lead It has an electrode 998 and is impregnated with an electrolyte inside the outer casings 991 and 992. Outer casing 991, 992 can be made of metal materials such as aluminum or resin materials. If resin material is used as the material for 991 and 992, when an external force is applied, the outer casing 9 By deforming 91 and 992, a flexible, thin storage battery can be fabricated. ru.

[0334] An electrode containing an active material according to one aspect of the present invention is used in a flexible, thin storage battery. Furthermore, even if stress is applied to the electrodes by repeatedly bending the thin battery, This prevents the substance from cleaving.

[0335] Therefore, using an active material in which at least a portion of the cleavage surface is covered with graphene as an electrode... This makes it possible to suppress the drop in battery voltage and the decrease in discharge capacity. This can improve the battery's cycle characteristics during charging and discharging.

[0336] <Example of an energy storage system structure> Furthermore, an example of the structure of an energy storage system will be explained using Figures 36 to 38. An electrical system refers to, for example, equipment equipped with an energy storage device.

[0337] Figures 36(A) and 36(B) show external views of the energy storage system. The system comprises a circuit board 900 and a storage battery 913. The storage battery 913 has a label 91 A 0 is attached. Furthermore, as shown in Figure 36(B), the energy storage system has terminal 951 and It has terminal 952, antenna 914, and antenna 915.

[0338] The circuit board 900 has terminal 911 and circuit 912. Terminal 911 is connected to terminal 95 1. It is connected to terminal 952, antenna 914, antenna 915, and circuit 912. Oh, multiple terminals 911 are provided, and each of the multiple terminals 911 is a control signal input terminal, a power supply terminal, etc. It can also be used as a terminal, etc.

[0339] Circuit 912 may be provided on the back surface of circuit board 900. Note that antenna 914 And the antenna 915 is not limited to a coil shape, but may be, for example, linear or plate-shaped. Planar antenna, aperture antenna, traveling wave antenna, EH antenna, magnetic field antenna, induction An antenna such as an electrostatic antenna may be used. Alternatively, antenna 914 or antenna 91 5 may be a flat conductor. This flat conductor functions as one of the conductors for electric field coupling. This is possible. In other words, as one of the two conductors of the capacitor, Antenna 914 or antenna 915 may be activated. This will generate an electromagnetic field and a magnetic field. Furthermore, it is also possible to exchange power using an electric field.

[0340] The line width of antenna 914 is preferably larger than the line width of antenna 915. This allows for a greater amount of power to be received by antenna 914.

[0341] The energy storage system has a layer 9 between antennas 914 and 915 and the battery 913. It has 16. Layer 916 can shield electromagnetic fields, for example, from a storage battery 913. It has the ability to do so. For layer 916, for example, a magnetic material can be used.

[0342] Note that the structure of the energy storage system is not limited to the structure shown in Figure 36.

[0343] For example, as shown in Figures 37(A-1) and 37(A-2), Figure 36(A) and In the battery 913 shown in Figure 36(B), antennas are provided on each of the two opposing sides. This is also acceptable. Figure 37(A-1) is an external view of the pair of surfaces as seen from one side, and Figure 3 Figure 7(A-2) is an external view of the pair of surfaces as seen from the other side. Note that Figure 36(A) And for the same parts as the energy storage system shown in Figure 36(B), see Figures 36(A) and 3 The explanation of the energy storage system shown in 6(B) can be used as appropriate.

[0344] As shown in Figure 37(A-1), a layer 916 is sandwiched between one of the pair of surfaces of the storage battery 913. An incubator 914 is provided, and as shown in Figure 37(A-2), on the other side of the battery 913 An antenna 915 is provided on one side, with layer 917 in between. Layer 917 is, for example, connected to a storage battery 913. It has the function of shielding electromagnetic fields. For layer 917, for example, a magnetic material is used. It is possible to be there.

[0345] By adopting the above structure, the size of both antenna 914 and antenna 915 can be increased. It is possible to hear.

[0346] Alternatively, as shown in Figures 37(B-1) and 37(B-2), Figure 36(A) and Of the storage battery 913 shown in Figure 36(B), a separate antenna is attached to each of the two opposing sides. It may be provided. Figure 37(B-1) is an external view of the pair of surfaces as seen from one side. Figure 37(B-2) is an external view of the pair of surfaces as seen from the other side. Note that Figure 36( For the same parts as the energy storage system shown in A) and Figure 36(B), see Figure 36(A) and The explanation of the energy storage system shown in Figure 36(B) can be used as appropriate.

[0347] As shown in Figure 37(B-1), a layer 916 is sandwiched between one of the pair of surfaces of the storage battery 913. An antenna 914 and an antenna 915 are provided, and as shown in Figure 37(B-2), the storage battery An antenna 918 is provided on the other side of the pair of faces of 913, with layer 917 in between. Antenna 91 8, for example, has the function of being able to communicate data with external devices. Antenna 91 For example, antennas with shapes applicable to antennas 914 and 915 can be applied to 8. This is possible. It is a communication method between the energy storage system and other devices via antenna 918. This involves applying response methods that can be used between the energy storage system and other devices, such as NFC. It is possible.

[0348] Alternatively, as shown in Figure 38(A), the storage battery 91 shown in Figures 36(A) and 36(B) A display device 920 may be provided at 3. The display device 920 is connected to terminal 911 via terminal 919. It is electrically connected to the display device 920. It is not necessary. Furthermore, the same parts as the energy storage system shown in Figures 36(A) and 36(B) In this regard, the explanation of the energy storage system shown in Figures 36(A) and 36(B) can be appropriately referenced.

[0349] The display device 920 may display, for example, an image indicating whether or not it is charging, an image indicating the amount of stored power, etc. It may be displayed. The display device 920 may be, for example, electronic paper, liquid crystal display device, etc. A trollescent (also known as EL) display device can be used. For example, an electronic paper By using a supercharger, the power consumption of the display device 920 can be reduced.

[0350] Alternatively, as shown in Figure 38(B), the storage battery 91 shown in Figures 36(A) and 36(B) A sensor 921 may be provided at 3. The sensor 921 receives power from terminal 911 via terminal 922. It is electrically connected. Note that it is the same part as the energy storage system shown in Figures 36(A) and 36(B). For details, please refer to the explanation of the energy storage system shown in Figures 36(A) and 36(B) as appropriate. Cut.

[0351] Examples of sensors 921 include force, displacement, position, velocity, acceleration, angular velocity, rotational speed, and distance. Separation, light, liquid, magnetism, temperature, chemical substances, sound, time, hardness, electric field, electric current, voltage, power, radiation Use a device that includes functions for measuring radiation, flow rate, humidity, gradient, vibration, odor, or infrared radiation. This is possible. By providing the sensor 921, for example, the environment in which the energy storage system is located can be detected. It is also possible to detect data indicating this (such as temperature) and store it in the memory within circuit 912. .

[0352] The battery and energy storage system shown in this embodiment use electrodes according to one aspect of the present invention. Therefore, the capacity of batteries and energy storage systems can be increased. Energy density can be increased. Reliability can be improved. Furthermore, lifespan can be extended. It can be done.

[0353] This embodiment can be implemented in appropriate combination with other embodiments.

[0354] (Embodiment 5) This embodiment describes an example of mounting a flexible storage battery in an electronic device.

[0355] Figure 39 shows an example of mounting the flexible storage battery shown in Embodiment 2 into an electronic device. Electronic devices that utilize energy storage devices with a flexible shape include, for example, television equipment. Televisions (also called televisions or television receivers), monitors for computers, digital cameras, etc. Cameras, digital video cameras, digital photo frames, mobile phones (mobile phones, portable cameras) (Also known as mobile phone devices), portable game consoles, personal digital assistants, sound playback devices, pachinko machines, etc. Examples include large game consoles.

[0356] Furthermore, energy storage devices with flexible shapes can be installed in the interior or exterior walls of houses and buildings, or in automated systems. It can also be integrated to conform to the curved surfaces of the car's interior or exterior.

[0357] Figure 39(A) shows an example of a mobile phone. The mobile phone 7400 has a housing 740 In addition to the display unit 7402 incorporated into 1, there are also operation buttons 7403, an external connection port 7404, It is equipped with speaker 7405, microphone 7406, etc. Note that the mobile phone 7400 is a storage It has an electrical device 7407.

[0358] Figure 39(B) shows the mobile phone 7400 in a curved state. When 00 is deformed by an external force and the whole thing is bent, the power storage device located inside it The 7407 is also bent. Figure 39 shows the state of the bent energy storage device 7407 at that time. As shown in C), the energy storage device 7407 is a thin battery. The energy storage device 7407 is bent. It is fixed in place. Furthermore, the energy storage device 7407 is electrically connected to the current collector 7409. It has a copper electrode 7408. For example, the current collector 7409 is copper foil, and partly gallium By alloying it, the adhesion between the current collector 7409 and the active material layer in contact with it is improved, and the energy storage device 7407 This configuration offers high reliability even when bent.

[0359] Figure 39(D) shows an example of a bangle-type display device. The portable display device 7100 is It comprises a housing 7101, a display unit 7102, operation buttons 7103, and a power storage device 7104. Figure 39(E) also shows the state of the bent energy storage device 7104. The energy storage device 7104 is When worn on the user's arm in a bent state, the casing deforms, causing part of the power storage device 7104 to be damaged. The curvature of the curve changes across the entire curve. Note that the degree of curvature at any point in the curve is the radius of the corresponding circle. The value expressed as is the radius of curvature, and the reciprocal of the radius of curvature is called the curvature. Specifically, the half of the radius of curvature A portion of the main surface of the housing or energy storage device 7104, within the range of 40 mm to 150 mm in diameter Or the whole thing changes. The radius of curvature on the main surface of the energy storage device 7104 is 40 mm or more 15 High reliability can be maintained within a range of 0 mm or less.

[0360] Figure 39(F) shows an example of a wristwatch-type personal information terminal. Personal information terminal 7200 The components are: housing 7201, display unit 7202, band 7203, buckle 7204, and operation button 7 It is equipped with terminals 205 and input / output terminals 7206, etc.

[0361] The 7200 mobile information terminal offers mobile phone calls, email, document viewing and creation, music playback, and more. It can run various applications such as internet communication and computer games. Cut.

[0362] The display unit 7202 has a curved display surface, and displays information along the curved surface. It is possible to do so. In addition, the display unit 7202 is equipped with a touch sensor, and the screen can be touched with a finger or stylus. It can be operated by touching it. For example, icon 7 displayed on the display unit 7202 Touching 207 will launch the application.

[0363] The 7205 control button is used for time setting, as well as power on / off, wireless communication on, and more. Various functions such as operation, activation and deactivation of silent mode, and activation and deactivation of power saving mode. It can be made to hold. For example, the operating system built into the personal digital assistant 7200 The system also allows you to freely configure the function of the control button 7205.

[0364] Furthermore, the 7200 portable information terminal is capable of performing standardized short-range wireless communication. For example, by communicating with a wireless headset, hands-free operation is possible. You can also make calls.

[0365] Furthermore, the portable information terminal 7200 is equipped with an input / output terminal 7206, and can connect to other information terminals. Data can be exchanged directly via this. Also, charging is possible via input / output terminal 7206. It can also perform electrical operations. Note that charging is done wirelessly without using input / output terminal 7206. You may go.

[0366] The display unit 7202 of the portable information terminal 7200 is equipped with an energy storage device comprising electrodes according to one aspect of the present invention. It has, for example, the energy storage device 7104 shown in Figure 39(E) inside the housing 7201. It can be incorporated in a curved state, or in a flexible state inside the band 7203. ru.

[0367] The personal information terminal 7200 preferably has a sensor. For example, a fingerprint sensor. Human body sensors such as pulse sensors and body temperature sensors, as well as touch sensors, pressure sensors, and accelerometers. It is preferable that sensors, etc., be installed.

[0368] Figure 39(G) shows an example of an armband-type display device. The display device 7300 is a display unit The device has 7304 and has an energy storage device according to one aspect of the present invention. Furthermore, the display device 7300 is The display unit 7304 can also be equipped with a touch sensor, and it can also function as a portable information terminal. It is also possible to do so.

[0369] The display unit 7304 has a curved display surface, and displays are performed along the curved display surface. This is possible. In addition, the display device 7300 can display information via standardized short-range wireless communication. The situation can be changed.

[0370] Furthermore, the display device 7300 is equipped with input / output terminals and can be directly connected to other information terminals via connectors. It can exchange data. It can also be charged via its input / output terminals. Furthermore, charging may be performed wirelessly without using input / output terminals.

[0371] This embodiment can be implemented in appropriate combination with other embodiments.

[0372] (Embodiment 6) This embodiment shows an example of an electronic device that can be equipped with an energy storage device.

[0373] Figures 40(A) and 40(B) show an example of a foldable tablet device. The tablet terminal 9600 shown in Figures 40(A) and 40(B) has a housing 9630a, Housing 9630b, movable part 9640 connecting housing 9630a and housing 9630b, display unit 9 Display unit 9631 having 631a and display unit 9631b, display mode switching switch 96 26. Power switch 9627, power saving mode switch 9625, fastener 9629 It has an operating switch 9628. Figure 40(A) shows the tablet terminal 9600 opened. Figure 40(B) shows the state in which the tablet terminal 9600 is closed.

[0374] Furthermore, the tablet terminal 9600 stores inside the housings 9630a and 9630b It has an electric body 9635. The electric body 9635 passes through the movable part 9640 and the housing 9630a and the housing It is provided across body 9630b.

[0375] The display unit 9631a can be partially designated as a touch panel area 9632a, and the display will Data can be entered by touching the operation key 9638. Note that the display unit 96 In 31a, as an example, one half of the area has a display-only function, and the other half of the area The area indicates a configuration having touch panel functionality, but is not limited to this configuration. Display unit 96 The entire area of ​​31a may also be configured to have touch panel functionality. For example, the display unit 9 The entire surface of 631a is used as a touch panel with keyboard buttons, and the display unit 9631b is displayed It can be used as a display screen.

[0376] In addition, in the display unit 9631b, similar to the display unit 9631a, one of the display units 9631b The area can be designated as the touch panel area 9632b. Also, the touch panel keyboard Touch the location where the display toggle button 9639 is displayed using your finger or stylus. This allows keyboard buttons to be displayed on the display unit 9631b.

[0377] Furthermore, simultaneously with respect to the touch panel area 9632a and the touch panel area 9632b You can also use touch input.

[0378] Additionally, the display mode switch 9626 changes the display orientation, such as portrait or landscape. You can switch between modes, such as switching between black and white and color displays. Power saving mode switching... The switch 9625 is used by the light sensor built into the tablet terminal 9600. The display brightness can be optimized according to the amount of ambient light at the time. (Tablet device) In addition to optical sensors, other sensors such as gyroscopes and accelerometers that detect tilt are also used. An output device may be built into the unit.

[0379] Furthermore, Figure 40(A) shows an example where the display area of ​​display unit 9631b and display unit 9631a are the same. However, this is not particularly limited, and one size may be different from the other. The display quality may also differ. For example, one display panel can provide a higher-resolution display than the other. You can also use "ru".

[0380] Figure 40(B) shows the closed state, and the tablet terminal consists of a housing 9630 and a solar cell 9 633, it has a charge / discharge control circuit 9634 including a DC-DC converter 9636. As body 9635, a power storage body according to one aspect of the present invention is used.

[0381] Furthermore, since the tablet device 9600 is foldable, the casing 9630a can be folded in half when not in use. The casing 9630b can be folded so that it overlaps with the other casing. Therefore, the display unit 9631a and the display unit 9631b can be protected, thus the tablet terminal 9600 Durability can be increased. Furthermore, the energy storage body 9635 using the energy storage body according to one aspect of the present invention is It is flexible and its charge / discharge capacity does not easily decrease even after repeated bending and stretching. Therefore, reliability We can provide excellent tablet devices.

[0382] In addition, there are various other tablet devices, as shown in Figures 40(A) and 40(B). Features that display information (still images, videos, text images, etc.), calendar, date or time. Functions that display such information on the display unit, and the ability to use touch input or edit the information displayed on the display unit. It has features such as input functionality and the ability to control processing through various software (programs). It is possible.

[0383] The touch panel is powered by a solar cell 9633 mounted on the surface of the tablet device. It can be supplied to the display unit or the video signal processing unit, etc. The solar cell 9633 is It can be installed on one or both sides of the housing 9630, and efficiently charges the energy storage unit 9635. This configuration can be achieved. Furthermore, if a lithium-ion battery is used as the energy storage element 9635, This offers advantages such as the ability to miniaturize the device.

[0384] Furthermore, the configuration and operation of the charge / discharge control circuit 9634 shown in Figure 40(B) are shown in Figure 40. (C) shows a block diagram and provides an explanation. Figure 40(C) shows a solar cell 9633 and a power storage unit 96 35. DC-DC converter 9636, converter 9637, switch SW1 to SW3, The display unit 9631 is shown, along with the energy storage unit 9635, the DC-DC converter 9636, and Converter 9637, switches SW1 to SW3, and the charge / discharge control circuit 9 shown in Figure 40(B) This corresponds to section 634.

[0385] First, let's explain an example of how the solar cell 9633 operates when generating electricity using ambient light. The electricity generated by the solar cells is converted into a DC-DC converter to provide the voltage necessary to charge the 9635 energy storage unit. The converter 9636 performs voltage boosting or bucking. Then, the solar power is used to control the operation of the display unit 9631. When power from pond 9633 is used, switch SW1 is turned ON, and converter 963 In step 7, the voltage is increased or decreased to the required voltage for the display unit 9631. Also, the display unit 963 If you do not want to display in step 1, turn SW1 off and turn SW2 on to enable the storage unit 9635. The configuration should include charging capabilities.

[0386] While solar cell 9633 is shown as an example of a power generation method, it is not particularly limited to this method. Storage using other power generation methods such as piezoelectric elements (piezo elements) and thermoelectric elements (Peltier elements) The configuration may also involve charging the battery 9635. For example, power may be transmitted and received wirelessly (contactlessly). This includes contactless power transmission modules that charge via this method, as well as configurations that combine this with other charging methods. You may do so.

[0387] Figure 41 shows an example of another electronic device. In Figure 41, the display device 8000 is the present invention. This is an example of an electronic device using a power storage device 8004 according to one embodiment. Specifically, the display device 80 00 corresponds to a display device for receiving TV broadcasts, and consists of a housing 8001, a display unit 8002, and a speaker. It has part 8003, a power storage device 8004, etc. A power storage device 8004 according to one aspect of the present invention is It is located inside the enclosure 8001. The display device 8000 receives power from the commercial power supply. You can receive power from it, or you can use the power stored in the energy storage device 8004. Therefore, even when power cannot be supplied from the commercial power source due to a power outage or the like, according to one aspect of the present invention By using the energy storage device 8004 as an uninterruptible power supply, the display device 8000 can be used. Yes.

[0388] The display unit 8002 has light-emitting elements such as liquid crystal display devices and organic EL elements in each pixel. Optical devices, electrophoresis display devices, DMDs (Digital Micromirror Dev ice), PDP (Plasma Display Panel), FED (Field Semiconductor display devices such as Emission Displays can be used.

[0389] In addition to being used for receiving TV broadcasts, the display devices are also used for personal computers and for displaying advertisements. This includes all information display devices.

[0390] In Figure 41, the fixed lighting device 8100 is a power storage device 8 according to one aspect of the present invention. This is an example of an electronic device using 103. Specifically, the lighting device 8100 has a housing 8101, It has a light source 8102, a power storage device 8103, etc. In Figure 41, the power storage device 8103 is located in the housing 8 For example, consider the case where 101 and the light source 8102 are installed inside the ceiling 8104. Although shown, the energy storage device 8103 may be located inside the housing 8101. The device 8100 can receive power from the commercial power supply, or from the energy storage device 8103. It is also possible to use stored power. Therefore, in the event of a power outage, etc., power supply from commercial power source Even when it is not possible to receive a power supply, the energy storage device 8103 according to one aspect of the present invention can be used as an uninterruptible power supply. This makes it possible to use the lighting device 8100.

[0391] In Figure 41, a fixed lighting device 8100 installed on the ceiling 8104 is shown as an example. However, in one aspect of the present invention, the energy storage device can be used not only on the ceiling 8104, but also on the side walls 8105, floor, etc. It can also be used in fixed lighting devices installed in windows such as 8106 and 8107, and also in tables It can also be used in overhead lighting fixtures and other applications.

[0392] Furthermore, the light source 8102 can use an artificial light source that artificially obtains light using electricity. Yes, it is possible. Specifically, this includes discharge lamps such as incandescent light bulbs and fluorescent lamps, and LEDs and organic EL elements. Optical elements are an example of the artificial light sources mentioned above.

[0393] In Figure 41, the air conditioner having an indoor unit 8200 and an outdoor unit 8204 is This is an example of an electronic device using the energy storage device 8203 according to one aspect of the present invention. Specifically, the room The internal unit 8200 includes a housing 8201, an air outlet 8202, a power storage device 8203, etc. (Figure 41) The example given is that the energy storage device 8203 is installed in the indoor unit 8200, The electrical device 8203 may be installed on the outdoor unit 8204. Alternatively, it may be installed on the indoor unit 8200 and the room Both outdoor units 8204 may be equipped with energy storage devices 8203. - It can receive power from the commercial power supply, or stored in the energy storage device 8203 Electricity can also be used. In particular, both the indoor unit 8200 and the outdoor unit 8204 are equipped with energy storage devices 8 If 203 is installed, when power cannot be supplied from the commercial power source due to a power outage, etc. However, by using the energy storage device 8203 according to one aspect of the present invention as an uninterruptible power supply, Conditioner can be used.

[0394] Figure 41 shows a separate-type air conditioner consisting of an indoor unit and an outdoor unit. The example shown is an integrated air conditioner that has both the indoor and outdoor unit functions in a single housing. A power storage device according to one aspect of the present invention can also be used as the conditioner.

[0395] In Figure 41, the electric refrigerator 8300 is a power storage device 8304 according to one aspect of the present invention. This is an example of an electronic device using [a specific component]. Specifically, the electric refrigerator 8300 has a casing 8301, It has a refrigerator door 8302, a freezer door 8303, an energy storage device 8304, etc. In Figure 41, The energy storage device 8304 is located inside the casing 8301. The electric refrigerator 8300 is It can also receive power from the commercial power supply, or the power stored in the energy storage device 8304 It is also possible to use this. Therefore, if power cannot be supplied from the commercial power source due to a power outage, etc. Even at times, by using the energy storage device 8304 according to one aspect of the present invention as an uninterruptible power supply, The 8300 refrigerator / freezer will become available for use.

[0396] Of the electronic devices mentioned above, high-frequency heating devices such as microwave ovens and electric rice cookers are included. Sub-devices require high power for short periods. Therefore, they need to supplement the power that cannot be supplied by the commercial power supply. By using an energy storage device according to one aspect of the present invention as an auxiliary power source to assist, electronic equipment This prevents the commercial power circuit breaker from tripping when using it.

[0397] Furthermore, during periods when electronic devices are not in use, especially the total amount of electricity that can be supplied by the commercial power source... Of these, during the time periods when the proportion of electricity actually used (called the electricity usage rate) is low, storage By storing electricity in the electrical equipment, the rate of electricity use outside of the above-mentioned time period can be suppressed. It is possible. For example, in the case of the electric refrigerator 8300, when the temperature is low, the refrigerator door 83 02. At night when the freezer door 8303 is not opened or closed, power is supplied to the energy storage device 8304. Store. Then, as the temperature rises, the refrigerator door 8302 and the freezer door 8303 are opened and closed. During the daytime, by using the energy storage device 8304 as an auxiliary power source, daytime electricity usage The rate can be kept low.

[0398] This embodiment can be implemented in appropriate combination with other embodiments.

[0399] (Embodiment 7) This embodiment shows an example in which a power storage device is installed in a vehicle.

[0400] Furthermore, when a battery storage device is installed in a vehicle, hybrid electric vehicles (HEVs) and electric vehicles (EVs) or next-generation clean energy vehicles such as plug-in hybrid vehicles (PHEVs) It can be expressed.

[0401] Figure 42 illustrates a vehicle using one aspect of the present invention. The automobile shown in Figure 42(A) The 8400 is an electric vehicle that uses an electric motor as its power source for propulsion. It is possible to appropriately select and use an electric motor and an engine as the power source for propulsion. This is a hybrid vehicle. By using one aspect of the present invention, a vehicle with a long driving range can be realized. It is possible. Furthermore, the automobile 8400 has a power storage device. The power storage device is an electric motor In addition to driving the 8406, it also powers the headlights 8401 and interior lights (not shown), etc. It can supply power to the light-emitting device.

[0402] Furthermore, the energy storage device is used for the speedometer, tachometer, and other displays of the 8400 automobile. It can supply power to the display device. In addition, the energy storage device is the navigation system of the automobile 8400. It can supply power to semiconductor devices such as gate systems.

[0403] The automobile 8500 shown in Figure 42(B) plugs into the energy storage device of the automobile 8500. It can be charged by receiving power from an external charging facility using methods such as contactless power supply. It can be done. Figure 42(B) shows the ground-mounted charging device 8021 being mounted on the automobile 8500. This shows the state in which the energy storage device 8024 is being charged via cable 8022. Therefore, charging methods and connector specifications are subject to the standards of CHAdeMO (registered trademark) and Combo, etc. This can be done as appropriate. The charging device 8021 is a charging station installed in a commercial facility. However, it is also fine to use a household power supply. For example, plug-in technology allows external power to be supplied. The power supply can be used to charge the energy storage device 8024 installed in the automobile 8500. Charging is performed by converting AC power to DC power via a conversion device such as an AC / DC converter. It is possible.

[0404] Although not shown in the diagram, a power receiving device is mounted on the vehicle, and power is supplied wirelessly from a ground-based power transmission device. It can also be charged by supplying power. In this contactless power supply method, the power transmission equipment is installed on the road or exterior wall. By incorporating this, charging can be performed not only when the vehicle is stopped but also while it is in motion. The electric system may be used to transmit and receive power between vehicles. Furthermore, the exterior of the vehicle Solar panels may be installed to charge the energy storage device when the vehicle is stopped or in motion. Electromagnetic induction and magnetic resonance methods can be used to supply power in this environment.

[0405] According to one aspect of the present invention, the cycle characteristics of the energy storage device are improved, and its reliability is enhanced. It is possible to do so. Furthermore, according to one aspect of the present invention, the characteristics of the energy storage device can be improved. Therefore, the energy storage device itself can be made smaller and lighter. This contributes to reducing the vehicle's weight, thus improving its driving range. The installed energy storage device can also be used as a power source other than the vehicle. In this case, the power demand This allows us to avoid using commercial power during peak hours.

[0406] This embodiment can be implemented in appropriate combination with other embodiments.

[0407] (Embodiment 8) Battery that can be used in combination with a battery cell containing the material described in the above embodiment Control unit (Battery Management Unit: BMU), and the power For transistors suitable for the circuits constituting the battery control unit, refer to Figures 43 to 49. This will be explained. In this embodiment, in particular, the power of a storage device having battery cells connected in series Let me explain the pond control unit.

[0408] When multiple battery cells connected in series are repeatedly charged and discharged, between each battery cell... As a result, variations occur in charge and discharge characteristics, causing the capacity (output voltage) of each battery cell to differ. In a series connection of multiple battery cells, the total discharge capacity is less than that of the smallest battery cell. It depends on the capacity of each battery cell. If there is variation in the capacity of each battery cell, the overall capacity during discharge will be smaller. Furthermore, charging based on a battery cell with a smaller capacity may result in insufficient charging. Charging based on a larger capacity battery cell may lead to overcharging.

[0409] Therefore, the battery control unit of an energy storage device having battery cells connected in series is unable to charge. It has a function to equalize the capacity variations between battery cells, which can cause problems such as overcharging. Circuit configurations to equalize the capacitance variations between components include resistor methods, capacitor methods, or inverter methods. There are duct-type methods, but here we use a transistor with a small off-current to handle capacitance variations. I will explain by giving an example of a circuit configuration that can provide these features.

[0410] As a transistor with a low off-current, a transistor having an oxide semiconductor in the channel formation region is... A transistor (OS transistor) is preferred. An OS transistor with a small off-current is used for energy storage. By using it in the circuit configuration of the device's battery control unit, the amount of charge leaking from the battery is reduced. This can suppress the decrease in capacity over time.

[0411] The oxide semiconductor used in the channel formation region is In-M-Zn oxide (where M is Ga, Sn (Y, Zr, La, Ce, or Nd) are used. Used to form oxide semiconductor films. In the target, the atomic ratio of the metal elements is In:M:Zn = x1:y1:z1. and 、 x1 / y1 is between 1 / 3 and 6, and moreover, between 1 and 6, and z1 / y1 is It is preferable that z1 / y1 is between 1 / 3 and 6, and more preferably between 1 and 6. By setting the value to 6 or less, the CAAC-OS film is more easily formed as an oxide semiconductor film. .

[0412] Now, let's discuss the CAAC-OS membrane.

[0413] CAAC-OS film is an oxide semiconductor film having multiple c-axis oriented crystalline regions. .

[0414] Transmission Electron Microscope (TEM) A composite image of the bright-field image and diffraction pattern of the CAAC-OS film was obtained using an optical scope. By observing (also known as high-resolution TEM images), multiple crystalline regions can be identified. On the other hand, high-resolution TEM images also clearly show the boundaries between crystal parts, i.e., grain boundaries. It is not possible to confirm the boundary (also called the boundary). Therefore, the CAAC-OS membrane is This means that a decrease in electron mobility due to grain boundaries is less likely to occur.

[0415] When observing a high-resolution TEM image of the cross-section of the CAAC-OS film from a direction approximately parallel to the sample surface, In the crystalline region, it can be confirmed that the metal atoms are arranged in layers. Each layer of metal atoms is This reflects the unevenness of the surface (also called the surface to be formed) or the upper surface of the CAAC-OS film. It has a specific shape and is arranged parallel to the surface or top surface of the CAAC-OS film to be formed.

[0416] On the other hand, a high-resolution TEM image of the CAAC-OS film plane was observed from a direction approximately perpendicular to the sample surface. Then, it was confirmed that the metal atoms in the crystalline region are arranged in a triangular or hexagonal shape. Yes, it is possible. However, no regularity is observed in the arrangement of metal atoms between different crystalline regions.

[0417] X-ray diffraction (XRD) of CAAC-OS film When structural analysis is performed using the instrument, for example, CAAC-OS having InGaZnO4 crystals is found. Out-of-plane analysis of the film showed a peak at a diffraction angle (2θ) of around 31°. This peak may appear. This peak is attributed to the (009) plane of the InGaZnO4 crystal. Therefore, the crystals of the CAAC-OS film have c-axis orientation, and the c-axis is on the surface to be formed or on the upper surface. It can be confirmed that it is facing in a nearly vertical direction.

[0418] Furthermore, the out-of-plane CAAC-OS film having InGaZnO4 crystals Analysis using this method revealed that in addition to the peak near 2θ = 31°, there is also a peak near 2θ = 36°. In some cases, this may occur. Peaks near 2θ of 36° indicate c-axis orientation in a portion of the CAAC-OS film. This indicates the presence of crystals that do not possess properties. The CAAC-OS film has a 2θ of approximately 31°. It is preferable that a peak is shown and that no peak is shown near 36° for 2θ.

[0419] CAAC-OS films are oxide semiconductor films with low impurity concentrations. The impurities include hydrogen and carbon. These are elements other than the main components of oxide semiconductor films, such as silicon and transition metal elements. In particular, silicon Elements such as condensate, which have a stronger bonding force with oxygen than the metal elements that make up oxide semiconductor films, are acidic. By removing oxygen from the oxide semiconductor film, the atomic arrangement of the oxide semiconductor film is disrupted, reducing its crystallinity. This is a contributing factor. Also, heavy metals such as iron and nickel, argon, and carbon dioxide have a high atomic ratio. Because of its large diameter (or molecular radius), when it is contained within an oxide semiconductor film, the oxide semiconductor film This disrupts the atomic arrangement and reduces crystallinity. Pure substances can act as carrier traps or carrier sources.

[0420] Furthermore, CAAC-OS films are oxide semiconductor films with a low defect level density. For example, oxidation Oxygen vacancies in semiconductor films can act as carrier traps or capture hydrogen. This can sometimes become a source of carrier transmission.

[0421] A low impurity concentration and low defect level density (few oxygen vacancies) are referred to as high-purity intrinsic or This is essentially called high-purity intrinsic. Oxide semiconductors that are high-purity intrinsic or substantially high-purity intrinsic. Because membranes have fewer carrier sources, they can have lower carrier densities. Therefore The transistor using the oxide semiconductor film exhibits electrical characteristics such as a negative threshold voltage. It rarely becomes (also called normally-on). Also, it is of high purity and is essentially high purity. Intrinsically pure oxide semiconductor films have few carrier traps. Therefore, the oxide semiconductor film Transistors using conductive films exhibit less variation in electrical characteristics and are highly reliable. Yes. Furthermore, the charge trapped in the carrier trap of the oxide semiconductor film requires time to be released. This process can last for a long time, sometimes behaving as if it were a fixed charge. Therefore, the impurity concentration... Transistors using oxide semiconductor films with high defect level density have unstable electrical properties. This can sometimes happen.

[0422] Furthermore, transistors using CAAC-OS films exhibit electrical properties when irradiated with visible light or ultraviolet light. Sexual variation is small.

[0423] OS transistors are transistors that have silicon in the channel formation region (Si Because it has a larger band gap compared to a transistor, dielectric breakdown when a high voltage is applied is It is unlikely to occur. When battery cells are connected in series, a voltage of several hundred volts will be generated, In energy storage devices, the circuit configuration of the battery control unit applied to such battery cells includes the following: It is suitable to construct it using the OS transistors described above.

[0424] Figure 43 shows an example of a block diagram of an energy storage device. The energy storage device BT00 shown in Figure 43 is Terminal pair BT01, terminal pair BT02, switching control circuit BT03, switching circuit BT 04, switching circuit BT05, transformer control circuit BT06, transformer circuit BT07, in series It has a battery section BT08 which includes a plurality of connected battery cells BT09.

[0425] Furthermore, in the energy storage device BT00 shown in Figure 43, terminal pair BT01 and terminal pair BT02 are connected. Switching control circuit BT03, switching circuit BT04, switching circuit BT05, and transformer control The part consisting of the control circuit BT06 and the transformer circuit BT07 is called the battery control unit. It can be done.

[0426] The switching control circuit BT03 controls the operation of switching circuits BT04 and BT05. It controls the following. Specifically, the switching control circuit BT03 measures each battery cell BT09 and Based on the voltage, the battery cells to be discharged (discharge battery cell group) and the battery cells to be charged (charge battery cell group) are selected. Determine the battery cell group.

[0427] Furthermore, the switching control circuit BT03 controls the determined group of discharged battery cells and the rechargeable battery cells. Based on the group, control signals S1 and S2 are output. Control signal S1 is a switching signal. The signal is output to circuit BT04. This control signal S1 connects terminal pair BT01 and the group of discharge battery cells. This is a signal that controls the switching circuit BT04 to connect. Also, the control signal S2 is, The signal is output to the switching circuit BT05. This control signal S2 is connected to the terminal pair BT02 and the rechargeable battery. This is a signal that controls the switching circuit BT05 to connect the group of elements.

[0428] Furthermore, the switching control circuit BT03 is connected to the switching circuit BT04, the switching circuit BT05, And based on the configuration of the transformer circuit BT07, between the terminal pair BT01 and the group of discharge battery cells, The terminals of the BT02 and the group of rechargeable battery cells are controlled to connect terminals of the same polarity. The system generates the official signal S1 and the control signal S2.

[0429] This section describes the operation of the switching control circuit BT03 in detail.

[0430] First, the switching control circuit BT03 measures the voltage of each of the multiple battery cells BT09. Then, the switching control circuit BT03, for example, switches the battery cell BT09 with a voltage above a predetermined threshold. High-voltage battery cells (high-voltage cells), BT09 battery cells with a voltage below a predetermined threshold, and low-voltage It is determined to be a battery cell (low-voltage cell).

[0431] Furthermore, various methods are used to determine whether a cell is high-voltage or low-voltage. This is possible. For example, the switching control circuit BT03 is the most important among the multiple battery cells BT09. Each battery cell BT09 is measured using the voltage of the highest or lowest voltage battery cell as a reference. It may also be possible to determine whether 09 is a high-voltage cell or a low-voltage cell. In this case, the switching control circuit BT0 Step 3 determines whether the voltage of each battery cell BT09 is above a predetermined percentage of the reference voltage. By doing so, it is possible to determine whether each battery cell BT09 is a high-voltage cell or a low-voltage cell. Then, based on this determination, the switching control circuit BT03 switches between the discharge battery cell group and the charging battery group. Determine the battery cell group.

[0432] Note that within multiple BT09 battery cells, high-voltage and low-voltage cells are mixed in various states. It is possible. For example, the switching control circuit BT03 is used when high-voltage cells and low-voltage cells are mixed together. The portion where the most high-voltage cells are connected in series is designated as the discharge battery cell group. The switching control circuit BT03 charges the portion where the most low-voltage cells are connected in series. This is a group of battery cells. Furthermore, the switching control circuit BT03 is used for batteries that are close to being overcharged or over-discharged. Cell BT09 is preferentially selected as either a discharge battery cell group or a recharge battery cell group. That's good too.

[0433] Here, an example of the operation of the switching control circuit BT03 in this embodiment will be explained using Figure 44. To clarify, Figure 44 is a diagram illustrating an example of the operation of the switching control circuit BT03. For the sake of explanation, Figure 44 shows an example where four BT09 battery cells are connected in series. explain.

[0434] First, in the example shown in Figure 44(A), the voltages of battery cells a through d are defined as voltages Va through Vd. This shows the case where Va=Vb=Vc>Vd. In other words, three consecutive high Voltage cells a through c and one low-voltage cell d are connected in series. In this case, switching The control circuit BT03 determines three consecutive high-voltage cells a to c as a discharge battery cell group. The switching control circuit BT03 also determines the low-voltage cell d as part of the rechargeable battery cell group. ru.

[0435] Next, the example in Figure 44(B) shows the case where Vc > Va = Vb >> Vd. In other words, two consecutive low-voltage cells a and b, one high-voltage cell c, and one over-discharge A nearby low-voltage cell d is connected in series. In this case, the switching control circuit BT03 The high-voltage cell c is determined to be the discharge battery cell group. Furthermore, the switching control circuit BT03 is... Because low-voltage cell d is close to over-discharge, instead of using the two consecutive low-voltage cells a and b, Voltage cell d is given priority as the group of rechargeable battery cells.

[0436] Finally, the example in Figure 44(C) shows the case where Va > Vb = Vc = Vd. In other words, one high-voltage cell a is connected in series with three consecutive low-voltage cells b through d. In this case, the switching control circuit BT03 switches the high-voltage cell a to the discharge battery cell group. The decision is made. Furthermore, the switching control circuit BT03 charges three consecutive low-voltage cells b through d. This will be determined as a group of battery cells.

[0437] The switching control circuit BT03 is determined as shown in the examples in Figures 44(A) to (C) above. Based on the results, information indicating the group of discharge battery cells to which the switching circuit BT04 is connected is set. The signal control S1 and information indicating the group of rechargeable battery cells to which the switching circuit BT05 is connected The set control signal S2 is sent to switching circuits BT04 and BT05. Output each separately.

[0438] The above is a detailed explanation of the operation of the switching control circuit BT03.

[0439] The switching circuit BT04 responds to the control signal S1 output from the switching control circuit BT03. Then, the destination of the terminal pair BT01 is determined by the switching control circuit BT03, which is the discharge battery. Set it to a group of cells.

[0440] Terminal pair BT01 is composed of the paired terminals F1 and F2. Switching circuit BT0 4. Of these terminals F1 and F2, one is the upstream (high) of the group of discharged battery cells. Connect the positive terminal of battery cell BT09 located on the potential side, and the other end within the group of discharge battery cells. By connecting to the negative terminal of the battery cell BT09, which is located furthest downstream (low potential side), the terminal Set the connection destination for the child BT01. Note that the switching circuit BT04 is set to control signal S1. The location of the discharge battery cells can be recognized using the collected information.

[0441] The switching circuit BT05 responds to the control signal S2 output from the switching control circuit BT03. Then, the connection destination of terminal pair BT02 is determined by the switching control circuit BT03 to the rechargeable battery. Set it to a group of cells.

[0442] Terminal pair BT02 consists of the paired terminals G1 and G2. Switching circuit BT0 5. Of these terminals G1 and G2, one is the most upstream (high) in the group of rechargeable battery cells. Connect the positive terminal of battery cell BT09 located on the potential side, and the other end within the group of rechargeable battery cells. By connecting to the negative terminal of the battery cell BT09, which is located furthest downstream (low potential side), the terminal Set the connection destination for the child BT02. Note that the switching circuit BT05 is set to control signal S2. The information obtained can be used to recognize the location of the battery cell group.

[0443] Figures 45 and 45 show circuit diagrams illustrating example configurations of switching circuits BT04 and BT05. This is shown in 46.

[0444] In Figure 45, the switching circuit BT04 consists of multiple transistors BT10 and bus BT11 It also has BT12. Bus BT11 is connected to terminal F1. Terminal 12 is connected to terminal F2. Multiple transistors BT10 are either source or drain. One of them is connected to buses BT11 and BT12 alternately, one after the other. Furthermore, the source or drain of each of the multiple transistors BT10 is connected to two adjacent ones. It is connected between the BT09 battery cells.

[0445] Of the multiple transistors BT10, the transistor BT10 located at the very top The other end of the source or drain is the positive terminal of battery cell BT09, which is located at the uppermost part of battery section BT08. It is connected to the polarity terminal. Also, it is located at the downstream end of the multiple transistors BT10. The source or drain of transistor BT10 is located at the furthest downstream end of the battery section BT08. It is connected to the negative terminal of the BT09 battery cell.

[0446] The switching circuit BT04 provides control signals S1 to the gates of multiple transistors BT10. Accordingly, one of the multiple transistors BT10 connected to bus BT11, and bus One of the multiple transistors BT10 connected to BT12 is set to conduction. This connects the discharge battery cell group and the terminal pair BT01. The positive terminal of battery cell BT09, which is located in the uppermost part of the cell group, is terminal F1 of the terminal pair or It is connected to either of the F2 cells. It is also the battery located furthest downstream in the group of discharge battery cells. The negative terminal of cell BT09 is the other terminal of the terminal pair, either F1 or F2, i.e., the positive terminal. It connects to the terminal that is not connected to the child.

[0447] It is preferable to use an OS transistor for transistor BT10. Because the off-current is small, the amount of charge leaking from battery cells that do not belong to the discharge battery cell group is small. This reduces the amount of power required, thus suppressing the decrease in capacity over time. Furthermore, OS transistors... Dielectric breakdown is less likely to occur when high voltage is applied. Therefore, the output voltage of the discharge battery cell group is large. Even if you hear it, the transistor BT10, which is in a non-conductive state, is connected to the battery cell BT09 and terminals. It is possible to isolate it from BT01.

[0448] Furthermore, in Figure 45, the switching circuit BT05 consists of multiple transistors BT13 and a current control It has a switch BT14, a bus BT15, and a bus BT16. Buses BT15 and B T16 is positioned between multiple transistors BT13 and the current control switch BT14. The source or drain of each of the multiple transistors BT13 is alternated every other one. They are connected to buses BT15 and BT16. Also, multiple transistors BT13 The source or drain of the other is connected between two adjacent battery cells BT09, respectively. It is being done.

[0449] Of the multiple transistors BT13, the transistor BT13 located at the very top The other end of the source or drain is the positive terminal of battery cell BT09, which is located at the uppermost part of battery section BT08. It is connected to the polarity terminal. Also, it is located at the downstream end of the multiple transistors BT13. The source or drain of transistor BT13 is located at the furthest downstream end of the battery section BT08. It is connected to the negative terminal of the BT09 battery cell.

[0450] Transistor BT13 uses an OS transistor, similar to transistor BT10. It is preferable that the OS transistor has a small off-current and therefore does not belong to the rechargeable battery cell group. This reduces the amount of charge leaking from the battery cell and suppresses the decrease in capacity over time. Yes, it is possible. Furthermore, OS transistors are less prone to dielectric breakdown when high voltage is applied. Therefore... Even if the voltage for charging the battery cells is high, transistor B will remain in a non-conductive state. T13 can be used to insulate the battery cell BT09 to which it is connected from the terminal pair BT02. .

[0451] The current control switch BT14 has a switch pair BT17 and a switch pair BT18. One end of the switch to BT17 is connected to terminal G1. Also, the switch to BT17 The other end is branched by two switches; one switch is connected to bus BT15, and the other... The switch is connected to bus BT16. One end of the switch to BT18 is connected to terminal G2. They are connected. Also, the other end of the switch to BT18 is branched by two switches, One switch is connected to bus BT15, and the other switch is connected to bus BT16. ru.

[0452] The switches in switch pair BT17 and switch pair BT18 are transistor BT1 Similar to transistor 0 and transistor BT13, it is preferable to use an OS transistor.

[0453] The switching circuit BT05 controls the transistor BT13 and the current control according to the control signal S2. By controlling the on / off state combination of the BT14 switch, the rechargeable battery cells Connect the group to the terminal pair BT02.

[0454] The switching circuit BT05, as an example, connects the rechargeable battery cell group and terminal pair BT as follows. Connect to 02.

[0455] The switching circuit BT05 provides control signals S2 to the gates of multiple transistors BT13. Accordingly, connect to the positive terminal of battery cell BT09, which is the most upstream battery cell in the rechargeable battery cell group. The transistor BT13 is made conductive. Also, the switching circuit BT05 is multiple In accordance with the control signal S2 applied to the gates of the transistors BT13, among the group of rechargeable battery cells Transistor BT1 is connected to the negative terminal of battery cell BT09, which is located furthest downstream. Connect 3 to a conductive state.

[0456] The polarity of the voltage applied to terminal pair BT02 is the same as that of the discharge battery cell connected to terminal pair BT01. This can vary depending on the group and the configuration of the BT07 transformer circuit. Also, the charging of the battery cell group To allow current to flow in one direction, terminals of the same polarity must be connected between the BT02 terminal pair and the group of rechargeable battery cells. They need to be connected to each other. Therefore, the current control switch BT14 is controlled by the control signal S2. Depending on the polarity of the voltage applied to terminal pair BT02, switch pair BT17 and switch pair B The T18 is controlled to switch between different connection destinations.

[0457] As an example, a voltage is applied to the terminal pair BT02 such that terminal G1 is the positive terminal and terminal G2 is the negative terminal. Let's explain by listing the conditions under which it is applied. At this time, the battery cell BT0, which is the downstream of the battery unit BT08 If 9 is a group of rechargeable battery cells, the switch to BT17 will, by the control signal S2, the battery It is controlled to connect to the positive terminal of cell BT09, i.e., switch to BT17. The switch connected to bus BT16 is turned ON, and the switch is connected to bus BT17. The switch connected to 15 is turned off. Meanwhile, the switch to BT18 receives the control signal S. According to 2, it is controlled to connect to the negative terminal of the battery cell BT09. That is, The switch connected to the BT15 bus of the switch to BT18 is turned ON, and the switch to The switch connected to the BT16 bus of BT18 is turned off. In this way, the terminal Between the BT02 and the rechargeable battery cell group, terminals with the same polarity are connected. The direction of the current flowing from the terminal pair BT02 is controlled to charge the battery cells. To be controlled.

[0458] Furthermore, the current control switch BT14 is not the switching circuit BT05, but the switching circuit B It may be included in T04.

[0459] Figure 46 shows the configuration of switching circuits BT04 and BT05, which differs from that of Figure 45. This is a circuit diagram illustrating an example.

[0460] In Figure 46, the switching circuit BT04 consists of multiple transistor pairs BT21 and bus BT2 It has 4 and bus BT25. Bus BT24 is connected to terminal F1. BT25 is connected to terminal F2. One end of the multiple transistor pair BT21 is connected to The signal branches off from transistors BT22 and BT23. Either the source or drain of the BT22 is connected to the BT24 bus. Either the source or drain of the converter BT23 is connected to the bus BT25. The other end of each pair of transistors BT21 is connected to two adjacent battery cells BT09. It is connected in between. Of the multiple transistor pairs BT21, the one located at the uppermost position The other end of the transistor pair BT21 is connected to the battery cell BT09, which is located at the uppermost part of the battery section BT08. It is connected to the positive terminal. Also, it is located at the downstream end of the multiple transistor pairs BT21. The other end of the transistor pair BT21 is connected to the battery cell BT located at the downstream end of the battery section BT08. It is connected to the negative terminal of 09.

[0461] The switching circuit BT04 controls transistor BT22 and transistor BT22 in response to the control signal S1. By switching the conduction / non-conduction state of BT23, the relationship between the transistor and BT21 is Switch the connection destination to either terminal F1 or terminal F2. For details, see the transistor. If BT22 is conducting, transistor BT23 will be non-conducting, and its connection point is Terminal F1. On the other hand, if transistor BT23 is conducting, then transistor BT2 Terminal 2 becomes non-conductive, and its connection point is terminal F2. Transistor BT22 and Transistor Which of the BT23 resistors becomes conductive is determined by the control signal S1.

[0462] To connect terminal pair BT01 to the group of discharge battery cells, two transistor pairs BT21 are used. It is used. In detail, the connection of two transistors to BT21 is based on the control signal S1. Once the destinations are determined, the group of discharge battery cells and the terminal pair BT01 are connected. The connections of the two transistors in BT21 are such that one is to terminal F1 and the other is to terminal It is controlled by the control signal S1 to become child F2.

[0463] The switching circuit BT05 consists of multiple transistor pairs BT31 and buses BT34 and B Bus BT34 has T35. Bus BT34 is connected to terminal G1. Bus BT35 is , connected to terminal G2. One end of each pair of transistors BT31 is connected to the transistor It branches off from transistor BT32 and transistor BT33. Transistor BT32 One of the branches is connected to bus BT34. Also, transistor BT33 One of the branched ends is connected to bus BT35. Also, multiple transistors are paired with BT35. The other end of 1 is connected between two adjacent battery cells BT09. Of the number of transistor pairs BT31, the other end of the upstream transistor pair BT31 is It is connected to the positive terminal of battery cell BT09, which is located at the uppermost part of the battery section BT08. Furthermore, among the multiple pairs of transistors BT31, the pair of transistors BT31 located at the furthest downstream The other end is connected to the negative terminal of battery cell BT09, which is located at the downstream end of battery section BT08. ru.

[0464] The switching circuit BT05 switches between transistors BT32 and transistors according to the control signal S2. By switching the conduction / non-conduction state of BT33, the relationship between the transistor and BT31 is Switch the connection destination to either terminal G1 or terminal G2. For details, see the transistor. If BT32 is conducting, transistor BT33 will be non-conducting, and its connection point is Terminal G1. Conversely, if transistor BT33 is conducting, then transistor BT3 Terminal 2 becomes non-conductive, and its connection point is terminal G2. Transistor BT32 and Transistor Which of the BT33 resistors becomes conductive is determined by the control signal S2.

[0465] To connect the terminal pair BT02 to the battery cell group, two transistor pairs BT31 are used. It is used. In detail, the connection of two transistors to BT31 is based on the control signal S2. Once the destinations are determined, the rechargeable battery cells are connected to the BT02 terminal pair. The connections of the two transistor pairs BT31 are such that one is to terminal G1 and the other is to the terminal It is controlled by the control signal S2 to become child G2.

[0466] Furthermore, the connections of the two transistor pairs BT31 are applied to the terminal pair BT02. It is determined by the polarity of the applied voltage. Specifically, terminal G1 is the positive terminal and terminal G2 is the negative terminal. If such a voltage is applied to terminal pair BT02, then the upstream transistor pair BT31 This results in transistor BT32 becoming conductive and transistor BT33 becoming non-conductive. Thus, it is controlled by the control signal S2. On the other hand, the downstream transistor pair BT31 is The control is set such that transistor BT33 is in a conductive state and transistor BT32 is in a non-conductive state. It is controlled by signal S2. Also, terminal G1 is the negative terminal and terminal G2 is the positive terminal. When voltage is applied to terminal pair BT02, the upstream transistor pair BT31 is Transistor BT33 becomes conductive and transistor BT32 becomes non-conductive. It is controlled by the control signal S2. On the other hand, the downstream transistor pair BT31 is Control signal S such that transistor BT32 is in a conducting state and transistor BT33 is in a non-conducting state. Controlled by 2. In this way, between the terminal pair BT02 and the group of rechargeable battery cells, Terminals with opposite polarity are connected. Then, the direction of the current flowing from terminal to terminal BT02 is, The system is controlled to charge the battery cells.

[0467] The transformer control circuit BT06 controls the operation of the transformer circuit BT07. Transformer control circuit BT06 This refers to the number of BT09 battery cells included in the discharge battery cell group and the number of BT09 battery cells included in the recharge battery cell group. Based on the number of battery cells BT09, a transform signal S3 is generated to control the operation of the transformer circuit BT07. It is generated and output to the transformer circuit BT07.

[0468] Note that the number of BT09 battery cells included in the discharge battery cell group is the same as the number of BT09 battery cells included in the recharge battery cell group. If the number of battery cells exceeds the number of BT09 cells, the charging power will be excessively large for the battery cell group. It is necessary to prevent pressure from being applied. Therefore, the voltage transformer control circuit BT06 controls the charging power The transformer circuit BT07 reduces the discharge voltage (Vdis) to a level that allows the battery cells to be charged. It outputs a transform signal S3 to control the voltage.

[0469] Furthermore, the number of BT09 battery cells included in the discharge battery cell group is the same as the number of BT09 battery cells included in the recharge battery cell group. If the number of BT09 battery cells is less than or equal to the number of BT09 battery cells, the amount of charge required to charge the battery cell group will be used. It is necessary to ensure sufficient voltage. Therefore, the transformer control circuit BT06 overloads the battery cell group. Transformer circuit B is configured to increase the discharge voltage (Vdis) within a range where no excess charging voltage is applied. Outputs a transformer signal S3 to control T07.

[0470] Note that the voltage value that constitutes excessive charging voltage is the BT09 battery cell used in the BT08 battery unit. The specifications can be determined in consideration of the product specifications, etc. Furthermore, the BT07 transformer circuit can be used for both step-up and step-down voltage conversion. The applied voltage is then applied to the terminal pair BT02 as the charging voltage (Vcha).

[0471] Here, an example of the operation of the transformer control circuit BT06 in this embodiment is shown in Figures 47(A) to (C) This will be explained using Figures 44(A) to 47(C). This section describes an example of the operation of the BT06 transformer control circuit, which corresponds to a group of electric battery cells and a group of rechargeable battery cells. This is a conceptual diagram for the purpose of [doing something]. Figures 47(A) to (C) show the battery control unit BT41. As shown above, the battery control unit BT41 has terminal pair BT01 and terminal pair BT02, switching control circuit BT03, switching circuit BT04, and switching circuit BT It consists of 05, the transformer control circuit BT06, and the transformer circuit BT07.

[0472] In the example shown in Figure 47(A), as explained in Figure 44(A), three consecutive high-voltage Voltage cells a through c and one low-voltage cell d are connected in series. In this case, see Figure 44( As explained using A), the switching control circuit BT03 discharges high-voltage cells a to c. The battery cell group is determined, and the low-voltage cell d is determined to be the rechargeable battery cell group. Then, the voltage is transformed. The control circuit BT06 is based on the number of battery cells BT09 included in the discharge battery cell group. Based on the ratio of the number of BT09 battery cells included in the rechargeable battery cell group, the discharge voltage (Vd Calculate the conversion ratio N from is to charging voltage (Vcha).

[0473] Note that the number of BT09 battery cells included in the discharge battery cell group is the same as the number of BT09 battery cells included in the recharge battery cell group. If the number of battery cells exceeds the number of BT09 cells, the discharge voltage is not transformed and is applied to the terminal pair BT02. When applied as is, the battery cell BT09 included in the rechargeable battery cell group is transmitted via terminal pair BT02. This could result in an excessive voltage being applied. Therefore, in cases like the one shown in Figure 47(A) Next, we will reduce the charging voltage (Vcha) applied to the terminal pair BT02 to a level lower than the discharge voltage. It is necessary. Furthermore, in order to charge the battery cell group, the charging voltage is the battery cell group The total voltage of the BT09 battery cells included must be greater than that of the transformer control circuit. BT06 is based on the number of BT09 battery cells included in the discharge battery cell group, and the charge The conversion ratio N is set to be greater than the ratio of the number of BT09 battery cells included in the battery cell group.

[0474] The voltage transformer control circuit BT06 is based on the number of battery cells BT09 included in the discharge battery cell group. When this is done, the conversion ratio N is applied to the ratio of the number of BT09 battery cells included in the group of rechargeable battery cells. It is preferable to increase it by about 1 to 10%. At this time, the charging voltage is different from the voltage of the battery cell group. Although the voltage will also increase, in reality the charging voltage will be equal to the voltage of the battery cell group. However, The voltage control circuit BT06 adjusts the voltage of the battery cell group to be equal to the charging voltage according to the conversion ratio N. This will supply current to charge the battery cells. This current is supplied by the BT06 transformer control circuit. The value set will be used.

[0475] In the example shown in Figure 47(A), the number of battery cells BT09 included in the discharge battery cell group is With 3 units, and since there is 1 BT09 battery cell in the rechargeable battery cell group, the voltage transformation control cycle For circuit BT06, the conversion ratio N is calculated to be slightly larger than 1 / 3. Then, the voltage transformation control cycle The circuit BT06 converts the discharge voltage into a charging voltage by stepping down the discharge voltage according to the conversion ratio N, and the resulting transform signal S The signal 3 is output to the transformer circuit BT07. Then, the transformer circuit BT07 responds to the transformer signal S3. The transformed charging voltage is applied to terminal pair BT02. The BT09 battery cell included in the rechargeable battery cell group is charged by the charging voltage.

[0476] Furthermore, in the examples shown in Figures 47(B) and 47(C), the conversion ratio is the same as in Figure 47(A). N is calculated. In the examples shown in Figures 47(B) and 47(C), the discharge battery cell group is The number of BT09 battery cells is less than or equal to the number of BT09 battery cells included in the rechargeable battery cell group. Therefore, the conversion ratio N will be 1 or greater. Thus, in this case, the voltage transformer control circuit BT06 is A transform signal S3 is output, which increases the discharge voltage and converts it into a charging voltage.

[0477] The transformer circuit BT07 applies a discharge voltage to the terminal pair BT01 based on the transformer signal S3. It converts the voltage to a charging voltage. Then, the transformer circuit BT07 converts the charged voltage to the terminals BT Apply to 02. Here, the transformer circuit BT07 is between terminal pair BT01 and terminal pair BT02. It is electrically isolated. As a result, the transformer circuit BT07 is the most in the group of discharge battery cells. The absolute voltage of the negative terminal of battery cell BT09 located downstream, and the lowest voltage among the group of rechargeable battery cells. This prevents short circuits caused by the difference in absolute voltage between the negative terminal of battery cell BT09 located in the current. Furthermore, as described above, the transformer circuit BT07 transforms the group of discharge battery cells based on the transformer signal S3. The discharge voltage, which is the total voltage, is converted to the charge voltage.

[0478] Furthermore, the BT07 transformer circuit is, for example, an isolated DC (Direct Current)-D transformer. A C converter or the like can be used. In this case, the transformer control circuit BT06 is an isolated DC converter. -The signal that controls the on / off ratio (duty cycle) of the DC converter is the transform signal S3. By outputting this signal, the charging voltage converted by the BT07 transformer circuit is controlled.

[0479] Isolated DC-DC converters include flyback, forward, and RCC types. (Ringing Choke Converter) method, push-pull method, half Bridge and full-bridge designs exist, but they depend on the desired output voltage level. The appropriate method will then be selected.

[0480] Figure 48 shows the configuration of the BT07 transformer circuit using an isolated DC-DC converter. The DC-DC converter BT51 has a switch section BT52 and a transformer section BT53. The BT52 switch unit switches the operation of the isolated DC-DC converter on and off. It is a switch, for example, a MOSFET (Metal-Oxide-Semiconductor) Field-effect transistors and bipolar transistors This is achieved using a switch, etc. Furthermore, the switch unit BT52 is connected to the transformer control circuit BT06. Based on the transform signal S3 that controls the on / off ratio, an isolated DC-DC converter is used. The ON and OFF states of BT51 are periodically switched. Note that the switch unit BT52 is... Various configurations are possible depending on the type of isolated DC-DC converter used. Part BT53 converts the discharge voltage applied from terminal pair BT01 into a charging voltage. The transformer section BT53 operates in conjunction with the on / off state of the switch section BT52, and The discharge voltage is converted to a charging voltage according to the on / off ratio. This charging voltage is used in the switch section BT. In a 52-period switching cycle, the longer the time spent in the ON state, the larger the value. The voltage is such that the ON state time is short during the switching cycle of the switch unit BT52. It becomes smaller. Note that when using an isolated DC-DC converter, the transformer section BT53 Within the structure, terminal pair BT01 and terminal pair BT02 can be isolated from each other.

[0481] The processing flow of the energy storage device BT00 in this embodiment will be explained using Figure 49. Figure 4 Figure 9 is a flowchart showing the processing flow of the energy storage device BT00.

[0482] First, the energy storage device BT00 acquires the voltage measured for each of the multiple battery cells BT09. Step S101). Then, the energy storage device BT00 equalizes the voltage of multiple battery cells BT09. It is determined whether the start condition for the operation is met (step S102). This start condition is, For example, the difference between the maximum and minimum voltage measured for each of the multiple battery cells BT09 is predetermined This can be determined by whether or not it is above a threshold, etc. If this starting condition is not met, (step S 102:NO), Since the voltage of each battery cell BT09 is balanced, storage The electrical device BT00 will not perform the subsequent processing. On the other hand, if the start condition is met (step S102:YES), the energy storage device BT00 performs a process to equalize the voltage of each battery cell BT09. The process is carried out. In this process, the energy storage device BT00 performs the following based on the measured voltage of each cell: It is determined whether each battery cell BT09 is a high-voltage cell or a low-voltage cell (step S103). Based on the determination result, the energy storage device BT00 determines the discharge battery cell group and the recharge battery cell group. Determine (step S104). Furthermore, the energy storage device BT00 determines the group of discharged battery cells. Control signal S1 sets the terminal pair BT01 as the connection destination, and the determined group of rechargeable battery cells is connected to the terminal A control signal S2 is generated to be set as the connection destination for the child BT02 (step S105). The BT00 unit receives the generated control signals S1 and S2 from the switching circuit BT04 and The output is sent to the switching circuit BT05. Then, the switching circuit BT04 sends the terminals The terminals BT01 and the group of discharge battery cells are connected, and the switching circuit BT05 switches the terminals BT0 2 is connected to the group of discharge battery cells (step S106). Also, the energy storage device BT00 is The number of BT09 battery cells included in the discharge battery cell group and the number of BT09 battery cells included in the recharge battery cell group Based on the number of BT09 units, a transform signal S3 is generated (step S107). Based on the voltage transformation signal S3, the energy storage device BT00 applies a discharge voltage to the terminal pair BT01. This is converted to a charging voltage and applied to the terminal pair BT02 (step S108). Charge is transferred from the group of battery cells to the group of rechargeable battery cells.

[0483] Also, although the flowchart in Figure 49 shows multiple steps in order, each step The execution order of the steps is not limited to the order in which they are listed.

[0484] As described above, according to this embodiment, when transferring charge from a group of discharge battery cells to a group of rechargeable battery cells Unlike the capacitor system, which temporarily stores charge from a group of discharge battery cells, the rechargeable battery cells... It does not require a configuration that releases to the group. This eliminates the charge transfer efficiency per unit time. The efficiency can be improved. Also, the switching circuits BT04 and BT05 Therefore, among the discharge battery cell group and the rechargeable battery cell group, the battery cells connected to the transformer circuit are individually selected. It can be switched to.

[0485] Furthermore, the transformer circuit BT07 controls the number of battery cells BT09 included in the discharge battery cell group. Based on the number of battery cells BT09 included in the rechargeable battery cell group, markings are made on the terminal pair BT01. The applied discharge voltage is converted into a charging voltage and applied to the terminal pair BT02. Regardless of how the BT09 battery cells on the charging and discharging sides are selected, charge transfer is performed without any problems. It can be expressed.

[0486] Furthermore, OS transistors are used for transistors BT10 and BT13. As a result, leakage occurs from battery cell BT09, which does not belong to the rechargeable battery cell group or the dischargeable battery cell group. This reduces the amount of charge that does not contribute to charging and discharging. The decrease in capacitance 9 can be suppressed. Also, OS transistors are Si transistors Compared to that, the variation in thermal properties is smaller. As a result, the temperature of the battery cell BT09 rises. However, normal operation such as switching between conductive and non-conductive states according to control signals S1 and S2 It can be made to work.

[0487] This embodiment can be implemented in appropriate combination with other embodiments. [Examples]

[0488] In this embodiment, the amount of moisture inside the outer casing of the energy storage device was measured when the energy storage device was repeatedly bent. I will now state the results.

[0489] The exterior was constructed using the four types of films shown in Table 1 of Embodiment 1. As a result, a thin storage battery as shown in Embodiment 2 was fabricated. Here, a storage device is provided for each outer casing. We made three of each.

[0490] The positive electrode consisted of a 20 μm thick aluminum current collector with an 80 μm thick positive electrode active material layer formed on one side. The electrode consisted of an 18 μm thick copper current collector with an 82 μm negative electrode active material layer formed on either one or both sides. The pallet used was 25 μm thick polypropylene. Lithium cobalt oxide was used as the positive electrode active material. Graphite was used as the negative electrode active material.

[0491] A laminate was fabricated by alternately stacking positive electrodes, separators, and negative electrodes. The configuration consists of six layers of positive electrode active material and six layers of negative electrode active material facing each other.

[0492] Next, the stacked tab regions of the positive electrode are connected to the positive electrode leads, and the stacked tab regions of the negative electrode are connected to the negative electrode leads. Next, the positive electrode, separator, and negative electrode were alternately stacked. The layers were sandwiched between outer films, and two sides were sealed by heat.

[0493] Next, 1800 μL of PC was injected, and the remaining side was sealed. Through the above process, storage An electrical device was fabricated. In this embodiment, no electrolyte such as lithium salt was added to the energy storage device. It doesn't function as a PC, but if you pour electrolyte into it instead, it will charge and discharge as an energy storage device. It is possible.

[0494] Next, a bending test was performed on the energy storage device. The testing apparatus used for bending stretches in the depth direction. It has a cylindrical support with a radius of curvature of 40 mm. The center of the energy storage device is directly above the support. It is installed as follows. The testing device has arms that extend in the left and right directions. The tip of the arms is held. It is mechanically connected to the plate. By moving the tip of the arm up and down, it moves along the support. This allows the holding plate to be bent. The bending test of the energy storage device involves bending the energy storage device between two holding plates. This is done while the object is held between the arms. Therefore, by moving the tip of the arm up and down, the cylindrical support is... The power storage device can be bent along the body. Specifically, the tip of the arm can be bent downwards. By doing so, the energy storage device can be bent with a radius of curvature of 40 mm. By performing this with the energy storage device sandwiched between two holding plates, any unwanted forces other than bending are stored. This prevents the force from being applied to the device. Furthermore, it ensures that the bending force is applied uniformly to the entire energy storage device. It is possible to obtain it.

[0495] The bending test conditions were: bending with a radius of curvature of 40 mm to 150 mm, and each bending cycle was 10 The process was performed at intervals of seconds. The bending was done 10,000 times.

[0496] After performing a bending test, a visual inspection was conducted, and it was found that the sealing of the outer casing was in the case of comparative sample C1. The vicinity of the part (for example, the region corresponding to region 509b in Figure 20, etc.) (for example, region 561 in Figure 24) In areas corresponding to, for example, sample A2 compared to the comparative sample It was able to suppress wrinkles better than C1.

[0497] Next, a storage test was conducted on the energy storage device that had undergone bending tests. Specifically, it had a pressure adjustment mechanism. The mixture was kept in a container with water at 130°C for 24 hours.

[0498] Next, one side of the energy storage device that underwent the storage test was cut open, and 1800 μL of PC was injected. Then, after the added solvent was allowed to permeate the entire interior of the outer casing with PC, the solvent inside the outer casing was dissolved. The fluid was squeezed out and recovered.

[0499] Next, the Karl Fischer moisture meter MKC-610-DT (manufactured by Kyoto Electronics Manufacturing Co., Ltd.) for coulometric titration. The water content of the recovered solvent was measured using [a specific method / tool]. The results are shown in Figure 50.

[0500] In the energy storage device using comparative sample C1, which was not embossed, the moisture concentration was 350p. Some energy storage devices had readings higher than pm, exceeding 900 ppm. Energy was stored by repeatedly bending the device. It is believed that cracks or other damage occurred in the device's exterior, reducing its airtightness and allowing moisture to enter the exterior. On the other hand, in the energy storage device using embossed samples A1 to A3, the moisture concentration is generally It was less than 300 ppm. The rigidity was reduced by the embossing process. It is believed that the occurrence of cracks in the exterior body caused by repeated bending was suppressed.

[0501] Furthermore, comparing samples A1 to A3, sample A2 had the lowest moisture content. i. As shown in Table 2, the strain at the fracture point in samples A1 and A2 is different from that in sample A3. It is larger and less prone to fracture. Sample A2 has lower rigidity than sample A1, and It is believed that the best results were obtained because it was less prone to fracture than sample A3. [Examples]

[0502] In this embodiment, the rigidity of a film that has been embossed was evaluated.

[0503] As sample B1, a 51 μm thick piece of stainless steel (SUS304 was used in this case) was used on both sides. A film coated with a resin layer was used. The thickness of sample B1 was 113 μm. Sample B1, which has been embossed, will be designated as sample B2. The surface of the film after embossing. The difference between the maximum and minimum heights of the surface was 0.5 mm.

[0504] Tensile tests were performed on samples B1 and B2 to determine stiffness k, stiffness modulus G, and parameters. The results of calculating -G' are shown in Table 3. The strain ε and force P at the fracture point are also shown in Table 3. vinegar.

[0505] [Table 3]

[0506] In sample B2, embossing was applied to determine the stiffness k, stiffness modulus G, and parameter G'. We were able to reduce it to 53% of that of sample B1. In addition, we were able to increase the strain ε at the fracture point. This was achieved. Furthermore, compared to the film used in Example 1, the strain ε at the fracture point was smaller. The result was a high stiffness modulus G. As a metal material used in the film, further Young's modulus By using a lower metal, the strain ε at the fracture point can be further increased, and the shear modulus G can also be lowered. It may be possible.

[0507] Next, using sample B2 as the outer casing, a thin battery as shown in Embodiment 2 is used as the energy storage device. Three of these were fabricated. The components and fabrication conditions of the storage batteries were as described in Example 1.

[0508] When bending tests were conducted on the energy storage devices, two of the three energy storage devices showed signs of solvent leakage after the test. A liquid leak was observed. Sample B2, which was used as the outer casing in this example, was the same as in Example 1. Because it has higher rigidity compared to the film used as the outer casing, the outer casing is more prone to cracking. It is thought that... [Explanation of symbols]

[0509] BT00 Power storage device BT01 terminal pair BT02 terminal pair BT03 control circuit BT04 Switching Circuit BT05 Switching Circuit BT06 Transformer Control Circuit BT07 Transformer Circuit BT08 battery part BT09 battery cell BT14 Current Control Switch BT51 Isolated DC-DC Converter BT52 Switch Section BT53 Transformer Section F1 terminal F2 terminal G1 terminal G2 terminal SW1 Switch SW2 Switch SW3 Switch 10 films 10a Convex part 10b protrusion 10c space 11 areas 50 film 51 film 52 film 53 Embossing Roll 53a Convex part 54 rolls 55 Embossing Roll 55a Convex part 56 Embossed Plate 56a Convex part 56b Recess 57 Embossed Plate 57a Convex part 57b recess 60 Direction of travel 61 Arrow 62 Arrows 101 Current collector 102 Active material layer 103 Active material 104 Binding agent 111 Positive electrode 111a positive electrode 115 Negative electrode 115a negative electrode 121 Positive electrode current collector 122 Cathode active material layer 123 Separator 125 Negative electrode current collector 126 Negative electrode active material layer 130 Electrode assembly 131 Electrode assembly 321 Graphene compounds 331 areas 332 areas 333 areas 351 depth 352 pitch 353 depth 354 distance 355 film thickness 356 Bottom thickness 357 Height 500 Energy Storage Devices 500a area 500c area 500d area 501 Positive electrode current collector 502 Positive electrode active material layer 503 Positive electrode 504 Negative electrode current collector 505 Negative electrode active material layer 506 negative electrode 507 Separator 508 Electrolyte 509 Exterior 509a area 509b area 509c area 510 Positive lead electrode 511 Negative lead electrode 512 Welding Area 513 Curved section 514 Sealing part 531 distance 533 distance 541 Structure 551 Display section 552 enclosures 554 Space 561 area 571 area 572 areas 700 equipment 900 Circuit Boards 910 Labels 911 terminal 912 Circuit 913 Storage Battery 914 Antenna 915 Antenna 916 layers 917 layers 918 Antenna 919 terminal 920 Display device 921 Sensor 922 terminals 951 terminal 952 terminals 981 film 982 film 990 Battery 991 Exterior 992 Exterior 993 Wound body 994 negative electrode 995 positive electrode 996 Separator 997 Lead Electrode 998 Lead Electrode 1700 curved surface 1701 Plane 1702 Curve 1703 Radius of curvature 1704 Center of curvature 1800 Center of curvature 1801 film 1802 radius of curvature 1803 film 1804 radius of curvature 7100 Portable Display Device 7101 enclosure 7102 Display section 7103 Operation Buttons 7104 Energy storage device 7200 Mobile Information Terminal 7201 enclosure 7202 Display section 7203 Band 7204 Buckle 7205 Operation Buttons 7206 Input / output terminal 7207 Icons 7300 display device 7304 Display section 7400 mobile phones 7401 enclosure 7402 Display section 7403 Operation Buttons 7404 External connection port 7405 Speaker 7406 Microphone 7407 Energy storage device 7408 Lead Electrode 7409 Current collector 8000 display device 8001 enclosure 8002 Display section 8003 Speaker section 8004 Energy Storage Device 8021 Charging device 8022 Cable 8024 Energy storage device 8100 Lighting device 8101 enclosure 8102 Light source 8103 Energy Storage Device 8104 Ceiling 8105 Side wall 8106 floor 8107 Window 8200 indoor unit 8201 enclosure 8202 Air outlet 8203 Energy Storage Device 8204 Outdoor unit 8300 Electric Refrigerator / Freezer 8301 enclosure 8302 Refrigerator door 8303 Freezer door 8304 Energy storage device 8400 automobiles 8401 Headlight 8406 Electric motor 8500 automobiles 9600 Tablet devices 9625 Switch 9626 Switch 9627 Power switch 9628 Operation switch 9629 Fastener 9630 cabinet 9630a enclosure 9630b enclosure 9631 Display section 9631a Display section 9631b Display section 9632a area 9632b area 9633 Solar Cell 9634 Charge / Discharge Control Circuit 9635 Energy Storage Unit 9636 DC-DC converter 9637 Converter 9638 Operation Keys 9639 button 9640 Moving parts

Claims

[Claim 1] The electronic device has a display unit and an energy storage device. The aforementioned energy storage device has an outer casing, The exterior body has a first region and a second region having a thinner maximum thickness compared to the first region. An electronic device having a circuit board in a position overlapping with the second region.

Images