Secondary batteries, electronic devices

Abstract

To provide a lithium-ion secondary battery with high capacity and excellent charge / discharge cycle characteristics. Provides a rechargeable battery with high capacity. Provides a rechargeable battery with excellent charge and discharge characteristics. Charged at high voltage. To provide a secondary battery in which capacity degradation is suppressed even when the state is maintained for a long period of time. [Solution] The system comprises a positive electrode, a negative electrode, an electrolyte, and an outer casing, the positive electrode having a positive electrode active material, and the positive electrode The active material contains lithium, cobalt, oxygen, magnesium, and fluorine, and the positive electrode active material is The number of magnesium atoms present is 0.001 times the number of cobalt atoms present in the positive electrode active material. The ratio is 0.1 or less, and the positive electrode active material has a region with a layered rock salt type crystal structure, and electrolysis The liquid is an ionic liquid, and the outer casing has a metal layer and a polymer layer laminated on the metal layer. Furthermore, the polymer layer is a secondary battery having a region that comes into contact with the electrolyte.

Description

[Technical Field]

[0001] One aspect of the present invention relates to a product, a method, or a method of manufacture. Alternatively, one aspect of the present invention relates to a product Processes, machines, manufacturers, or compositions of matter This relates to semiconductor devices, display devices, light-emitting devices, energy storage devices, lighting devices, and This relates to electronic devices or methods for manufacturing them. In particular, positive The present invention relates to active materials, secondary batteries, electronic devices having secondary batteries, and vehicles having secondary batteries. .

[0002] Alternatively, one aspect of the present invention relates to an energy storage system having a secondary battery and a battery control circuit. Alternatively, one aspect of the present invention relates to electronic equipment having an energy storage system, and to a vehicle.

[0003] In this specification, the term "energy storage device" refers to all elements and devices that have an energy storage function. For example, lithium-ion secondary batteries and other rechargeable batteries (also called secondary batteries) This includes muon capacitors and electric double-layer capacitors.

[0004] Furthermore, in this specification, "electronic equipment" refers to all devices that have an energy storage device, and the energy storage device is All electronic devices, including electro-optical devices and information terminal devices with energy storage systems, are considered electronic equipment. [Background technology]

[0005] In recent years, various energy storage devices such as lithium-ion secondary batteries, lithium-ion capacitors, and air batteries have been developed. Development of new devices is actively underway. In particular, lithium-ion batteries, which have high power output and high energy density, are being developed. The next battery is used in mobile phones, smartphones, tablets, or laptop computers, etc. Personal digital assistants, portable music players, digital cameras, medical devices, next-generation clean energy - Automobiles (hybrid vehicles (HV), electric vehicles (EV), plug-in hybrid vehicles ( With the development of the semiconductor industry, the demand for rechargeable energy sources such as PHVs (plug-in hybrid vehicles) is rapidly expanding. As a source of energy, it has become indispensable in today's information society.

[0006] The characteristics required of lithium-ion secondary batteries include further increases in energy density, These improvements include enhanced cycle characteristics, safety in various operating environments, and improved long-term reliability.

[0007] Therefore, in order to improve the cycle characteristics and increase the capacity of lithium-ion secondary batteries, positive electrode activity Improvements to the material are being considered (Patent Documents 1 and 2). Also, the crystal of the positive electrode active material. Research on the structure has also been conducted (Non-Patent Documents 1 to 3).

[0008] Non-patent document 4 describes the physical properties of metal fluorides.

[0009] X-ray diffraction (XRD) is one of the techniques used to analyze the crystal structure of positive electrode active materials. ICSD (Inorganic Crystal Structural Impulse) is introduced in Patent Document 5. By using a photodata database, it is possible to analyze XRD data. can. [Prior art documents] [Patent Documents]

[0010] [Patent Document 1] Japanese Patent Publication No. 2002-216760 [Patent Document 2] Japanese Patent Publication No. 2006-261132 [Non-patent literature]

[0011] [Non-Patent Document 1] Toyoki Okumura et al, “Correlation of lithium ion distribution and X-ray absorption near-edge structure in O3-and O2-lithium cobalt oxides from first-principle calculation”, Journal of Materials Chemistry, 2012, 22, p.17340-17348 [Non-Patent Document 2] Motohashi, T. et al, “Electronic phase diagram of the layered cobalt oxide system LixCoO2(0.0≦x≦1.0)”, Physical Review B, 80(16);165114 [Non-Patent Document 3] Zhaohui Chen et al, “Staging Phase Transitions in LixCoO2”, Journal of The Electrochemical Society, 2002, 149(12) A1604-A1609 [Non-Patent Document 4] WE Counts et al, “Flouride Model Systems: II, The Binary Systems CaF2-BeF2, MgF2-BeF2, and LiF-MgF2”, Journal of the American Ceramic Society,(1953) 36[1] 12-17. Fig.01471 [Non-Patent Document 5] Belsky, A. et al., “New developments in the Inorganic Crystal Structure Database (ICSD): accessibility in support of materials research and design”, Acta Cryst., (2002) B58 364-369 [Overview of the project] [Problems that the invention aims to solve]

[0012] One aspect of the present invention is a lithium-ion secondary battery with high capacity and excellent charge-discharge cycle characteristics, One of the objectives of this invention is to provide a method for producing the same. Alternatively, one aspect of this invention is rapid charging One of the objectives is to provide a rechargeable secondary battery and a method for manufacturing the same. One aspect of the present invention aims to provide a high-capacity secondary battery and a method for manufacturing the same. Alternatively, one aspect of the present invention provides a secondary battery with excellent charge-discharge characteristics and a method for manufacturing the same. One of the challenges is to ensure that even when a high-voltage charge is maintained for a long period of time, One of the objectives is to provide a secondary battery in which the decrease in quantity is suppressed, and a method for manufacturing the same. Alternatively, one aspect of the present invention provides a safe or highly reliable secondary battery and a method for manufacturing the same. One of the objectives is to provide a solution that prevents capacity degradation even at high temperatures. Alternatively, one aspect of the present invention provides a solution that prevents capacity degradation even at high temperatures. One of the objectives is to provide a secondary battery with suppressed emissions and a method for manufacturing the same. One aspect of the invention aims to provide a long-life secondary battery and a method for manufacturing the same. do.

[0013] One aspect of the present invention allows for rapid charging, operation at high temperatures, and increased charging voltage for energy efficiency. To provide a high-performance, safe, long-lasting, and extremely superior rechargeable battery. This will be one of the issues to address.

[0014] One aspect of the present invention relates to a lithium-ion secondary battery with high capacity and excellent charge-discharge cycle characteristics. One of the objectives is to provide highly active materials and methods for producing them. Alternatively, to provide a highly productive method. One objective is to provide a method for producing a positive electrode active material. Alternatively, one aspect of the present invention is to provide a method for producing a positive electrode active material. When used in lithium-ion secondary batteries, the decrease in capacity during charge-discharge cycles is suppressed. One objective of this invention is to provide a positive electrode active material. Alternatively, one aspect of this invention relates to a charge at high voltage. A positive electrode active material in which the leaching of transition metals such as cobalt is suppressed even when the state is maintained for a long period of time. One of the objectives is to provide [this].

[0015] Alternatively, one aspect of the present invention relates to a novel substance, active material particles, energy storage device, or a method for producing the same. One of the objectives is to provide [this].

[0016] Furthermore, the description of these problems does not preclude the existence of other problems. The embodiments do not need to solve all of these problems. It is possible to extract other issues from the description of the requested terms. [Means for solving the problem]

[0017] One aspect of the present invention comprises a positive electrode, a negative electrode, an electrolyte, and an outer casing, wherein the positive electrode comprises a positive electrode active material. The positive electrode active material has lithium, cobalt, oxygen, magnesium, and fluorine, and the positive electrode active The number of magnesium atoms in the substance is 0.00 times the number of cobalt atoms in the positive electrode active material. The ratio is between 1 and 0.1, and the positive electrode active material has regions with a layered rock salt-type crystalline structure. The electrolyte has an ionic liquid, and the outer casing has a metal layer and a polymer layer laminated on the metal layer. The polymer layer has a region that is in contact with the electrolyte, making it a secondary battery.

[0018] Furthermore, in the above configuration, the ionic liquid is imidazolium cati, which is represented by the general formula (G1). It has ON, R 1 R represents an alkyl group with 1 to 4 carbon atoms. 2 ~R 4 That Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 5 is, Alki A group consisting of two or more atoms selected from C, O, Si, N, S, and P. It is preferable to represent a chain.

[0019] [ka]

[0020] Furthermore, in the above configuration, the ionic liquid is pyridinium cathodic, represented by the general formula (G2). It has R 6 This is an alkyl group, or an atom selected from C, O, Si, N, S, P. R represents a main chain composed of two or more elements. 7 ~R 11 Each of them independently consists of a hydrogen atom or Preferably, represents an alkyl group having 1 to 4 carbon atoms.

[0021] [ka]

[0022] Furthermore, in the above configuration, it is preferable that the ionic liquid has a quaternary ammonium cation. It's nice.

[0023] In addition, in the above configuration, the quaternary ammonium cation is one or more selected from general formula (G4), general formula (G5 ), and general formula (G6), and R 12 to R 17 and R 18 to R 24 each independently represents an alkyl group having 1 to 20 carbon atoms, a methoxy group, a methoxy methyl group, a methoxyethyl group, or a hydrogen atom, n and m are 1 or more and 3 or less and α is 0 or more and 6 or less, β is 0 or more and 6 or less, and X or Y is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, or a linear or branched alkoxyalkyl group having 1 to 4 carbon atoms as a substituent.

[0024]

Chemical formula

[0025]

Chemical formula

[0026]

Chemical formula

[0027] In addition, in the above configuration, the ionic liquid has a tertiary sulfonium cation represented by general formula (G7), and R to R 25 to R 27 each independently represents a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a main chain composed of two or more selected from the atoms C, O, Si, N, S, P, preferably.

[0028] ​​​​​​​​​​ [ka]

[0029] Furthermore, in the above configuration, the ionic liquid is a quaternary phosphonium ion represented by the general formula (G8). It has thione, R 32 ~R 35 Each of these independently consists of a hydrogen atom or a carbon atom with one or more carbon atoms. From alkyl groups with 4 or fewer members, or phenyl groups, or atoms of C, O, Si, N, S, or P It is preferable to represent a main chain composed of two or more selected elements.

[0030] [ka]

[0031] Furthermore, in the above configuration, (FSO2)2N is used as the anion of the ionic liquid. - or (CF 3SO2)2N - It is preferable that it has

[0032] Furthermore, in the above configuration, (FSO2)2N is used as the anion of the ionic liquid. - or (CF 3SO2)2N - It is preferable that the negative electrode has graphite.

[0033] Alternatively, one aspect of the present invention comprises a positive electrode, a negative electrode, an electrolyte, and an outer casing, wherein the positive electrode is a positive electrode active material The positive electrode active material has the properties of lithium, cobalt, oxygen, magnesium, and fluorine. The positive electrode active material has regions with a layered rock salt-type crystalline structure, and the electrolyte is an ionic liquid. Ionic liquids include aromatic cations, quaternary ammonium cations, and tertiary sulfonium cations. It has one or more cations selected from ON and quaternary phosphonium cations, and the outer layer The body has a metal layer and a polymer layer laminated on the metal layer, and the polymer layer is in contact with the electrolyte. It has a region, the negative electrode has graphite, and the battery voltage becomes 4.5V in a 25°C environment. After constant current charging, and then constant voltage charging until the current value becomes 0.01C, the positive electrode is connected to CuK When analyzed by powder X-ray diffraction using α1 rays, 2θ was between 19.10° and 19.50°. A secondary battery having diffraction peaks at 2θ between 45.45° and 45.65°. That is the case.

[0034] Furthermore, in the above configuration, (FSO2)2N is used as the anion of the ionic liquid. - or (CF 3SO2)2N - It is preferable that it has

[0035] Alternatively, one aspect of the present invention comprises a positive electrode, a negative electrode, and an electrolyte, wherein the positive electrode comprises a positive electrode active material. The positive electrode active material has lithium, cobalt, and oxygen, and the temperature during charging is the first temperature If the temperature is above a certain temperature and below the second temperature, the upper limit voltage for charging shall be the first value, and during charging... If the temperature is above the second temperature, the upper limit voltage for charging will be set to the second value, and the first temperature will be 5°C. The first temperature is less than 15°C, the second temperature is 25°C or more and less than 55°C, and the first value is equal to the second value. A secondary battery whose voltage is 0.02V or higher than the first value, and whose first value is between 4.45V and 4.6V. ru.

[0036] Furthermore, in the above configuration, it is preferable that the positive electrode active material contains magnesium and fluorine. stomach.

[0037] Furthermore, in the above configuration, it is preferable that the negative electrode has graphite.

[0038] Alternatively, one aspect of the present invention comprises a secondary battery as described in any one of the above, and a temperature sensor. It is an electronic device.

[0039] Alternatively, one aspect of the present invention comprises a secondary battery as described in any one of the above, and a temperature sensor. It is a vehicle that does that. [Effects of the Invention]

[0040] According to one aspect of the present invention, a lithium-ion secondary battery with high capacity and excellent charge-discharge cycle characteristics is provided. The present invention can provide a method for producing the same. Furthermore, according to one aspect of the present invention, rapid charging We can provide a rechargeable battery and a method for manufacturing the same. A secondary battery in which capacity degradation is suppressed even when the state is maintained for a long period of time, and a method for manufacturing the same. It can be provided. Furthermore, according to one aspect of the present invention, a safe or highly reliable secondary battery The present invention can provide a method for producing the same. Furthermore, according to one aspect of the present invention, at high temperatures This invention provides a secondary battery in which capacity degradation is suppressed, as well as a method for manufacturing the same. Furthermore, according to one aspect of the present invention, a rechargeable battery with a long lifespan and a method for manufacturing the same are provided. It is possible.

[0041] According to one aspect of the present invention, rapid charging is possible, it can be used at high temperatures, and the charging voltage is increased to increase energy. - To provide extremely superior rechargeable batteries that are high-density, safe, and have a long lifespan. It is possible.

[0042] According to one aspect of the present invention, a lithium-ion secondary battery with high capacity and excellent charge-discharge cycle characteristics is provided. This can provide a positive electrode active material and a method for producing the same. Furthermore, it can provide a positive electrode active material with high productivity. A method for producing a substance can be provided. Furthermore, according to one aspect of the present invention, lithium ion A positive electrode active material that, when used in secondary batteries, suppresses the decrease in capacity during charge-discharge cycles. It can be provided. Furthermore, according to one aspect of the present invention, it is possible to maintain a high-voltage charged state for a long period of time. Even in such cases, it is possible to provide a positive electrode active material in which the elution of transition metals such as cobalt is suppressed. Cut.

[0043] Alternatively, one aspect of the present invention relates to a novel substance, active material particles, energy storage device, or a method for producing the same. We can provide this.

[0044] Furthermore, the description of these effects does not preclude the existence of other effects. The embodiment does not necessarily have to have all of these effects. Furthermore, other effects are... This will become clear from the description in the specification, drawings, claims, etc., and the specification, drawings Furthermore, it is possible to extract other effects from the descriptions in the claims and other documents. [Brief explanation of the drawing]

[0045] [Figure 1] Figure 1 shows an example of a secondary battery. [Figure 2] Figure 2A shows an example of a cross-section of a secondary battery. Figure 2B shows an example of a cross-section of a secondary battery. [Figure 3] Figure 3 shows an example of a secondary battery. [Figure 4] Figure 4A shows an example of an electrode. Figure 4B shows an example of a method for manufacturing a secondary battery. Figure 4C shows an example of a method for manufacturing a secondary battery. [Figure 5] Figure 5A shows an example of a method for manufacturing a secondary battery. Figure 5B shows an example of a method for manufacturing a secondary battery. [Figure 6]Figure 6A shows an example of an electrode. Figure 6B shows an example of a method for manufacturing a secondary battery. Figure 6C shows an example of a method for manufacturing a secondary battery. Figure 6D shows an example of a method for manufacturing a secondary battery. [Figure 7] Figure 7A shows an example of the configuration of a secondary battery. Figure 7B shows an example of the configuration of a secondary battery. Figure 7C shows an example of the configuration of a secondary battery. [Figure 8] Figure 8 shows an example of a secondary battery configuration. [Figure 9] Figure 9A shows an example of the battery pack configuration. Figure 9B shows an example of the battery pack configuration. [Figure 10] Figure 10A shows an example of the battery pack configuration. Figure 10B shows an example of the battery pack configuration. Figure 10C shows an example of the battery pack configuration. Figure 10D shows an example of the battery pack configuration. [Figure 11] Figure 11A illustrates a bendable secondary battery. Figure 11B illustrates a bendable secondary battery. Figure 11C illustrates a bendable secondary battery. Figure 11D illustrates a bendable secondary battery. Figure 11E illustrates a bendable secondary battery. [Figure 12] Figure 12A is a diagram illustrating the radius of curvature. Figure 12B is a diagram illustrating the radius of curvature. Figure 12C is a diagram illustrating the radius of curvature. [Figure 13] Figure 13A is a diagram illustrating the radius of curvature. Figure 13B is a diagram illustrating the radius of curvature. Figure 13C is a diagram illustrating the radius of curvature. Figure 13D is a diagram illustrating the radius of curvature. [Figure 14] Figure 14A shows an example of a cylindrical secondary battery. Figure 14B shows an example of a cylindrical secondary battery. Figure 14C shows an example of multiple cylindrical secondary batteries. Figure 14D shows an example of an energy storage system with multiple cylindrical secondary batteries. [Figure 15] Figure 15A shows an example of the battery pack configuration. Figure 15B shows an example of the battery pack configuration. Figure 15C shows an example of the battery pack configuration. [Figure 16] Figure 16A shows an example of the configuration of an energy storage system. Figure 16B shows an example of a method for manufacturing an energy storage system. Figure 16C shows an example of a method for manufacturing an energy storage system. Figure 16D shows an example of a method for manufacturing an energy storage system. [Figure 17] Figure 17A is a diagram illustrating an example of a vehicle. Figure 17B is a diagram illustrating an example of a vehicle. Figure 17C is a diagram illustrating an example of a vehicle. [Figure 18] Figure 18A is a diagram illustrating an example of a vehicle. Figure 18B is a diagram illustrating an example of an energy storage system. [Figure 19] Figure 19A is a diagram illustrating an example of electronic equipment. Figure 19B is a diagram illustrating an example of electronic equipment. Figure 19C is a diagram illustrating an example of electronic equipment. [Figure 20] Figure 20 is a diagram illustrating an example of an electronic device. [Figure 21] Figure 21A illustrates an example of electronic equipment. Figure 21B illustrates an example of electronic equipment. Figure 21C illustrates an example of a rechargeable battery. Figure 21D illustrates an example of electronic equipment. Figure 21E illustrates an example of a rechargeable battery. Figure 21F illustrates an example of electronic equipment. Figure 21G illustrates an example of electronic equipment. [Figure 22] Figure 22 illustrates an example of an electronic device. [Figure 23] Figure 23A is a diagram illustrating an example of an electronic device. Figure 23B is a diagram illustrating an example of an electronic device. Figure 23C is a diagram illustrating an example of an electronic device. [Figure 24] Figure 24A shows the cycle characteristics of a secondary battery. Figure 24B shows the cycle characteristics of a secondary battery. [Figure 25] Figure 25 shows the cycle characteristics of a secondary battery. [Figure 26] Figure 26A shows the charge and discharge curve of a secondary battery. Figure 26B shows the charge and discharge curve of a secondary battery. [Figure 27]Figure 27A shows the charge and discharge curve of a secondary battery. Figure 27B shows the charge and discharge curve of a secondary battery. [Figure 28] Figure 28A shows the charge and discharge curve of a secondary battery. Figure 28B shows the charge and discharge curve of a secondary battery. [Figure 29] Figure 29A shows the charge and discharge curve of a secondary battery. Figure 29B shows the charge and discharge curve of a secondary battery. [Figure 30] Figure 30A shows the charge and discharge curve of a secondary battery. Figure 30B shows the charge and discharge curve of a secondary battery. [Figure 31] Figure 31 shows the charge and discharge curves of a secondary battery. [Modes for carrying out the invention]

[0046] The embodiments of the present invention will be described in detail below with reference to the drawings. However, the present invention is... Not limited to the following description, the form and details can be modified in various ways, as any person skilled in the art would know. This is easily understood. Furthermore, the present invention shall be interpreted as being limited to the contents of the embodiments described below. It's not something that can be done.

[0047] Furthermore, in this specification, crystal planes and directions are indicated by Miller indices. Table of crystal planes and directions In crystallography, numbers are preceded by a superscript bar, but in this specification, due to limitations on application notation, numbers are not preceded by a superscript bar. Sometimes, instead of placing a bar above the number, a minus sign (-) is placed before the number to represent it. Furthermore, the individual orientations indicating directions within a crystal are [ ], and the collective orientation showing all equivalent directions is < >The individual planes that represent crystal planes are ( ), and the set of planes with equivalent symmetry are {}. To express

[0048] In this specification, segregation refers to the segregation of a solid composed of multiple elements (e.g., A, B, C). This refers to the phenomenon in which a certain element (for example, B) is distributed non-uniformly in space.

[0049] In this specification, the surface layer of particles such as active material refers to the region from the surface up to approximately 10 nm. It can also be said that surfaces created by cracks or fissures are considered surfaces. Furthermore, the region deeper than the surface layer is called a surface. It's called the interior.

[0050] In this specification, etc., the layered rock salt type crystal structure of a composite oxide containing lithium and a transition metal This structure has a rock salt-type ionic arrangement in which cations and anions are arranged alternately, and it contains transition metals and Because lithium is arranged in a regular pattern to form a two-dimensional plane, two-dimensional diffusion of lithium is possible. This refers to the crystal structure. It may contain defects such as vacancies in cations or anions. Also, layers... Strictly speaking, the rock salt crystal structure is a structure in which the lattice of the rock salt crystal is distorted. be.

[0051] Furthermore, in this specification, a rock salt-type crystal structure is defined as a structure in which cations and anions are arranged alternately. This refers to a structure that contains certain elements. It is also acceptable for there to be deficiencies in cations or anions.

[0052] Furthermore, in this specification, etc., the pseudo-spinel type of composite oxide containing lithium and a transition metal The crystal structure is R-3m, and although it is not a spinel-type crystal structure, cobalt, Magnesium and other ions occupy the 6-coordinate position of oxygen, and the arrangement of cations is similar to that of a spinel. This refers to a crystal structure that exhibits symmetry. Note that pseudo-spinel crystal structures are found in light elements such as lithium. It can occupy the oxygen 4-coordinate position, and in this case as well, the ion arrangement is symmetrical, similar to the spinel type. It has a sexual nature.

[0053] Furthermore, the pseudo-spinel type crystal structure has Li randomly placed between the layers, but is a CdCl2 type structure. It can also be said that it is a crystal structure similar to the crystal structure. This is a crystal similar to the CdCl2 type. The structure is such that when lithium nickelate is charged to a charging depth of 0.94 (Li 0.06 NiO 2) A layered rock with a crystal structure similar to that of pure lithium cobaltate, or rich in cobalt. It is known that salt-type cathode active materials do not usually adopt this crystal structure.

[0054] Layered rock salt crystals, and the anions of rock salt crystals, have a cubic close-packed structure (face-centered cubic lattice structure). It takes this form. It is also presumed that in pseudo-spinel crystals, the anions adopt a cubic close-packed structure. When they come into contact, there exists a crystal plane in which the orientation of the cubic close-packed structure composed of anions is aligned. However, the space group of layered rock salt crystals and pseudo-spinel crystals is R-3m, and rock salt crystals The space groups of crystals Fm-3m (the space group of typical rock salt crystals) and Fd-3m (the simplest space group) Because it is different from the space group of rock salt crystals with symmetry, the mirror of the crystal plane that satisfies the above conditions The index differs between layered rock salt crystals, pseudo-spinel crystals, and rock salt crystals. In layered rock salt crystals, pseudo-spinel crystals, and rock salt crystals, the structure is composed of anions. When the orientations of the resulting cubic close-packed structure are aligned, it can be said that the crystal orientations are roughly the same. be.

[0055] A secondary battery has, for example, a positive electrode and a negative electrode. The positive electrode is made up of a positive electrode active material. The positive electrode active material is, for example, a substance that performs a reaction that contributes to the charge and discharge capacity. The substance may include, in part, substances that do not contribute to the charge and discharge capacity.

[0056] In this specification, the positive electrode active material of one aspect of the present invention is a positive electrode material, or a positive electrode active material for a secondary battery. It may be expressed as electrode material, etc. Also, in this specification, etc., positive electrode active material of one aspect of the present invention The quality preferably contains a compound. Furthermore, in this specification, etc., the positive electrode of one aspect of the present invention The active material preferably has a composition. Furthermore, in this specification, etc., one aspect of the present invention The positive electrode active material preferably has a composite structure.

[0057] (Embodiment 1) This embodiment describes an example of a secondary battery according to one aspect of the present invention.

[0058] In secondary batteries, increasing the charging voltage can increase the discharge capacity. It can also increase energy density.

[0059] On the other hand, with secondary batteries, increasing the charging voltage results in a significant decrease in capacity with each charge-discharge cycle. This can happen. For example, at high charging voltages, the crystal structure of the positive electrode active material may become unstable. be.

[0060] For example, a material having a metal (hereinafter referred to as metal A) that acts as a carrier ion is used as the positive electrode active material. Let's consider the case where metal A is present. During the charging reaction, metal A is detached from the positive electrode active material. Increase the charging voltage. As a result, a large amount of metal A is detached from the positive electrode active material, and the crystal structure of the positive electrode active material changes significantly. In some cases, this may occur. If the change in crystal structure due to the insertion and removal of metal A is irreversible, then gradual The crystal structure may collapse, and a significant decrease in capacity may occur with each charge-discharge cycle.

[0061] A secondary battery using a positive electrode active material according to one aspect of the present invention can be repeatedly charged at a high charging voltage. Even when this is done, the breakdown of the crystal structure is suppressed, and the decrease in capacity associated with charge-discharge cycles is suppressed. It is possible.

[0062] Furthermore, as shown in the examples described later, in a secondary battery using a positive electrode active material according to one embodiment of the present invention, Furthermore, a positive electrode having a positive electrode active material according to one embodiment of the present invention is used as the positive electrode, and the main solution of the electrolyte is By using an ionic liquid as the fluid medium, the decrease in capacity associated with charge-discharge cycles is further suppressed. It was found that this resulted in remarkably superior characteristics for secondary batteries.

[0063] Ionic liquids are salts composed of a combination of cations and anions. Ionic liquids are found at room temperature. It is sometimes called a molten salt.

[0064] Ionic liquids have low volatility and flammability, and are stable over a wide temperature range. Because it is less likely to volatilize, it can suppress the expansion of secondary batteries caused by gas generation from the electrolyte. Therefore, the secondary battery operates stably even at high temperatures. Furthermore, it has low flammability and is flame-retardant. It is a sexual thing.

[0065] By using ionic liquids, it is possible to operate at high temperatures and realize a highly safe secondary battery. It can be expressed.

[0066] For example, organic compounds such as diethyl carbonate (DEC) and ethyl methyl carbonate (EMC). In solvents, its boiling point is lower than 150°C and it is highly volatile, therefore, when used at high temperatures... Gas may be generated, causing the casing of the secondary battery to expand. Also, organic solvents should be used below 50°C. It may have a flash point.

[0067] On the other hand, ionic liquids have low volatility and can be reacted at temperatures lower than the temperature at which decomposition and other reactions occur, for example, 3 It can be said to be extremely stable down to around 0°C.

[0068] Thus, it can be seen that ionic liquids are stable even at high temperatures. On the other hand, when constructing a secondary battery... Other components, such as the positive electrode active material, negative electrode active material, and outer casing, change at high temperatures. In addition, especially in cases of irreversible changes, this can lead to a significant decrease in the capacity of secondary batteries.

[0069] For example, charging at high temperatures can cause irreversible changes in the crystal structure of the material constituting the positive electrode active material. When this occurs, significant degradation occurs in secondary batteries. For example, during the charge-discharge cycle. A significant decrease in capacity may occur as a result. This can happen when the temperature is high and the charging voltage is also high. The crystal structure of the positive electrode may become even more unstable.

[0070] In a secondary battery according to one aspect of the present invention, the crystal structure is maintained at high charging voltage and high temperature. However, by using an extremely stable positive electrode active material, when the temperature is high and the charging voltage is also high... Even in this case, excellent properties can be achieved, and the effects of ionic liquids can be fully demonstrated. This can be achieved. In other words, remarkable results can be obtained by using the configuration of a secondary battery according to one aspect of the present invention. Such improved properties are found by combining with a positive electrode active material according to one embodiment of the present invention. ru.

[0071] Furthermore, the positive electrode active material in one aspect of the present invention preferably contains element X, as will be described later. Preferably, the positive electrode active material has a halogen in addition to element X. Alternatively, by having a halogen in addition to element X, ions on the surface of the positive electrode active material This suggests that the reaction with liquids is suppressed. As mentioned above, ionic liquids are extremely stable even at high temperatures. On the other hand, in a secondary battery according to one aspect of the present invention, the range of reaction potential is extremely wide. In a wide range of reaction potentials, there is a concern that the active material surface may react with the ionic liquid. By using a positive electrode active material according to one aspect of the present invention, the reaction with the ionic liquid is suppressed. Furthermore, this suggests the possibility of realizing even more stable secondary batteries.

[0072] By using the configuration of a secondary battery according to one aspect of the present invention, for example, the upper limit voltage for charging can be increased. This also makes it possible to realize a rechargeable battery that can be recharged repeatedly. For example, charging The upper limit voltage is preferably 4.45V or higher, more preferably 4.47V or higher, and even more preferably The voltage should be 4.49V or higher, for example around 4.5V, and the secondary battery should be capable of repeated charging. A pond can be realized. Furthermore, by using the configuration of a secondary battery according to one aspect of the present invention... This significantly suppresses the decrease in discharge capacity even when the upper limit voltage for charging is increased.

[0073] In one embodiment of the present invention, the configuration of a secondary battery is such that the temperature during charging is t(1)[°C] or higher. 2) If the temperature is below [℃], the upper limit voltage for charging shall be v(1)[V], and during charging If the temperature is t(2)[°C] or higher, the upper limit voltage for charging shall be v(2)[V]. This is preferable. Here, t(1) is preferably a value between 5 and 15, and t(2) is It is preferable that the value be between 25 and 55. Also, v(1) should be 0.02 or less greater than v(2). It is preferable that the value is large, and that v(1) is between 4.45 and 4.6. preferable.

[0074] By using the configuration of a secondary battery according to one aspect of the present invention, for example, at high temperatures of 42°C or higher Furthermore, it is possible to realize a secondary battery that can be repeatedly charged at a high charging voltage. Yes, it is possible. For example, the ambient temperature can be set to 42°C or higher, and the upper limit voltage for charging can be set to preferably 4.37V or higher. More preferably 4.40V or higher, even more preferably 4.42V or higher, even more preferably The secondary battery should be 4.44V or higher, for example around 4.45V, and capable of repeated charging. It is possible to create a battery.

[0075] Furthermore, it is possible to realize excellent secondary batteries even at even higher temperatures. For example, 4 2°C to 200°C, or 42°C to 180°C, or 42°C to 150°C Below, or 42°C to 120°C, or 42°C to 100°C, or 4 In some cases, it may be possible to create a secondary battery that operates stably between 2°C and 90°C.

[0076] A secondary battery according to one aspect of the present invention, for example, performs a discharge of a cumulative charge amount of 57,000 mAh / g. The subsequent discharge capacity is 160mAh / g or more. Here, for example, the discharge capacity is 0.2C. It is preferable that the measurement be performed using the positive electrode active material weight. Furthermore, the cumulative charge and discharge capacity are measured using the positive electrode active material weight. It is preferable to calculate it on a per-unit basis.

[0077] Furthermore, in one embodiment of the present invention, a secondary battery has a charging voltage of 4.5V at 25°C, The discharge capacity after 300 charge cycles is 160mAh / g or more. For example, The discharge capacity is preferably measured at 0.2C. Also, the cumulative charge and discharge capacity are measured. The capacity is preferably calculated per unit weight of the positive electrode active material.

[0078] Furthermore, a secondary battery according to one embodiment of the present invention is preferably used in combination with a battery control circuit. The battery control circuit preferably has a function to control charging, for example. Control, for example, involves monitoring the parameters of a secondary battery and changing the charging conditions according to its state. This refers to monitoring the following parameters of a secondary battery: voltage, current, and temperature. Examples include degree, charge quantity, impedance, etc.

[0079] Furthermore, a secondary battery according to one embodiment of the present invention is preferably used in combination with a sensor. The sensor can measure, for example, displacement, position, velocity, acceleration, angular velocity, rotational speed, distance, light, liquid, magnetism, Temperature, chemical substances, sound, time, hardness, electric field, electric current, voltage, power, radiation, flow rate, humidity, gradient It is preferable to have the ability to measure one or more of the following: temperature, vibration, odor, and infrared radiation. It seems so.

[0080] Furthermore, in one embodiment of the present invention, the secondary battery controls charging according to a value measured by a sensor. It is preferable that this be done. An example of controlling a secondary battery using a temperature sensor will be described later. .

[0081] [Cathode active material] The following describes a positive electrode active material that is preferable for use in a secondary battery according to one embodiment of the present invention. .

[0082] <Structure of positive electrode active material> The positive electrode active material preferably contains a metal (hereinafter referred to as element A) that acts as a carrier ion. Element A can be, for example, alkali metals such as lithium, sodium, and potassium, and calcium. Elements from Group 2, such as beryllium and magnesium, can be used.

[0083] In the positive electrode active material, carrier ions are released from the positive electrode active material during charging. If there is a large separation, there are more ions that contribute to the capacity of the secondary battery, and the capacity increases. On the other hand, element A If there is a lot of desorption, the crystalline structure of the compound in the positive electrode active material is more likely to collapse. Disruption of the crystal structure can lead to a decrease in discharge capacity with charge-discharge cycles. The positive electrode active material of this embodiment contains element X, so that carrier ions are removed during charging of the secondary battery. In some cases, the collapse of the crystal structure during separation is suppressed. For example, element X may have a part of it that is element A It is substituted in the position of element X. Magnesium, calcium, zirconium, lanthanum Elements such as barium can be used. Also, for example, copper, potassium, sodium can be used as element X. Elements such as lium and zinc can be used. Also, two of the elements listed above can be used as element X. The above can be used in combination.

[0084] Furthermore, in one embodiment of the present invention, it is preferable that the positive electrode active material has a halogen in addition to element X. It is preferable that the positive electrode active material has halogens such as fluorine and chlorine. The presence of halogens may facilitate the substitution of element X at the position of element A.

[0085] In one embodiment of the present invention, the positive electrode active material contains element X, or, in addition to element X, a halogen is present. If present, the electrical conductivity on the surface of the positive electrode active material may be suppressed.

[0086] Furthermore, the positive electrode active material according to one aspect of the present invention changes its valency due to charging and discharging of the secondary battery. The present invention comprises a metal (hereinafter referred to as element M). Element M is, for example, a transition metal. The highly active material, for example, has one or more of the elements M, such as cobalt, nickel, and manganese, and in particular It contains cobalt. Furthermore, at the position of element M, there is no change in valence, such as aluminum, and the element It may also have elements that can take the same valency as element M, more specifically, for example, trivalent typical elements. The aforementioned element X may be substituted, for example, at the position of element M. Also, the positive electrode activity of one aspect of the present invention If the substance is an oxide, element X may be substituted at the position of oxygen.

[0087] As a positive electrode active material in one aspect of the present invention, for example, a lithium composite acid having a layered rock salt-type crystal structure It is preferable to use a methyl ion. More specifically, for example, lithium having a layered rock salt crystal structure. As a composite oxide, lithium cobalt oxide, lithium nickelate, nickel, manganese Lithium composite oxide containing cobalt, nickel, cobalt, and aluminum Lithium composite oxides, etc., can be used. Furthermore, these positive electrode active materials are space group It is preferable that it be represented as R-3m.

[0088] In a cathode active material having a layered rock salt crystal structure, increasing the charging depth causes the crystal structure to collapse. This can occur. Here, a breakdown of the crystal structure refers to, for example, a shift in layers. In irreversible cases, repeated charging and discharging may lead to a decrease in the capacity of the secondary battery. ru.

[0089] In one aspect of the present invention, the positive electrode active material contains element X, which for example increases the depth of charge. Furthermore, the shifting of the above layers is suppressed. By suppressing the shifting, the volume change during charging and discharging is reduced. The change can be reduced. Therefore, the positive electrode active material of one aspect of the present invention has excellent cycle The characteristics can be realized. Furthermore, the positive electrode active material in one embodiment of the present invention is in a high-voltage charged state. It can adopt a stable crystal structure in this context. Therefore, the positive electrode active material of one aspect of the present invention is suitable for high voltage applications. When the charging state is maintained, a short circuit may be less likely to occur. This is preferable because it improves safety.

[0090] In one embodiment of the present invention, the positive electrode active material is in a fully discharged state and a state charged at a high voltage. In this case, the difference in volume when comparing the change in crystal structure and the same number of transition metal atoms is small. Sai.

[0091] The positive electrode active material in one aspect of the present invention has the chemical formula AM y O Z The case where it can be expressed as (y>0, z>0) Yes, there are. For example, lithium cobalt oxide is sometimes represented as LiCoO2. Also, for example, Ni Lithium kellate is sometimes represented as LiNiO2.

[0092] In a positive electrode active material according to one aspect of the present invention, which contains element X, when the charging depth is 0.8 or greater, It is represented by the space group R-3m, and although it is not a spinel-type crystal structure, it is composed of elements M (for example, cobalt). Ions of elements such as ether (e.g., magnesium) occupy the 6-coordinate position of oxygen, and cations The arrangement may have symmetry similar to that of a spinel. This structure is referred to as a pseudo-spinel in this specification. This is called a spinel-type crystal structure. Note that in pseudo-spinel-type crystal structures, light elements such as lithium are oxygen-based. It can occupy four coordination positions, and in this case as well, the ion arrangement exhibits symmetry similar to that of the spinel type. do.

[0093] The desorption of carrier ions during charging destabilizes the structure of the positive electrode active material. (Pseudo-spinel) The crystal structure can maintain high stability even after carrier ions have been removed. It can be said that it has that kind of structure.

[0094] In the present invention, when the depth of charge is high, the positive electrode active material having a pseudo-spinel type structure is used in a secondary battery. By using it, for example, with the potential of lithium metal as the reference, 4.57V to 4.65V At voltages less than 4.59V or between 4.59V and 4.63V, for example around 4.6V, the positive terminal The active material has a stable structure, which suppresses capacity reduction due to charging and discharging. In batteries, for example, when graphite is used as the negative electrode active material, the voltage of the secondary battery is favorable. More preferably 4.45V or more and 4.6V or less, more preferably 4.47V or more and less than 4.55V. More preferably, the positive electrode activity is active at 4.49V or higher and less than 4.53V, for example, around 4.5V. The material has a stable structure, which helps to suppress capacity degradation due to charging and discharging.

[0095] Furthermore, the pseudo-spinel type crystal structure has Li randomly placed between the layers, but is a CdCl2 type structure. It can also be said that it is a crystal structure similar to the crystal structure. This is a crystal similar to the CdCl2 type. The structure is such that when lithium nickelate is charged to a charging depth of 0.94 (Li 0.06 NiO 2) A layered rock with a crystal structure similar to that of pure lithium cobaltate, or rich in cobalt. It is known that salt-type cathode active materials do not usually adopt this crystal structure.

[0096] Layered rock salt crystals, and the anions of rock salt crystals, have a cubic close-packed structure (face-centered cubic lattice structure). It takes this form. It is also presumed that in pseudo-spinel crystals, the anions adopt a cubic close-packed structure. When they come into contact, there exists a crystal plane in which the orientation of the cubic close-packed structure composed of anions is aligned. However, the space group of layered rock salt crystals and pseudo-spinel crystals is R-3m, and rock salt crystals The space groups of crystals Fm-3m (the space group of typical rock salt crystals) and Fd-3m (the simplest space group) Because it is different from the space group of rock salt crystals with symmetry, the mirror of the crystal plane that satisfies the above conditions The index differs between layered rock salt crystals, pseudo-spinel crystals, and rock salt crystals. In the case of layered rock salt type crystals, pseudo-spinel type crystals, and rock salt type crystals, when the orientations of the cubic close-packed structures formed by anions are aligned, it can be said that the crystal orientations are generally consistent. The pseudo-spinel type crystal structure can be shown by the coordinates of cobalt and oxygen in the unit cell within the range of Co(0, 0, 0.5), O(0, 0, x), where 0.20 ≤ x ≤ 0.25.

[0097] 0, 0.5), O(0, 0, x), 0.20 ≤ x ≤ 0.25. 0, 0.5), O(0, 0, x), 0.20 ≤ x ≤ 0.25.

[0098] In the cathode active material of one embodiment of the present invention, the difference between the volume of the unit cell in the volume at a charge depth of 0 and the volume per unit cell of the pseudo-spinel type crystal structure at a charge depth of 0.82 is preferably 2.5% or less, and more preferably 2.2% or less.

[0099] In the pseudo-spinel type crystal structure, diffraction peaks appear at 2θ = 19.30 ± 0.20° (19.10° or more and 19. 50° or less), and 2θ = 45.55 ± 0.10° (45.45° or more and 45.65° or less). More specifically, sharp diffraction peaks appear at 2θ = 19.30 ± 0.10° (1 9.20° or more and 19.40° or less), and 2θ = 45.55 ± 0.05° (45.50 ° or more and 45.60 or less).

[0100] The cathode active material of one embodiment of the present invention has a pseudo-spinel type crystal structure when charged at a high voltage, but not all of the particles need to have a pseudo-spinel type crystal structure. It may contain other crystal structures, or some may be amorphous. However, when Rietveld analysis is performed on the XRD pattern, it is preferably 50 wt% or more, more preferably 60 wt% or more, and even more preferably 66 wt% or more of the pseudo-spinel type crystal structure. ​​​​​i. The pseudo-spinel type crystal structure is 50 wt% or more, more preferably 60 wt% or more, and further Preferably, if the content is 66 wt% or more, it can be made into a cathode active material with sufficiently excellent cycle characteristics. can.

[0101] The number of atoms of element X is preferably 0.001 times or more and 0.1 times or less the number of atoms of element M, and 0.0 A value greater than 1 and less than 0.04 is more preferable, and around 0.02 is even more preferable. The concentration of element X is determined, for example, by performing elemental analysis of the entire particle of the positive electrode active material using ICP-MS. It may be a value obtained by hand, or it may be based on the values ​​of the raw material composition during the process of manufacturing the positive electrode active material. stomach.

[0102] If element M is cobalt and nickel, the number of atoms of cobalt and nickel The ratio of nickel atoms (Ni) to the sum (Co+Ni), Ni / (Co+Ni), is: It is preferable that the value be less than 0.1, and more preferably 0.075 or less.

[0103] The positive electrode active material according to one aspect of the present invention is not limited to the materials listed above.

[0104] For example, a composite oxide having a spinel-type crystal structure can be used as the positive electrode active material. Furthermore, for example, a polyanionic material can be used as the positive electrode active material. Examples of anionic materials include materials with an olivine-type crystal structure and materials with a nasicone-type crystal structure. Examples include, for example, a material containing sulfur can be used as the positive electrode active material. Cut.

[0105] As a material having a spinel-type crystal structure, for example, a composite oxide represented by LiM2O4 It can be used. Preferably, the element M is Mn. For example, LiMn2O 4 can be used. Also, by having Ni in addition to Mn as element M, two The discharge voltage of the next battery may improve, and the energy density may also improve, which is desirable. Lithium-containing materials having a spinel-type crystal structure containing manganese, such as iMn2O4, have a small amount of Amount of lithium nickelate (LiNiO2 or LiNi 1-x M x O2 (M=Co, Al, etc.) Mixing ) can improve the characteristics of the secondary battery, which is preferable.

[0106] A polyanionic material may include, for example, oxygen, metal A, metal M, and element Z. A composite oxide can be used. Metal A is one or more of Li, Na, and Mg, and metal M is Fe, Mn, Co, Ni, Ti, V, Nb (one or more), and element Z is S, P, Mo, W. As and Si are one or more of the above.

[0107] For example, composite materials (general formula LiMPO4(M)) have an olivine-type crystal structure. Use one or more of the following: Fe(II), Mn(II), Co(II), Ni(II). This is possible. Typical examples of general formula LiMPO4 include LiFePO4, LiNiPO4, and L iCoPO4, LiMnPO4, LiFe a Ni b PO4, LiFe a Co b PO4, L iFe a Mn b PO4, LiNi a Co b PO4, LiNi a Mn b PO4(a+b is 1 Below, 0 <a<1、0<b<1)、LiFe c Ni d Co e PO4, LiFe c Nid M n e PO4, LiNi c Co d Mn e PO4 (where c + d + e is less than or equal to 1, 0 < c < 1, 0 < d < 1, 0 < e < 1), LiFe f Ni g Co h Mn i PO4 (where f + g + h + i is less than or equal to 1, 0 < f < 1, 0 < g < 1, 0 < h < 1, 0 < i < 1), etc., lithium compounds can be used. It is possible. <00009​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​m Ni n Mn q SiO4, Li (2-j) Ni m Co n Mn q SiO4 (where 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 (where 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 for this.

[0109] Also, A x M2(XO4)3 (A = Li, Na, Mg, M = Fe, Mn, Ti, V, Nb , X = S, P, Mo, W, As, Si) Nasicon-type compounds represented by the general formula can be used for this. Examples of Nasicon-type compounds include Fe2(MnO4)3, Fe2(SO4)3, Li3Fe2(PO4)3, etc. Also, as the positive electrode active material, compounds represented by the general formula Li2MPO4F, Li 2MP2O7, Li5MO4 (M = Fe, Mn) can be used for this.

[0110] Also, as the positive electrode active material, perovskite-type fluorides such as NaFeF3, FeF3, metal chalcogenides (sulfides, selenides, tellurides) such as TiS2, MoS2, LiMV O4, etc., oxides having an inverse spinel-type crystal structure, vanadium oxide-based (V2O5, V6 O 13 , LiV3O8, etc.), manganese oxides, organic sulfur compounds, etc. can be used as materials.

[0111] Also, as the positive electrode active material, the general formula LiMBO3 (M is Fe(II), Mn(II), C A borate-based material represented by o(II)) may also be used.

[0112] Examples of materials having sodium include NaFeO2 and Na 2 / 3 [Fe 1 / 2 Mn1 / 2 O2, Na 2 / 3 [Ni 1 / 3 Mn 2 / 3 O2, Na2Fe2(SO4)3, N a3V2(PO4)3, Na2FePO4F, NaVPO4F, NaMPO4 (M is F e(II), Mn(II), Co(II), Ni(II)), Na2FePO4F, Na 4Co3(PO4)2P2O7, etc., sodium-containing oxides may be used as the positive electrode active material as well.

[0113] Also, a lithium-containing metal sulfide may be used as the positive electrode active material. For example, Li2Ti S3, Li3NbS4, etc. may be mentioned.

[0114] As the positive electrode active material of one aspect of the present invention, two or more of the materials listed above may be mixed and used as well.

[0115] In a general secondary battery, as the charging voltage increases, the structure of the positive electrode active material becomes unstable and the element M contained in the positive electrode active material may dissolve into the electrolyte. When the element M dissolves into the electrolyte for example, the capacity of the positive electrode may decrease. The decrease in the capacity of the positive electrode leads to a decrease in the capacity of the secondary battery. Also, the element M dissolved in the electrolyte may deposit on the surface of the negative electrode of the secondary battery of the secondary battery. The inhibition of the reaction of the deposited element M on the negative electrode leads to a decrease in the capacity of the secondary battery as well.

[0116] In a secondary battery using the positive electrode active material of one aspect of the present invention, even at a high charging voltage, the positive electrode active material Because its structure is stable, it suppresses the elution of element M from the positive electrode active material into the electrolyte. It is possible.

[0117] [Electrolyte] A secondary battery according to one aspect of the present invention preferably has an electrolyte. The electrolyte in the pond consists of an ionic liquid and a salt containing a metal that acts as a carrier ion. This is preferable.

[0118] When the metal that acts as the carrier ion is lithium, the metal that acts as the carrier ion contains Examples of salts include LiN(FSO2)2, LiN(CF3SO2)2, and LiN(C4F9 SO2)(CF3SO2), LiN(C2F5SO2)2, LiC(FSO2)3, Li C(CF3SO2)3, LiC(C2F5SO2)3, LiCF3SO3, LiC4F9 SO3, LiAsF6, LiBF4, LiAlCl4, LiSCN, LiBr, LiI, Li2SO4, Li2B 10 Cl 10 Li2B 12 Cl 12 LiPF6, LiClO One or more of the 4th class lithium salts, or any combination and ratio thereof. It can be used.

[0119] Metal salts with fluorosulfonate anions and fluoroalkylsulfonate anions are particularly preferred. There are cases where it is difficult, especially (C n F 2n+1 SO2)2N - (n=0 or greater, 3 or less) The metal salts formed with amide anions exhibit high stability at high temperatures and high resistance to oxidation-reduction reactions. There are cases where this is preferable.

[0120] Ionic liquids consist of cations and anions, including organic cations and anions. (Electrolyte) Organic cations used include imidazolium cations and pyridinium cations, etc. Aromatic cations, quaternary ammonium cations, tertiary sulfonium cations, and quaternary cations Aliphatic onium cations such as phosphonium cations are examples. Also, used in electrolytes Anions include monovalent amide anions, monovalent methide anions, and fluorosulfones. Acid anions, perfluoroalkyl sulfonate anions, tetrafluoroborate anions n, perfluoroalkylborate anion, hexafluorophosphate anion, ma Other examples include perfluoroalkyl phosphate anions.

[0121] In addition, the electrolyte may contain, for example, ethylene carbonate (EC) and propylene. Carbonate (PC), butylene carbonate, chloroethylene carbonate, vinylene Carbonate, γ-butyrolactone, γ-valerolactone, dimethyl carbonate (DM) C) DEC, EMC, methyl formate, methyl acetate, ethyl acetate, methyl propionate, pr Ethyl ropionate, propyl propionate, methyl butyrate, 1,3-dioxane, 1,4- Dioxane, dimethoxyethane (DME), dimethyl sulfoxide, diethyl ether, Methyl diglyme, acetonitrile, benzonitrile, tetrahydrofuran, sulfolane One of these, such as sultone, or two or more of these, mixed in any combination and ratio. It may have an aprotic solvent.

[0122] Furthermore, the electrolyte contains vinylene carbonate (VC), propane sultone (PS), tert- Butylbenzene (TBB), fluoroethylene carbonate (FEC), lithium bis( Oxalate borate (LiBOB), succinonitrile, adiponitrile, fluoro Additives such as benzene, cyclohexylbenzene, and dinitrile compounds such as biphenyl are added. It may be added. The concentration of the added material should be, for example, 0.1 wt% to 5 wt% relative to the total solvent. It should be less than or equal to a percent.

[0123] An ionic liquid having an imidazolium cation is, for example, represented by the following general formula (G1): An ionic liquid can be used. In general formula (G1), R 1 is a carbon number of 1 or less The above 4 represents alkyl groups, R 2 ~R 4 Each of these independently represents a hydrogen atom or a number of carbon atoms. R represents an alkyl group of 1 to 4, 5 is an alkyl group, or C, O, Si, N, It represents a main chain composed of two or more atoms selected from S and P. Also, R 5 Substituted in the main chain A substituent may be introduced. Examples of substituents that can be introduced include alkyl groups and alcohols. Examples include xy groups.

[0124] [ka]

[0125] An ionic liquid containing a pyridinium cation is, for example, represented by the following general formula (G2). Ionic liquids may also be used. In general formula (G2), R 6 is an alkyl group, or R represents a main chain composed of two or more atoms selected from C, O, Si, N, S, and P. 7 ~R 11Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Yes. Also, R 6 A substituent may be introduced into the main chain. The substituent to be introduced is Examples include alkyl groups and alkoxy groups.

[0126] [ka]

[0127] Examples of ionic liquids having quaternary ammonium cations include the following general formulas (G3), (G 4) Ionic liquids represented by (G5) and (G6) can be used.

[0128] [ka]

[0129] In general formula (G3), R 28 ~R 31 Each of these is independently of the number of carbon atoms between 1 and 20. Any of the following: hydroxyl group, methoxy group, methoxymethyl group, methoxyethyl group, or hydrogen atom It represents ka.

[0130] [ka]

[0131] In general formula (G4), R 12 ~R 17 Each of these is independently of the number of carbon atoms between 1 and 20. Any of the following: hydroxyl group, methoxy group, methoxymethyl group, methoxyethyl group, or hydrogen atom It represents ka.

[0132] [ka]

[0133] In general formula (G5), R 18 ~R 24 Each of these is independently of the number of carbon atoms between 1 and 20. Any of the following: hydroxyl group, methoxy group, methoxymethyl group, methoxyethyl group, or hydrogen atom It represents ka.

[0134] [ka]

[0135] In the general formula (G6), n and m are between 1 and 3. α is between 0 and 6, and when n is 1... The sum α is between 0 and 4, when n is 2 α is between 0 and 5, and when n is 3 α is 0 The above is 6 or less. β is 0 or more and 6 or less, and when m is 1, β is 0 or more and 4 or less, and m is In the case of 2, β is between 0 and 5, and in the case of m is 3, β is between 0 and 6. When β is 0, it means there is no substitution. The case where both α and β are 0 is excluded. X or Y shall be a linear or side-chain substituent having 1 to 4 carbon atoms. Alkyl groups, linear or side-chain alkoxy groups with 1 to 4 carbon atoms, or carbon number This represents a linear or side-chain alkoxyalkyl group with a range of 1 to 4 units.

[0136] For example, an ionic liquid having a tertiary sulfonium cation is represented by the following general formula (G7). An ionic liquid can be used. In general formula (G7), R 25 ~R 27 teeth Each independently comprises a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms, or a phenyl atom. It represents the R group. 25 ~R 27 From the atoms C, O, Si, N, S, and P A main chain composed of two or more selected elements may also be used.

[0137] [ka]

[0138] For example, an ionic liquid having a quaternary phosphonium cation is represented by the following general formula (G8). An ionic liquid can be used. In general formula (G8), R 32 ~R 35 teeth Each independently comprises a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms, or a phenyl atom. It represents the R group. 32 ~R 35 From the atoms C, O, Si, N, S, and P A main chain composed of two or more selected elements may also be used.

[0139] [ka]

[0140] A shown in general formulas (G1) to (G8) - For example, monovalent amide anions, monovalent methides Anions, fluorosulfonate anions, perfluoroalkyl sulfonate anions, Tetrafluoroborate anions, perfluoroalkylborate anions, hexaful Olophosphate anions and perfluoroalkyl phosphate anions, etc. The above can be used.

[0141] As for monovalent amide anions, (C n F 2n+1 SO2)2N - (n=0 or more and 3 or less ), as a monovalent cyclic amide anion, (CF2SO2)2N - use This is possible. As a monovalent methide anion, (C n F 2n+1 SO2)3C - (n=0 (3 or less above), as a monovalent cyclic methide anion, (CF2SO2)2C - (CF 3SO2) and others can be used. As for fluoroalkyl sulfonate anions, (C m F 2m+1 SO3) - Examples include (m=0 or greater and 4 or less). Fluoroalkyl As a borate anion, {BF n (C m H k F 2m+1-k ) 4-n} - (n=0 or more Examples include (up to 3, m=1 to 4, k=0 to 2m). Fluoroalkyl As a phosphate anion, {PF n (C m H k F 2m+1-k ) 6-n} - (n Examples include k = 0 or greater and 5 or less, m = 1 or greater and 4 or less, k = 0 or greater and 2m or less.

[0142] Furthermore, as a monovalent amide anion, for example, bis(fluorosulfonyl)amide anion The use of one or more of the following is possible: can.

[0143] Furthermore, ionic liquids include hexafluorophosphate anions and tetrafluoroborates. It may have one or more anions.

[0144] From here on, (FSO2)2N - The anion represented by (CF3SO2)2N is called the FSA anion. -The anion represented by is sometimes referred to as the TFSA anion.

[0145] Specific examples of the cation of the above general formula (G1) include, for example, structural formula (111) to structural formula (1 74) is one example.

[0146] [ka]

[0147] [ka]

[0148] [ka]

[0149] [ka]

[0150] [ka]

[0151] [ka]

[0152] Specific examples of the cation of the above general formula (G2) include, for example, structural formula (701) to structural formula (7 19) is one example.

[0153] [ka]

[0154] [ka]

[0155] Specific examples of the cation of the above general formula (G4) include, for example, structural formula (501) to structural formula (5 20) is one example.

[0156] [ka]

[0157] Specific examples of the cation of the above general formula (G5) include, for example, structural formula (601) to structural formula (6 30) is one example.

[0158] [ka]

[0159] [ka]

[0160] Specific examples of the cation of the above general formula (G6) include, for example, structural formula (301) to structural formula (3 Examples include 09), and structural formulas (401) to (419).

[0161] [ka]

[0162] [ka]

[0163] Also, structural formulas (301) to (309), and structural formulas (401) to (4 19) shows an example where m is 1 in general formula (G6), but structural formula (301) or structure In formula (309) and structural formulas (401) to (419), m is 2, or You can replace it with 3.

[0164] Furthermore, as a specific example of the cation of the general formula (G7) above, for example, structural formula (201) to structure Equation (215) is given.

[0165] [ka]

[0166] In a secondary battery according to one aspect of the present invention, a positive electrode active material according to one aspect of the present invention is used, and electrolysis Because the liquid contains the ionic liquid described above, the secondary battery can be repeatedly charged at high charging voltages. Even when used in this manner, it is possible to suppress the decrease in capacity and achieve remarkably superior characteristics. Cut.

[0167] [Negative electrode active material] As an active material for the negative electrode of a secondary battery, it can perform charge and discharge reactions through the insertion and removal of carrier ions. Charge and discharge occur through alloying and dealloying reactions with the available materials and metal A, which acts as a carrier ion. Materials capable of carrying out the reaction, etc., can be used.

[0168] As negative electrode materials, graphite, easily graphitizable carbon (soft carbon), and difficult-to-graphitize carbon (hard carbon) are used. Using carbon-based materials such as carbon, carbon nanotubes, graphene, and carbon black It is possible.

[0169] Examples of graphite include synthetic graphite and natural graphite. An example of synthetic graphite is Mesoca. Examples include carbon microbeads (MCMB), coke-based synthetic graphite, and pitch-based synthetic graphite. Here, spheroidal graphite, which has a spherical shape, can be used as artificial graphite. Furthermore, MCMB may have a spherical shape, which is preferable. Also, the surface area of ​​MCMB Reducing the size is relatively easy and sometimes preferable. Examples of natural graphite include, Examples include flaky graphite and spheroidized natural graphite.

[0170] Graphite is formed when lithium ions are inserted into it (during the formation of lithium-graphite intercalation compounds). It exhibits a potential as low as lithium metal (0.05V to 0.3V vs. Li / Li + This allows lithium-ion secondary batteries to exhibit a high operating voltage. For example, it is possible to increase the charging voltage of a lithium-ion secondary battery. This can increase the energy density of um-ion secondary batteries. Furthermore, graphite, per unit volume It has a relatively high capacity per unit area, relatively small volume expansion, and is inexpensive compared to lithium metal. It is preferable because it has advantages such as high safety.

[0171] Furthermore, examples of negative electrode active materials include silicon, tin, gallium, aluminum, and germanium. At least one of the following: luminous, lead, antimony, bismuth, silver, zinc, cadmium, indium, etc. Materials containing one of these elements can be used. Such elements have a larger capacity compared to carbon, and Silicon has a high theoretical capacity of 4200mAh / g. Therefore, silicon is used as the negative electrode active material. It is preferable to use them. Compounds containing these elements may also be used. For example, S iO, Mg2Si, Mg2Ge, SnO, SnO2, Mg2Sn, SnS2, V2Sn3 , FeSn2, CoSn2, Ni3Sn2, Cu6Sn5, Ag3Sn, Ag3Sb, N i2MnSb, CeSb3, LaSn3, La3Co2Sn7, CoSb3, InSb, Examples include SbSn. Here, charge and discharge reactions are carried out through alloying and dealloying reactions with lithium. Elements that can perform this function, and compounds containing such elements, are sometimes referred to as alloying materials.

[0172] In this specification, SiO refers to silicon monoxide, for example. Alternatively, SiO refers to SiO x It can also be expressed as follows. Here, it is preferable that x has one neighboring value. Alternatively, x is For example, a value of 0.2 or more and 1.5 or less is preferred, and a value of 0.3 or more and 1.2 or less is more preferred.

[0173] Furthermore, titanium dioxide (TiO2) and lithium titanium oxide (Li4T) are used as negative electrode active materials. i5O 12 ), lithium-graphite intercalation compound (Li x C6), Niobium pentoxide (Nb2O5) Oxides such as tungsten oxide (WO2) and molybdenum oxide (MoO2) can be used. can.

[0174] Furthermore, the negative electrode active material has a Li3N-type structure, which is a lithium and transition metal binitride. Li 3-x M x N (M = Co, Ni, Cu) can be used. For example, Li 2.6 Co 0.4 The N3 has a large charge / discharge capacity (900mAh / g, 1890mAh / cm²). 3 ) indicates And it is preferable.

[0175] When a lithium-transition metal binitride is used, lithium ions are included in the negative electrode active material, Combined with lithium-ion-free materials such as V2O5 and Cr3O8 as positive electrode active materials. This is preferable. By pre-desorbing the lithium ions contained in the positive electrode active material, the negative electrode active material is used. A lithium-transition metal composite can be used.

[0176] Furthermore, materials that undergo a conversion reaction can also be used as the negative electrode active material. For example, Lithium oxide, such as cobalt oxide (CoO), nickel oxide (NiO), and iron oxide (FeO). Transition metal oxides that do not form alloys with the negative electrode active material may be used. The resulting materials include Fe2O3, CuO, Cu2O, RuO2, Cr2O3, etc. CoS oxides 0.89 , sulfides such as NiS and CuS, Zn3N2, Cu3N, Ge3 Nitrides such as N4, phosphides such as NiP2, FeP2, CoP3, FeF3, BiF3, etc. It can also occur with fluoride.

[0177] In a typical secondary battery, element M from the positive electrode active material dissolves into the electrolyte. It may precipitate on the negative electrode surface. The inhibition of the reaction at the negative electrode by the precipitated element M affects the capacity of the secondary battery. This leads to a decrease.

[0178] For example, consider the case where graphite is used as the negative electrode active material. Graphite acts as an interlayer carboxyl group in the battery reaction. Carrier ions are inserted and removed. For example, the cross-section of a layer on the surface of graphite particles is exposed. Insertion and deinsertion of carrier ions occur in a specific region on the surface of the particle. Because the battery reaction occurs efficiently only when the element M is deposited on the particle surface, for example, the effect of element M deposition on the particle surface is reduced. This suggests that they are significantly more susceptible.

[0179] In a secondary battery using a positive electrode active material according to one aspect of the present invention, as described above, the positive electrode active material possesses the element The elution of element M into the electrolyte can be suppressed. Therefore, for example, graphite can be used as the negative electrode active material. Even when used, the high battery capacity can be maintained even when the secondary battery is used repeatedly with a high charging voltage. It can be maintained.

[0180] Furthermore, using ionic liquids may suppress the degradation of graphite associated with charging and discharging. ru.

[0181] Furthermore, in a secondary battery according to one aspect of the present invention, the concentration of carrier ions in the electrolyte is increased. This suppresses the insertion of cations into graphite, which can extend the lifespan of secondary batteries. be.

[0182] In an electrolyte containing an ionic liquid, lithium iodine is used as the carrier ion in the electrolyte. When using , for example, the lithium salt concentration is preferably 0.8 mol / L or higher, and 1 m More preferably between ol / L and 2.5 mol / L, and more preferably between 1.2 mol / L and 2 mol / L. Less than is even preferable.

[0183] [Example of a secondary battery] Figure 1 shows a secondary battery using a film-like outer casing as an example of an energy storage device. A secondary battery using a flexible outer casing can have a flexible structure, thus reducing the number of flexible parts. Even if not present, if implemented in electronic devices that possess some of these features, the secondary battery will bend in accordance with the deformation of the electronic device. It is also possible.

[0184] Figure 1 shows the external view of the secondary battery 500, which uses a film-like outer casing. Furthermore, Figures 2A and 2B show the A1-A2 and B1-B2 sections, respectively, as indicated by the dashed lines in Figure 1. This shows that the secondary battery 500 has a positive electrode current collector 501 and a positive electrode active material layer 502. 03, a negative electrode 506 having a negative electrode current collector 504 and a negative electrode active material layer 505, and a separator It comprises 507, an electrolyte 508, and an outer casing 509. A positive is provided inside the outer casing 509. A separator 507 is installed between electrode 503 and negative electrode 506. Also, the outer casing 509 The inside is filled with electrolyte solution 508.

[0185] In the secondary battery 500 shown in Figures 1 and 2, the positive electrode lead electrode 510 has a positive electrode 503 The positive electrode current collector 501 and the negative electrode lead electrode 511 are connected to the negative electrode current collector 504 of the negative electrode 506. Each is then ultrasonically bonded. Furthermore, the positive electrode acts as a terminal for obtaining electrical contact with the outside, collecting current. The body 501 and the negative electrode current collector 504 can also serve this purpose. In that case, lead electrodes are used. Without doing so, a portion of the positive electrode current collector 501 and the negative electrode current collector 504 are exposed to the outside from the outer casing 509. You can arrange them in this way.

[0186] Furthermore, in Figure 1, the positive lead electrode 510 and the negative lead electrode 511 are arranged on the same side. However, as shown in Figure 3, the positive lead electrode 510 and the negative lead electrode 511 are arranged on different sides. This may be done. Thus, in one aspect of the present invention, the secondary battery allows the lead electrodes to be freely arranged. Because this is possible, the design flexibility is high. Therefore, products using a secondary battery according to one embodiment of the present invention This allows for increased design flexibility. Furthermore, it facilitates the production of products using a secondary battery according to one embodiment of the present invention. It can enhance sexual performance.

[0187] <Exterior> In the secondary battery 500, the outer casing 509 is, for example, coated with a polymer layer on both sides of a thin metal film. A covered film can be used. More specifically, for example, as a thin metal film, Using highly flexible metal thin films such as aluminum, stainless steel, copper, and nickel, the inner surface of the exterior A first polymer layer is provided on the surface that becomes the outer surface of the exterior body, and a second polymer layer is provided on the surface that becomes the outer surface of the exterior body. A first polymer layer, a metal thin film on the first polymer layer, a second polymer layer on the metal thin film, A three-layer film can be used. The first polymer layer and the second polymer layer are Preferably, it is an insulating synthetic resin film. Also, the first polymer layer and the second polymer A thermoplastic resin can be used as the first polymer layer, and in particular, a thermoplastic resin can be used for the first polymer layer. It is preferable to use it.

[0188] The first polymer layer and the second polymer layer are materials that suppress the reaction with ionic liquids. For example, polyethylene, polypropylene, polycarbonate, ionomer, polyamide A film made of materials such as polyester can be used. For example, a polyamide can be used. Iron can be used.

[0189] Furthermore, in Figure 2, 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 sets is not limited to five; there may be more or fewer sets. When the number of layers is increased, a secondary battery with a larger capacity can be created. Also, electrodes When the number of layers is small, the battery can be made thinner and have excellent flexibility.

[0190] In the above configuration, the outer casing 509 of the secondary battery 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 secondary battery consists of one or two layers, and has a laminated structure. In the case of a battery, the curved cross-sectional structure of the battery is formed by the two curves of the outer film. It will be a sandwiched structure.

[0191] [Example of a method for manufacturing a secondary battery] Next, we will explain one example of a method for manufacturing a secondary battery.

[0192] First, the negative electrode 506, separator 507 and positive electrode 503 are stacked. Figure 4A shows the positive electrode 503 and The external view of the negative electrode 506 is shown. The positive electrode 503 has a positive electrode current collector 501 and a positive electrode active material layer 50 2 is formed on the surface of the positive electrode current collector 501. Also, the positive electrode 503 is formed on the positive electrode current collector 501 It has a partially exposed area (hereinafter referred to as the tab area). The negative electrode 506 is connected to the negative electrode current collector 504. The negative electrode active material layer 505 is formed on the surface of the negative electrode current collector 504. 6 has a region in which the negative electrode current collector 504 is partially exposed, i.e., a tab region. The positive electrode and the negative electrode are The area and shape of the tab region are not limited to the example shown in Figure 4A.

[0193] Figure 4B shows the stacked negative electrode 506, separator 507, and positive electrode 503. An example using 5 sets of negative electrodes and 4 sets of positive electrodes is shown. Next, the joining of the tab regions of the positive electrode 503, The positive lead electrode 510 is joined to the tab region of the outermost positive electrode. For example, ultrasonic bonding is performed. Wave welding or similar methods can be used. Similarly, the joining of the tab regions of the negative electrode 506 and the outermost surface of the negative electrode The negative lead electrode 511 is joined to the tab region.

[0194] Next, the negative electrode 506, separator 507, and positive electrode 503 are placed on the outer casing 509.

[0195] Next, as shown in Figure 4C, fold the outer casing 509 at the part indicated by the dashed line. Then, the outer The outer periphery of the assembly 509 is joined. For joining, for example, heat sealing may be used. At this time, later A part (or one side) of the outer casing 509 is joined to allow the electrolyte 508 to be added. A restricted area (hereinafter referred to as the entry point) is provided.

[0196] Next, the electrolyte 508 (not shown) is introduced into the outer casing 509 through the inlet provided in the outer casing 5 It is introduced into the inside of 09. For example, as shown in Figure 5A, in the outer body 509, the first side The sealing portion 521 along the side and the sealing portion 522 along the second side are sealed, but the third side is not sealed. Here, in the sealing portion 522, between the positive lead electrode 510 and the outer casing 509, and the negative A bonding layer is placed between the electrode lead 511 and the outer casing 509, and the outer casing 509 Sealing may be performed. Next, the electrolyte 508 is introduced through the opening located on the third side. Then, as shown in Figure 5B, the sealing portion 523 along the third side is sealed. The introduction is preferably carried out under a reduced pressure atmosphere or an inert atmosphere. And finally, The inlet is joined. In this way, a laminate-type secondary battery 500 can be manufactured. ru.

[0197] Next, we will explain the aging process after the secondary battery has been manufactured. It is preferable to perform aging. An example of aging conditions is described below. First First, charge at a rate of 0.001C to 0.2C. The temperature should be, for example, above room temperature, 5 The temperature should be below 0°C. Here, the reaction potentials of the positive and negative electrodes should be within the potential window range of the electrolyte 508. If the charge / discharge of the secondary battery exceeds this limit, the electrolyte may decompose. If gas is generated during the solution process, and this gas accumulates inside the cell, the electrolyte will come into contact with the electrode surface. This results in areas where the reaction cannot occur. In other words, the effective reaction area of ​​the electrode decreases, and This corresponds to an increase in effective resistance.

[0198] Furthermore, if the resistance becomes excessively high, the negative electrode potential decreases, which leads to lithium insertion into the graphite. At the same time that this occurs, lithium deposition also occurs on the graphite surface. This lithium deposition is capacity This can lead to a decrease in performance. For example, after lithium is deposited, a film or other material may grow on the surface. As a result, lithium precipitated on the surface cannot be re-dissolved, and the amount of lithium that does not contribute to the volume increases. This can happen. Also, if the deposited lithium physically collapses and loses conductivity with the electrode, As a result, lithium that does not contribute to the capacity is produced. Therefore, the potential of the negative electrode is above the charging voltage. It is preferable to release the gas before the lithium potential is reached by the voltage rise.

[0199] Furthermore, after degassing, the temperature should be higher than room temperature, preferably 30°C to 60°C. More preferably, charging at a temperature of 35°C to 50°C for, for example, 1 hour to 100 hours. It may be kept in this state. During the initial charging, the electrolyte that decomposed on the surface will cover the surface of the graphite. A film 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.

[0200] [Example of stacking of positive electrode, negative electrode, and separator] Next, various examples of stacking of positive, negative, and separator electrodes are shown.

[0201] In the configuration shown in Figure 6A, one separator 123 separates the positive electrode active material layer 122 and the negative electrode active material layer 1 It is folded back multiple times, sandwiched between 26. In the configuration shown in Figure 6A, the positive electrode 111 In this configuration, the positive electrode active material layer 122 is provided on both sides or one side of the positive electrode current collector 121, and the negative electrode 1 In 15, the negative electrode active material layer 126 is provided on both sides or one side of the negative electrode current collector 125. In the configuration shown in Figure 6A, six sets of positive electrode active material layers 122 and negative electrode active material layers 126 form a separator 1 They face each other with 23 in between, and the separator 123 can be folded back at least 5 times. It is preferable. Also, the separator 123 is between the positive electrode active material layer 122 and the negative electrode active material layer 126. In addition to being positioned so as to be sandwiched, it is also extended to bundle multiple positive electrodes 111 and negative electrodes 115 together. You can tie them together.

[0202] Figure 6D shows an example in which a wound separator covers multiple electrode assemblies. Figure 6B shows the first electrode Figure 6C shows a cross-sectional view of the second electrode assembly 131, which is part of the electrode assembly 130. Figure 6D shows a cross-sectional view of the second electrode assembly 131, which is part of the electrode assembly 130. This is a cross-sectional view along the dashed line A1-A2. Note that in Figure 6D, to make the diagram clearer, the first The electrode assembly 130, the second electrode assembly 131, and the separator 123 are shown as excerpts.

[0203] As shown in Figure 6B, in the first electrode assembly 130, positive electrode active material is attached to 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 has a material layer 126, the separator 123, and the positive electrode current collector 121 has positive electrodes on both sides. The positive electrode 111a having the active material layer 122 is stacked in this order. Also, as shown in Figure 6C In the second electrode assembly 131, the negative electrode current collector 125 has a negative electrode active material layer 126 on both sides. The negative electrode 115a, separator 123, and positive electrode current collector 121 have positive electrode active material layers 122 on both sides. The positive electrode 111a, the separator 123, and the negative electrode current collector 125 are each covered with a negative electrode active material layer 126. The negative electrodes 115a are stacked in this order.

[0204] As shown in Figure 6D, the secondary battery 500 comprises a plurality of first electrode assemblies 130 and a plurality of other It has two electrode assemblies 131. Furthermore, as shown in Figure 6D, there are multiple first electrode assemblies 1 The 30 and multiple second electrode assemblies 131 are covered by a wound separator 123. It is.

[0205] [Example 2 of a secondary battery] The wound body 950 shown in Figure 7A has a negative electrode 931, a positive electrode 932, and a separator 933. The coiled body 950 has the negative electrode 931 and the positive electrode 932 overlapping with the separator 933 in between. The laminated sheets are stacked and then wound up to form a wound body. The negative electrode 931 and the positive electrode 93 Multiple layers of 2 and separator 933 may be stacked. Negative electrode 931, positive electrode 93 The number of stacks of the stack consisting of 2 and separator 933 is determined appropriately according to the required capacitance and element volume. Just design it.

[0206] As shown in Figure 7B, the outer casing is made of film 981 and film 982 having a recess. By housing the aforementioned wound body 950 in a space formed by bonding together by heat sealing or the like, Thus, a secondary battery 913 as shown in Figure 7C can be manufactured. The wound body 950 has terminals 951. It has terminals 952 and electrolysis occurs inside the film 981 and the film 982 which has recesses. It is impregnated with liquid. Terminals 951 and 952 are, for example, lead electrodes.

[0207] The film 981 and the film 982 having a recess contain the material described as the exterior body 509. And form, etc., can be used.

[0208] Furthermore, although Figures 7B and 7C show examples using two films, one film is used. By folding the material, a space is formed, and the aforementioned coiled body 950 is stored in that space. That's good too.

[0209] Figure 8 also shows an example in which a rectangular prism-shaped case is used as the housing 930. For example, a rectangular prism-shaped can can be used. Also, the housing 930 may have a shape such as a cylinder. You may do so. For information on cans, see, for example, the description regarding battery cans, which will be discussed later. .

[0210] The wound body 950 is impregnated with electrolyte inside the housing 930. The terminal 952 is connected to the housing 930. The terminal 951 is not in contact with the housing 930, as insulating material is used. In Figure 8, for convenience, the housing 930 is shown separated, but in reality, the winding body 950 is The terminals 951 and 952 are covered by the housing 930 and extend outside the housing 930. 930 can be made of a metal material (such as aluminum) or a resin material. ru.

[0211] [Example of a battery pack 1] Figures 9A and 9B show the external view of the battery pack. The battery pack is connected to the circuit board 90 It has a power supply unit (0) and a secondary battery (913). The secondary battery (913) has a label (910) attached to it. Furthermore, as shown in Figure 9B, the secondary battery 913 has terminals 951 and 952. The circuit board 900 is also secured with a seal 915.

[0212] The circuit board 900 has terminal 911 and battery control circuit 912. Terminal 911 is Through the circuit board 900, terminals 951, 952, antenna 914, and battery control circuit 9 It is connected to 12. Furthermore, multiple terminals 911 are provided, and each of the multiple terminals 911 is controlled These may also be used as signal input terminals, power terminals, etc.

[0213] The battery control circuit 912 may be located on the back surface of the circuit board 900. 914 is not limited to a coil shape, but may be, for example, linear or plate-shaped. Also, a planar antenna Aperture antennas, traveling wave antennas, EH antennas, magnetic field antennas, dielectric antennas, etc. An antenna may be used. Alternatively, antenna 914 may be a flat conductor. A conductor of this shape can function as one of the conductors for electric field coupling. In other words, it can function as a capacitor. Antenna 914 may function as one of the two conductors it possesses. This allows for the exchange of power not only through electromagnetic and magnetic fields, but also through electric fields.

[0214] The battery pack has a layer 916 between the antenna 914 and the secondary battery 913. For example, layer 916 has the function of shielding electromagnetic fields caused by secondary batteries 913. For example, magnetic materials can be used.

[0215] Furthermore, it is preferable that the battery pack includes a temperature sensor.

[0216] <Battery control circuit> The battery control circuit 912 can be used as a battery control circuit. It is preferable to have a charging control circuit. Furthermore, the battery control circuit 912 has a switch. The switch can be constructed, for example, using a transistor.

[0217] It is connected to terminal 951 of the secondary battery 913 and transmits the power output from the secondary battery 913. The first transmission line is electrically connected to the terminals of the charging control circuit of the battery control circuit 912. Furthermore, the second transmission path connected to terminal 952 of the secondary battery 913 is connected to the battery control circuit 9 It is electrically connected to a switch provided at 12. The switch interrupts the second transmission path. It has the function of controlling conduction and interruption. The switch controls the conduction and interruption operation, and switches between supply and interruption. It could also be called a means of switching or changing.

[0218] If the battery control circuit 912 detects an abnormality such as a micro-short, the second transmission path By inputting a signal to the gate of the switch to be blocked, the second transmission path can be blocked. If the second transmission path is interrupted, the supply of current from the charger will stop, or the secondary battery 913 will... It is possible to stop the supply of current to the mobile device installed. Also, the second transmission line The signal voltage applied to the gate of the switch that blocks the signal is a memory circuit (using an oxide semiconductor). By holding it in place (including a transistor), the blockage can be maintained for a long time. This can result in a highly efficient charging control system.

[0219] When the secondary battery 913 is charged by supplying power from the charger, the secondary battery 913 is in a charged state and The battery control circuit 912 controls the behavior of electrodes 971 and 972, such as voltage and current. The system monitors the system, and if an abnormality is detected, it shuts off the second transmission path to stop charging.

[0220] A charger is, for example, a device that has an adapter to connect to an external power source, or a device that uses wireless signals to charge. This refers to a device that transmits power. Note that chargers are built into electronic devices such as mobile devices. Sometimes they exist.

[0221] <Example of temperature-based control> Next, an example of controlling a secondary battery according to one aspect of the present invention in accordance with ambient temperature will be described. Temperature can be measured using a temperature sensor.

[0222] A secondary battery according to one aspect of the present invention can be repeatedly charged and discharged using an extremely high charging voltage. Furthermore, as shown in the examples described later, in a secondary battery according to one aspect of the present invention, the temperature If the voltage is low, it may be difficult to stably and repeatedly operate the secondary battery at a higher charging voltage. can.

[0223] The following describes an example of controlling the charging conditions according to temperature in a secondary battery according to one embodiment of the present invention. do.

[0224] If the charging temperature is within the range of above the first temperature and below the second temperature, the upper limit voltage for charging is... Let this be the first value. If the temperature during charging is above the second temperature, the upper limit voltage of charging is set to the second. Let the value be 2.

[0225] The first temperature is, for example, 5°C or more and less than 15°C, and the second temperature is 25°C or more and less than 55°C. Alternatively, the first temperature may be, for example, 8°C or more and less than 15°C, and the second temperature may be 30°C or more and less than 5°C. It is below 5℃.

[0226] The first value is 0.02V or more higher than the second value, or 0.04V or more higher. The voltage is 0.06V or higher, or 0.08V or higher, for example, 0.05V.

[0227] The first value is 4.45V or more and 4.6V or less, more preferably 4.47V or more and less than 4.6V. More preferably, 4.47V or more and less than 4.55V, 4.49V or more and less than 4.53V, for example It is approximately 4.5V.

[0228] As described above, by controlling the charging conditions of the secondary battery, the degradation of the secondary battery is suppressed and its lifespan is extended. It can be extended.

[0229] [Example of a battery pack 2] Note that the structure of the battery pack is not limited to that shown in Figure 9.

[0230] For example, as shown in Figures 10A and 10B, the secondary battery 913 shown in Figures 9A and 9B Antennas may be provided on each of the opposing pairs of surfaces. Figure 10A shows the pair mentioned above. Figure 10B is an external view showing one of the surfaces, and Figure 10B is an external view showing the other of the pair of surfaces. Furthermore, the same parts as the secondary battery shown in Figures 8A and 8B are shown in Figures 9A and 9B. The explanation of secondary batteries can be used as appropriate.

[0231] As shown in Figure 10A, the antenna 9 is placed on one of the pair of surfaces of the secondary battery 913 with a layer 916 in between. 14 is provided, and as shown in Figure 10B, layer 917 is attached to the other side of the pair of sides of the secondary battery 913. An antenna 918 is provided on either side. Layer 917 provides, for example, an electromagnetic field from a secondary battery 913. It has the function of being able to shield. For layer 917, for example, a magnetic material can be used. Cut.

[0232] By adopting the above structure, the size of both antenna 914 and antenna 918 can be increased. It is possible. Antenna 918 can, for example, perform data communication with external devices. It has the function of being able to do so. Antenna 918 has an antenna shape that can be applied to, for example, antenna 914. An antenna can be applied. This is a communication method between a secondary battery and other devices via antenna 918. For example, it can be used between a rechargeable battery and other devices, such as NFC (Near Field Communication). A response method that can be applied can be used.

[0233] Alternatively, as shown in Figure 10C, the display device 920 is connected to the secondary battery 913 shown in Figures 9A and 9B. A display device 920 may be provided. The display device 920 is electrically connected to terminal 911. Label 910 does not need to be provided in the area where 920 is provided. Note that in Figures 9A and 9B For parts that are the same as those shown in the secondary battery, refer to the explanation of the secondary battery shown in Figures 9A and 9B as appropriate. can.

[0234] The display device 920 displays, for example, an image indicating whether or not it is charging, an image indicating the amount of stored power, etc. It may be shown. The display device 920 may be, for example, electronic paper, liquid crystal display device, or electronic A luminescent (also known as EL) display device can be used. For example, an electronic paper By using this method, the power consumption of the display device 920 can be reduced.

[0235] Alternatively, as shown in Figure 10D, the sensor 921 is connected to the secondary battery 913 shown in Figures 9A and 9B. It may be provided. Sensor 921 is electrically connected to terminal 911 via terminal 922. Note that the same parts as the secondary battery shown in Figures 9A and 9B are shown in Figures 9A and 9B. The explanation of rechargeable batteries can be used as appropriate.

[0236] Examples of sensors 921 include displacement, position, velocity, acceleration, angular velocity, rotational speed, distance, and light. Liquid, magnetism, temperature, chemicals, sound, time, hardness, electric field, electric current, voltage, power, radiation, flow It should have the ability to measure quantity, humidity, gradient, vibration, odor, or infrared radiation. By providing the sensor 921, for example, data indicating the environment in which the secondary battery is placed can be collected. It can also detect (temperature, etc.) and store it in the memory of the battery control circuit 912.

[0237] Furthermore, an example of the structure of the secondary battery 913 will be explained using Figures 11A to 11E.

[0238] [Various configuration examples] Figure 11A shows a schematic top view of a bendable secondary battery 250. Figures 11B and 11 Figures C, 11D, and 11E correspond to the cutting lines C1-C2 and C3-C4 in Figure 11A, respectively. These are schematic cross-sectional views along cutting lines A1-A2 and B1-B2. Secondary battery 25 0 comprises an outer casing 251 and an electrode stack 210 housed inside the outer casing 251. The electrode stack 210 has a structure in which at least a positive electrode 211a and a negative electrode 211b are stacked. It has a lead 212a electrically connected to the positive electrode 211a, and an electrical lead 212a connected to the negative electrode 211b. The lead 212b that is directly connected extends to the outside of the outer casing 251. The region enclosed by 1 contains the positive electrode 211a and the negative electrode 211b, as well as the electrolyte (not shown). It is sealed inside. Although not shown in Figure 11B, etc., between the positive electrode 211a and the negative electrode 211b For example, a separator is placed.

[0239] Next, the outer casing 251 will be explained using Figures 11B, 11C, 11D, and 11E. ru.

[0240] The outer casing 251 has a film-like shape and sandwiches the positive electrode 211a and the negative electrode 211b. It is folded in half. The outer casing 251 has a folded portion 261 and a pair of sealing portions It has a 262 and a sealing portion 263. The pair of sealing portions 262 are positive electrode 211a and It is provided on either side of the negative electrode 211b and can also be called a side seal. Also, seal portion 2 Section 63 has a portion that overlaps with leads 212a and 212b, and is also called the top seal. It is possible.

[0241] The outer casing 251 has ridges 271 and valleys in the portion that overlaps with the positive electrode 211a and the negative electrode 211b. It is preferable that the 272 have a wave shape arranged alternately. Also, the sealing portion 2 of the outer casing 251 It is preferable that 62 and the sealing portion 263 are flat.

[0242] Figure 11B shows a cross-section cut at the point where it overlaps with ridge line 271, and Figure 11C shows the valley line 272 Figures 11B and 11C both show the secondary battery 250 and the positive This corresponds to the cross-section in the width direction of pole 211a and negative pole 211b.

[0243] Here, the end of the negative electrode 211b in the width direction, that is, the end of the negative electrode 211b, and the seal portion 26 Let the distance between 2 and 2 be distance La. When the secondary battery 250 is subjected to deformation such as bending, As described above, the positive electrode 211a and the negative electrode 211b are deformed so that they are offset from each other in the longitudinal direction. In that case, if the distance La is too short, the outer casing 251 and the positive electrode 211a and negative electrode 211b Strong friction can cause damage to the outer casing 251, especially the metal film of the outer casing 251. If exposed, the metal film may be corroded by the electrolyte. Therefore Therefore, it is preferable to set the distance La to be as long as possible. On the other hand, if the distance La is large If this is done, the volume of the 250 secondary battery will increase.

[0244] Furthermore, the thicker the combined thickness of the stacked positive electrode 211a and negative electrode 211b, the greater the positive electrode 21 It is preferable to increase the distance La between 1a and the negative electrode 211b and the seal portion 262. stomach.

[0245] More specifically, stacked positive electrode 211a and negative electrode 211b and (not shown) separate When the total thickness of 214 is t, the distance La is between 0.8 and 3.0 times the thickness t. Preferably, the ratio is 0.9 times or more and 2.5 times or less, more preferably 1.0 times or more and 2.0 times or less. It is preferable that the distance La is within this range, making it compact and resistant to bending. This enables the creation of highly reliable batteries.

[0246] Furthermore, when the distance between the pair of sealing portions 262 is denoted as distance Lb, distance Lb is set to the positive electrode 211 Make it sufficiently larger than the width of a and the negative electrode 211b (here, the width Wb of the negative electrode 211b). This is preferable. This allows the secondary battery 250 to be subjected to repeated bending or other deformations. Even if the positive electrode 211a and the negative electrode 211b come into contact with the outer casing 251, the positive electrode 211a and Because a portion of the negative electrode 211b can be shifted in the width direction, the positive electrode 211a and the negative electrode 211 This effectively prevents friction between b and the outer casing 251.

[0247] For example, the difference between the distance Lb between the pair of sealing portions 262 and the width Wb of the negative electrode 211b is positive. The thickness t of electrode 211a and negative electrode 211b is 1.6 times or more and 6.0 times or less, preferably 1.8 It is preferable that the ratio be between 2.0 and 4.0 times, and more preferably between 2.0 and 4.0 times. stomach.

[0248] Furthermore, Figure 11D is a cross-section including lead 212a, and the secondary battery 250, positive electrode 211a This corresponds to the longitudinal cross-section of the negative electrode 211b. As shown in Figure 11D, the bent portion 26 In 1, between the longitudinal ends of the positive electrode 211a and the negative electrode 211b and the outer casing 251 It is preferable to have space 273. Lead 212a is positive electrode 21 in region 215a It is joined to 1a.

[0249] Figure 11E shows a schematic cross-sectional view of the secondary battery 250 when it is bent. This corresponds to the cross-section at the cutting line B1-B2 in 11A.

[0250] When the secondary battery 250 is bent, a portion of the outer casing 251 located on the outside of the bend stretches inwards. Other parts located there deform to shrink. More specifically, the parts located on the outside of the outer casing 251 The part deforms so that the wave amplitude is small and the wave period is large. On the other hand, the outer body The portion located inside 251 is modified so that the wave amplitude is large and the wave period is small. Shape. In this way, the outer casing 251 deforms, and as it bends, the outer casing 251 Because the stress is relieved, the material that makes up the exterior 251 does not need to expand or contract. As a result, the outer casing 251 does not get damaged, and the secondary battery 250 can be bent with a small force. can.

[0251] Also, as shown in Figure 11E, when the secondary battery 250 is bent, the positive electrode 211a and the negative electrode 2 11b and the other are relatively shifted. At this time, multiple stacked positive electrodes 211a and negative electrodes are shifted. Since one end of pole 211b on the sealing portion 263 side is fixed by the fixing member 217, it is not foldable. Each part shifts such that the amount of shift increases the closer it is to the recessed part 261. As a result, the positive electrode 2 The stress on 11a and the negative electrode 211b is relieved, and the positive electrode 211a and the negative electrode 211b themselves The body does not need to expand or contract. As a result, the positive electrode 211a and the negative electrode 211b are not damaged. The 250 secondary battery can be bent.

[0252] Furthermore, there is a space 273 between the positive electrode 211a and the negative electrode 211b and the outer casing 251. By doing so, the positive electrode 211a and negative electrode 211b, which are located on the inside when bent, are positioned within the outer casing 25 It can shift relative to point 1 without making contact.

[0253] The radius of curvature of a surface will be explained using Figures 12A, 12B, and 12C. In Figure 12A... Furthermore, in the plane 1701 obtained by cutting the curved surface 1700, the curve 17 included in the curved surface 1700 Approximate a portion of 02 as an arc of a circle, set the radius of that circle as the radius of curvature 1703, and set the center of the circle as the radius of curvature Let the center be 1704. Figure 12B shows a top view of the curved surface 1700. Figure 12C shows the plane 170 The cross-sectional view of the curved surface 1700 cut in 1 is shown. When a curved surface is cut with a plane, the plane relative to the curved surface Depending on the angle of the surface and the cutting position, the radius of curvature of the curve that appears in the cross-section will differ, but Honmyo In detailed specifications, the smallest radius of curvature is defined as the radius of curvature of the surface.

[0254] A curved secondary battery with two films as the outer casing, sandwiching the electrodes, electrolyte, etc., and 1805 microelectrolyte. 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 is , smaller than the radius of curvature 1804 of film 1803 on the side farther from the center of curvature 1800 (Figure) 13A). When a secondary battery is curved to create an arc-shaped cross-section, the film's center of curvature is close to 1800. The surface is subjected to compressive stress, while the surface of the film far from the center of curvature 1800 is subjected to tensile stress. A force is applied (Figure 13B). When a pattern is formed on the surface of the exterior body with recesses or protrusions, Even when compressive or tensile stress is applied in this way, the effects of strain remain within acceptable limits. It can be contained within. Therefore, the secondary battery has the smallest curvature of the outer casing on the side closest to the center of curvature. The radius of change is, for example, 3 mm or more and 30 mm or less, more preferably 3 mm or more and 10 mm or less. It can be transformed in that way.

[0255] Furthermore, the cross-sectional shape of a secondary battery is not limited to a simple arc shape, but may have a shape in which part of it is an arc. It is possible to create shapes such as the one shown in Figure 13C, or a wavy shape (Figure 13D), or an S-shape. It is also possible. If the curved surface of the secondary battery has a shape with multiple centers of curvature, then the multiple centers of curvature In the curved surface with the smallest radius of curvature among the radii of curvature at each heart, the two outer bodies The minimum radius of curvature of the outer casing closest to the center of curvature is, for example, 3 mm to 30 mm. Preferably, it can be deformed to be between 3 mm and 10 mm.

[0256] [Cylindrical rechargeable battery] An example of a cylindrical secondary battery will be explained with reference to Figure 14A. The cylindrical secondary battery 400 is As shown in Figure 14A, the top surface has a positive electrode cap (battery cover) 401, and the sides and bottom surface It has a battery can (outer casing) 402. These positive electrode cap 401 and battery can (outer casing) 4 02 is insulated by gasket (insulating packing) 410.

[0257] Figure 14B is a schematic diagram showing a cross-section of a cylindrical secondary battery. The secondary battery has a positive electrode cap (battery cover) 601 on the top surface, and a battery case on the sides and bottom. It has an outer casing (outer casing) 602. These positive electrode caps and battery casing (outer casing) 602 are gas It is insulated by a 610 insulating packing.

[0258] Inside the hollow cylindrical battery can 602, there is a strip-shaped positive electrode 604 and a negative electrode 606 separated by a separator 6 A battery element is provided wound with 05 sandwiched in between. Although not shown in the diagram, the battery element is a sensor It is wound around the turpin. Battery can 602 is closed at one end and open at the other. The battery can 602 contains nickel, aluminum, titanium, etc., which are corrosion-resistant to the electrolyte. Using metals, or alloys thereof, or alloys of these with other metals (for example, stainless steel, etc.) It is possible to do so. Also, to prevent corrosion by the electrolyte, nickel, aluminum, etc. are used. It is preferable to cover the battery container 602. Inside the battery container 602, the positive electrode, the negative electrode and The battery element, around which the separator is wound, is sandwiched between a pair of opposing insulating plates 608 and 609. Furthermore, the inside of the battery can 602, which is equipped with the battery element, contains a non-aqueous electrolyte (not shown). It is being injected. A non-aqueous electrolyte similar to that used in coin-type rechargeable batteries can be used. .

[0259] Since the positive and negative electrodes used in cylindrical storage batteries are wound, active material is formed on both sides of the current collector. It is preferable that the positive electrode 604 is connected to the positive electrode terminal (positive electrode current collector lead) 603, and the negative electrode The negative terminal (negative current collector lead) 607 is connected to 606. Positive terminal 603 and negative terminal Terminals 607 can both be made of metal materials such as aluminum. Positive terminal 60 Terminal 3 is resistance-welded to the safety valve mechanism 613, and the negative terminal 607 is resistance-welded to the bottom of the battery can 602. The safety valve mechanism 613 is a PTC (Positive Temperature Cofferdam). It is electrically connected to the positive electrode cap 601 via the (ficient) element 611. The valve mechanism 613 activates when the internal pressure of the battery exceeds a predetermined threshold, and the positive electrode cap 601 This disconnects the electrical connection with the positive electrode 604. Also, the PTC element 611 is at a higher temperature. This is a thermal resistance element whose resistance increases when the temperature rises, and by increasing the resistance, it limits the amount of current. This prevents overheating. The PTC element uses a barium titanate (BaTiO3) semiconductor. Conductive ceramics and the like can be used.

[0260] Figure 14C shows an example of an energy storage system 415. The energy storage system 415 consists of multiple secondary batteries 40 It has 0. The positive electrode of each secondary battery is in contact with the conductor 424 separated by the insulator 425. They are in contact and electrically connected. Conductor 424 is connected to control circuit 420 via wiring 423. They are electrically connected. Furthermore, the negative terminal of each secondary battery is controlled via wiring 426. It is electrically connected to circuit 420. The control circuit 420 is the battery control circuit described above. Route 912 can be applied.

[0261] Figure 14D shows an example of an energy storage system 415. The energy storage system 415 consists of multiple secondary batteries 4 Having 00, multiple secondary batteries 400 are sandwiched between conductive plates 413 and 414. Multiple secondary batteries 400 are electrically connected to conductive plates 413 and 414 by wiring 416. It is connected to the following. Multiple secondary batteries 400 may be connected in parallel or in series. They may be connected in parallel and then in series. Multiple secondary batteries By configuring a power storage system 415 having 400, a large amount of power can be extracted. ru.

[0262] Multiple secondary batteries 400 may be connected in parallel and then further connected in series.

[0263] Multiple secondary batteries 400 may have a temperature control device between them. If the secondary batteries 400 overheat... When this happens, the temperature control device will cool it down, and if the secondary battery 400 gets too cold, the temperature control device will be used to cool it down. The device can be heated. Therefore, the performance of the energy storage system 415 is affected by the outside temperature. It becomes less likely to happen.

[0264] Also, in Figure 14D, the energy storage system 415 has wiring 421 and wiring 420 connected to the control circuit 420. It is electrically connected via 22. Wiring 421 is connected to multiple secondary power via conductive plate 413. The wiring 422 is connected to the positive electrode of the battery 400, and via the conductive plate 414 to the negative electrode of multiple secondary batteries 400. They are electrically connected to each other.

[0265] [Example 3 of battery packs] Next, an example of an energy storage system according to one aspect of the present invention will be described with reference to Figure 15.

[0266] Figure 15A shows the external appearance of the secondary battery pack 531. Figure 15B shows the secondary battery pack 5 This is a diagram illustrating the configuration of 31. The secondary battery pack 531 consists of a circuit board 540 and a secondary battery It has 513 and a label 529 attached to the secondary battery 513. Circuit board 54 0 is secured by seal 515. Also, the secondary battery pack 531 is connected to antenna 5 It has 17.

[0267] In the secondary battery pack 531, for example, as shown in Figure 15B, on the circuit board 540, It has a circuit 590. The circuit board 540 is also electrically connected to terminal 514. The circuit board 540 also includes the antenna 517 and the positive and negative leads of the secondary battery 513. One end 551 is electrically connected to the positive lead and the other end 552 to the negative lead. Control circuit The battery control circuit 912 described above can be applied to 590.

[0268] Alternatively, as shown in Figure 15C, a circuit system 590a is provided on the circuit board 540. And, a circuit system 590b that is electrically connected to the circuit board 540 via terminal 514, It may have a control circuit in one aspect of the present invention. The other parts are provided in the circuit system 590b.

[0269] Furthermore, the antenna 517 is not limited to a coil shape; for example, it may be linear or plate-shaped. Planar antenna, aperture antenna, traveling wave antenna, EH antenna, magnetic field antenna, dielectric An antenna such as a body antenna may be used. Alternatively, antenna 517 may be a flat conductor. This flat conductor can function as one of the conductors for electric field coupling. Antenna 517 functions as one of the two conductors of the capacitor. This is also possible. This allows for the exchange of power not only through electromagnetic and magnetic fields, but also through electric fields. Cut.

[0270] The secondary battery pack 531 has a layer 519 between the antenna 517 and the secondary battery 513. The layer 519 has the function of shielding electromagnetic fields, for example, from the secondary battery 513. For layer 519, for example, a magnetic material can be used.

[0271] As the secondary battery 513, the various secondary batteries mentioned above can be used.

[0272] This embodiment can be appropriately combined with descriptions of other embodiments.

[0273] (Embodiment 2) This embodiment shows a secondary battery according to one aspect of the present invention and an energy storage system equipped with a battery control circuit. Let me explain an example of "M".

[0274] Figure 16A shows a battery control circuit 91 formed on a flexible substrate, which is a flexible film. This is a conceptual diagram of an energy storage system in which 2 is implemented on a secondary battery 913. The circuit board 900 is flexible. It is constructed using a circuit board. Also, Figures 16B, 16C, and 16D show the energy storage system shown in Figure 16A. This is a diagram illustrating the method for manufacturing stems.

[0275] Figure 16B shows the secondary battery 913. The secondary battery 913 has terminals 951 and 952. Figure 16C shows the circuit board 900 spread out.

[0276] As shown in Figure 16D, the circuit board 900 is bent and wrapped around the secondary battery 913. This allows for the formation of the energy storage system shown in Figure 16A.

[0277] A power storage system according to one aspect of the present invention comprises a secondary battery 913 and a battery control circuit 912. Furthermore, the battery control circuit 912 has a switch. This switch uses, for example, a transistor. It can be constructed using this method.

[0278] Furthermore, an energy storage system according to one aspect of the present invention includes a layer 916 and an a It is preferable to have an antenna 914. The layer 916 is, for example, an insulating sheet. For example, component 914 is electrically connected to the battery control circuit 912. For example, circuits for sending and receiving signals from antenna 914, such as modulation circuits, demodulation circuits, etc. It holds.

[0279] It is connected to terminal 951 of the secondary battery 913 and transmits the power output from the secondary battery 913. The first transmission line is electrically connected to the terminals of the charging control circuit via electrode 971. The second transmission path connected to terminal 952 of secondary battery 913 is connected to the second electrode 972 It is connected to a switch that interrupts the transmission path. The switch controls the conduction and interruption operations. It functions as a switching mechanism for switching between supply and interruption.

[0280] A method for forming the battery control circuit 912 on the circuit board 900 is to form it on a semiconductor substrate. Afterward, a method is used to fix the circuit board 900 after peeling using a peeling method. In this case, known techniques can be used. Also, after forming on a semiconductor substrate, the back surface can be polished. Alternatively, the part may be polished and then fixed onto the circuit board 900. Alternatively, one could cut it out using a laser cut and then fix it onto the circuit board 900. Alternatively, the battery control circuit 912 may be directly formed on the circuit board 900. A method is used in which the battery control circuit 912 formed on the substrate is peeled off and fixed onto the circuit board 900. It is also possible to do so.

[0281] If the battery control circuit 912 detects an abnormality such as a micro-short, the second transmission path By inputting a signal to the gate of the switch to be blocked, the second transmission path can be blocked. If the second transmission path is interrupted, the supply of current from the charger will be stopped, or the battery control circuit 91 The supply of current to electronic devices connected to 2 can be stopped. Also, the second transmission The signal voltage applied to the gate of the switch that blocks the path is stored in a memory circuit (using oxide semiconductors). By holding it in place with a transistor, the interruption can be maintained for a long time. Therefore, This allows for a highly safe energy storage system.

[0282] When the secondary battery 913 is charged by supplying power from the charger, the secondary battery 913 is in a charged state and The battery control circuit 912 controls the behavior of electrodes 971 and 972, such as voltage and current. The system monitors the system, and if an abnormality is detected, it shuts off the second transmission path to stop charging.

[0283] A charger is, for example, a device that has an adapter to connect to an external power source, or a device that uses wireless signals to charge. This refers to a device that transmits power. Note that chargers are built into electronic devices such as mobile devices. Sometimes they exist.

[0284] This embodiment can be appropriately combined with descriptions of other embodiments.

[0285] (Embodiment 3) This embodiment shows an example in which a secondary battery according to one aspect of the present invention is mounted on a vehicle. Examples include automobiles, motorcycles, and bicycles.

[0286] A secondary battery according to one aspect of the present invention has high energy density, a long lifespan, and excellent reliability. Furthermore, by using the secondary battery according to one aspect of the present invention in combination with a battery control circuit, the secondary battery In some cases, the lifespan of the pond can be further extended, which is desirable. Also, a secondary battery according to one embodiment of the present invention When used in combination with a battery control circuit, the secondary battery can be used in electronic devices and vehicles equipped with the battery. This can enhance safety in areas such as safety.

[0287] The following describes an energy storage system combining a secondary battery according to one aspect of the present invention and a battery control circuit. Next, we will explain an example of installation in a vehicle, but in the configuration shown below, the storage installed in the vehicle The electrical system can also be configured without the battery control circuit described above. For example, Only a secondary battery according to one embodiment of the present invention may be applied to the following vehicle.

[0288] When a battery storage system is installed in a vehicle, it can be used in hybrid vehicles (HV), electric vehicles (EV), or This will enable the realization of next-generation clean energy vehicles such as plug-in hybrid vehicles (PHVs). .

[0289] Figures 17A, 17B, and 17C show a vehicle using an energy storage system according to one embodiment of the present invention. Let's illustrate with two examples. The automobile 8400 shown in Figure 17A uses an electric motor as the power source for driving. - is an electric vehicle that uses an electric motor and engine as the power source for driving. This is a hybrid vehicle in which the appropriate components can be selected and used. Using one aspect of the present invention This makes it possible to create vehicles with a long driving range. The Automobile 8400 is an energy storage system The energy storage system not only drives the electric motor 8406, but also the headlights 8 It can supply power to light-emitting devices such as the 401 and room lights (not shown).

[0290] Furthermore, the energy storage system is used in the speedometer, tachometer, etc. of the 8400 automobile. It can supply power to the display device. Furthermore, the energy storage system is provided by the vehicle 8400. It can supply power to navigation systems and other devices.

[0291] The automobile 8500 shown in Figure 17B is connected to the energy storage system 8024 of the automobile 8500. It can be charged by receiving power from an external charging facility using methods such as the ignition system or contactless power supply system. This is possible. Figure 17B shows the ground-mounted charging device 8021 being mounted on the automobile 8500. This shows the state in which the energy storage system 8024 is being charged via cable 8022. Regarding electricity, charging methods and connector standards include CHAdeMO (registered trademark) and Combo, etc. This can be done as appropriate in the prescribed manner. The charging device 8021 is a charging station installed in a commercial facility. It can be an external power source, or a household power source. For example, using plug-in technology, The power supply from the unit charges the energy storage system 8024 installed in the vehicle 8500. This is possible. Charging is done by converting AC power to DC power via a conversion device such as an AC / DC converter. It can be done by conversion.

[0292] 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 doing so. In this contactless power supply method, power transmission equipment is installed in roads or exterior walls. By incorporating this, charging can be performed not only when the vehicle is stopped but also while it is in motion. Furthermore, this contactless power supply... This method 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 system when the vehicle is stopped or in motion. For power supply via contact, electromagnetic induction or magnetic resonance methods can be used.

[0293] Furthermore, Figure 17C shows an example of a motorcycle using an energy storage system according to one embodiment of the present invention. Figure 17 The scooter 8600 shown in C includes a power storage system 8602, side mirrors 8601, and turn signals. It is equipped with a lamp 8603. The energy storage system 8602 supplies electricity to the turn signal lamp 8603. It is possible.

[0294] Furthermore, the scooter 8600 shown in Figure 17C has a power storage system 860 in the under-seat storage compartment 8604. It can store 2. The power storage system 8602 is small and the under-seat storage 8604 is small. However, it can be stored in the under-seat storage compartment 8604.

[0295] Figure 18A also shows an example of an electric bicycle using a power storage system according to one embodiment of the present invention. An energy storage system according to one embodiment of the present invention can be applied to the electric bicycle 8700 shown in 18A. Cut.

[0296] The electric bicycle 8700 is equipped with a power storage system 8702. The power storage system 8702 is used for driving It can supply electricity to the motor that assists the driver. Also, the energy storage system 8702 It is portable, and Figure 18B shows it detached from the bicycle. It also has a battery storage system. Stem 8702 incorporates multiple storage batteries 8701, which are part of a power storage system according to one aspect of the present invention. It is designed so that the remaining battery level and other information can be displayed on the display unit 8703. The energy storage system 8702 has a control circuit 8704 according to one aspect of the present invention. Control circuit 870 4 is electrically connected to the positive and negative terminals of the battery 8701. Control circuit 8704 Therefore, the battery control circuit shown in the previous embodiment can be used.

[0297] This embodiment can be appropriately combined with descriptions of other embodiments.

[0298] (Embodiment 4) This embodiment describes an example of mounting a secondary battery according to one aspect of the present invention in an electronic device.

[0299] A secondary battery according to one aspect of the present invention has high energy density, a long lifespan, and excellent reliability. Furthermore, by using the secondary battery according to one aspect of the present invention in combination with a battery control circuit, the secondary battery In some cases, the lifespan of the pond can be further extended, which is desirable. Also, a secondary battery according to one embodiment of the present invention When used in combination with a battery control circuit, the secondary battery can be used in electronic devices and vehicles equipped with the battery. This can enhance safety in areas such as safety.

[0300] The following describes an energy storage system combining a secondary battery according to one aspect of the present invention and a battery control circuit. The following describes an example of mounting it in an electronic device, but in the configuration shown below, it is implemented in an electronic device. The energy storage system can also be configured without the battery control circuit described above. For example, only a secondary battery according to one embodiment of the present invention may be applied to the electronic device shown below.

[0301] Figures 19A and 19B show foldable tablet devices (including clamshell devices). An example of (m) is shown. The tablet terminal 9600 shown in Figures 19A and 19B has a housing 96 30a, housing 9630b, movable part 9640 connecting housing 9630a and housing 9630b, Display unit 9631, display mode selector switch 9626, power switch 9627, power saving It has a mode switching switch 9625, a fastener 9629, and an operation switch 9628. The display unit 9631 uses a flexible panel, which allows for a larger display area. It can be used as a tablet device. Figure 19A shows the tablet device 9600 in an open state. Figure 19B shows the tablet terminal 9600 in a closed state.

[0302] Furthermore, the tablet terminal 9600 has a power storage unit inside the housing 9630a and housing 9630b. It has 9635. The energy storage unit 9635 passes through the movable part 9640 and the housing 9630a and housing 9 It is provided over 630b.

[0303] The display unit 9631 can be partially designated as a touch panel area, and the displayed operation keys can be accessed. Data can be entered by touching the screen. Additionally, the touchscreen keyboard display can be turned off. By touching the location where the replacement button is displayed with your finger or stylus, the display unit 9631 will activate. Keyboard buttons can be displayed.

[0304] Additionally, the display mode switch 9626 switches the display orientation, such as portrait or landscape. You can switch between black and white and color displays. Power saving mode switch. The 9625 is detected by the light sensor built into the tablet terminal 9600 when in use. The display brightness can be optimized according to the amount of ambient light. In addition to optical sensors, other detection sensors such as gyroscopes and accelerometers that detect tilt are also used. The device may be built-in.

[0305] Figure 19B shows the closed state, and the tablet terminal consists of a housing 9630 and a solar cell 9633. , and a power storage system according to one aspect of the present invention. The power storage system includes a control circuit 9634, It has a battery storage unit 9635. The control circuit 9634 is the same as the battery shown in the previous embodiment. A control circuit can be used.

[0306] Furthermore, since the tablet terminal 9600 is foldable, the casing 9630a and The casing 9630b can be folded so that the two halves overlap. By folding it, the front Since the display unit 9631 can be protected, the durability of the tablet terminal 9600 can be increased. ru.

[0307] In addition, the tablet devices shown in Figures 19A and 19B can display various types of information (static Functions to display images, videos, text, etc., calendar, date or time, etc. A function to display information on the screen, a touch input function to operate or edit the information displayed on the screen, It can have functions to control processing using various software (programs), etc. ru.

[0308] The solar cell 9633 mounted on the surface of the tablet device powers the touch panel. It can be supplied to the display unit or the video signal processing unit, etc. Note that the solar cell 9633 is housed in a casing. A structure that can be provided on one or both sides of the body 9630 and efficiently charges the energy storage body 9635. It can be considered a success.

[0309] In Figures 19A and 19B, the foldable tablet terminal is shown in the above embodiment. Although we have described a configuration that applies a control circuit using a battery control circuit, other configurations are also acceptable. For example, as shown in Figure 19C, a clamshell-type terminal such as a notebook personal computer It can also be applied to computers. In Figure 19C, the display unit 9631 is located in the housing 9630a, housing The 9601 is a notebook personal computer that combines the 9630b with the 9650 keyboard unit. As illustrated in the diagram, the notebook personal computer 9601 contains the following: It has the control circuit 9634 described above and the energy storage unit 9635. The battery control circuit shown in the previous embodiment can be used.

[0310] Figure 20 shows an example of another electronic device. In Figure 20, the display device 8000 is one of the present inventions. This is an example of an electronic device that implements an energy storage system of the form. Specifically, the display device 8000 is This corresponds to a display device for receiving TV broadcasts, and consists of a housing 8001, a display unit 8002, and a speaker unit 800. 3. The system includes a secondary battery 8004, etc. The detection system according to one aspect of the present invention includes a housing 8001 It is located inside. The display device 8000 can also receive power from the commercial power supply. Yes, it is possible, and it is also possible to use the power stored in the secondary battery 8004.

[0311] The display unit 8002 has light-emitting elements such as liquid crystal display devices and organic EL elements in each pixel. Equipment, electrophoresis display device, DMD (Digital Micromirror Display) ce), PDP (Plasma Display Panel), FED (Field Semiconductor display devices such as Emission Displays can be used.

[0312] Furthermore, the voice input device 8005 also uses a secondary battery. The system has an energy storage system as shown in the embodiment. The voice input device 8005 is a wireless communication element In addition, sensors including microphones (optical sensors, temperature sensors, humidity sensors, barometric pressure sensors, illuminance sensors) It has multiple sensors (such as motion sensors) and can control other devices based on the user's commands. For example, it can be used to control the power supply of the display device 8000, adjust the light intensity of the lighting device 8100, etc. The 8005 voice input device allows you to control peripherals by voice, replacing a manual remote control. This is the result.

[0313] Furthermore, the voice input device 8005 has wheels or mechanical means of movement, and the user's voice It moves in the direction from which the sound can be heard, and accurately hears the command with its built-in microphone, and The configuration allows the content to be displayed on the display unit 8008, or allows touch input operation of the display unit 8008. That is what they say.

[0314] Furthermore, the voice input device 8005 charges the mobile information terminal 8009, such as a smartphone. It can also function as a dock. (Mobile information terminal 8009 and voice input device 80) 05 enables the exchange of power via wired or wireless connection. The portable information terminal 8009 is indoors. In this case, there is no need to carry it around, and it ensures the necessary capacity while not putting a load on the secondary battery. To avoid degradation, the secondary battery is managed by the voice input device 8005. It is desirable that maintenance and other tasks be performed. Also, the voice input device 8005 is a speaker. Because it has 8007 and a microphone, even when the portable information terminal 8009 is charging, Hands You can also have free conversations. Also, the rechargeable battery capacity of the voice input device 8005 is low. When lowered, it moves in the direction of the arrow and wirelessly connects to the external power supply and the charging module 8010. You can charge it by charging it.

[0315] The voice input device 8005 may also be placed on a stand. It may be moved to the desired position by providing wheels or mechanical means of movement, or by providing a platform or wheels Alternatively, the voice input device 8005 may be fixed in a desired position, for example, on the floor.

[0316] In addition to being used for receiving TV broadcasts, display devices are also used for personal computers, advertising displays, and more. This includes all information display devices.

[0317] In Figure 20, the fixed lighting device 8100 has a microprocessor that controls charging. This is an example of an electronic device using a secondary battery 8103 controlled by (including APS). The lighting device 8100 includes a housing 8101, a light source 8102, a secondary battery 8103, and the like. In Figure 20, the secondary battery 8103 is located on the ceiling where the housing 8101 and light source 8102 are installed. The example shows the case where it is located inside 8104, but the secondary battery 8103 is located inside the housing 81 It may be located inside 01. The lighting device 8100 receives power from the commercial power supply. It can be used as a power source, or it can use the power stored in the secondary battery 8103.

[0318] Note that Figure 20 illustrates a fixed lighting device 8100 installed on the ceiling 8104. However, the secondary battery 8103 is located in places other than the ceiling 8104, such as the side wall 8105, floor 8106, and window 8 It can be used in fixed lighting fixtures installed in 107, etc., as well as in tabletop lighting fixtures. It can also be used for things like this.

[0319] Furthermore, the light source 8102 can be an artificial light source that uses electricity to artificially produce light. Specifically, this includes incandescent light bulbs, discharge lamps such as fluorescent lamps, and light-emitting elements such as LEDs and organic EL elements. The element is an example of the artificial light source mentioned above.

[0320] In Figure 20, the air conditioner having an indoor unit 8200 and an outdoor unit 8204 is, This is an example of an electronic device using a secondary battery 8203. Specifically, the indoor unit 8200 is housed in a casing 8 It has components such as 201, an air outlet 8202, and a secondary battery 8203. In Figure 20, the secondary battery 8203 However, the example given is that it is located in the indoor unit 8200, but the secondary battery 8203 is located in the outdoor unit It may be provided in 8204. Alternatively, it may be provided in both the indoor unit 8200 and the outdoor unit 8204. A secondary battery 8203 may be provided. The air conditioner draws power from the commercial power supply. It can also receive power from the secondary battery 8203, or it can use the power stored in the secondary battery 8203. ru.

[0321] In Figure 20, the electric refrigerator 8300 is an example of an electronic device using a secondary battery 8304. Specifically, the electric refrigerator-freezer 8300 consists of a casing 8301, a refrigerator door 8302, and a refrigerator door. It has a freezer door 8303, a secondary battery 8304, etc. In Figure 20, the secondary battery 8304 is enclosed in a box. It is located inside the body 8301. The electric refrigerator 8300 receives power from the commercial power supply. It can receive power from the battery, or it can use the power stored in the secondary battery 8304.

[0322] 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 periods when the proportion of electricity actually used (called the electricity usage rate) is low, secondary By storing power in the battery, the rate of power consumption outside of the above-mentioned time period is suppressed. It is possible. For example, in the case of the electric refrigerator 8300, when the temperature is low, the refrigerator door 830 2. At night when the freezer door 8303 is not opened or closed, power is stored in the secondary battery 8304. And as the temperature rises, the refrigerator door 8302 and the freezer door 8303 are opened and closed. During the daytime, by using the secondary battery 8304 as an auxiliary power source, the daytime power usage rate It can be kept low.

[0323] In addition to the electronic devices mentioned above, secondary batteries can be installed in any electronic device. Depending on the embodiment, the cycle characteristics of the secondary battery will be improved. Therefore, in one embodiment of the present invention, A microprocessor (including APS) that controls electricity is provided in the electronic device described in this embodiment. By incorporating this, electronic devices can be made to have a longer lifespan. This embodiment is not applicable to other embodiments. It can be implemented in various forms and combinations as appropriate.

[0324] Figures 21A to 21G show examples of how an energy storage system according to one aspect of the present invention is implemented in an electronic device. An electronic device to which an energy storage system according to one aspect of the present invention is applied is, for example, a television device. Television (also called a television receiver), monitors for computers, digital cameras, etc. Cameras, digital video cameras, digital photo frames, mobile phones (mobile phones, portable phones) Large devices such as (also called communication devices), portable game consoles, portable information terminals, sound playback devices, and pachinko machines. Examples include game consoles.

[0325] Figure 21A shows an example of a mobile phone. The mobile phone 7400 is assembled in the housing 7401. In addition to the embedded display unit 7402, there are operation buttons 7403, an external connection port 7404, and a speaker It is equipped with components such as the CA 7405 and the microphone 7406. Furthermore, the mobile phone 7400 is based on the present invention. One embodiment of the present invention has an energy storage system. One embodiment of the present invention has an energy storage system, for example, a storage battery 740 It comprises 7 and the battery control circuit shown in the previous embodiment.

[0326] Figure 21B shows the mobile phone 7400 in a curved state. When deformed by an external force and the entire structure is bent, the storage battery 740 located inside 7 may also be curved. In such cases, the storage battery 7407 has flexibility. It is preferable to use a flexible battery. Figure 21C shows the bent state of a flexible battery. As shown, the battery is electrically connected to the control circuit 7408. The battery control circuit shown in the previous embodiment can be used.

[0327] Furthermore, the flexible battery can be installed in the interior or exterior walls of houses and buildings, or in automobiles. It can also be incorporated along curved surfaces of the interior or exterior.

[0328] Figure 21D shows an example of a bangle-type display device. The portable display device 7100 has a housing. 7101, display unit 7102, operation button 7103, and a power storage system according to one aspect of the present invention A power storage system according to one aspect of the present invention includes, for example, a battery 7104 and, in the previous embodiment... It has a battery control circuit as shown.

[0329] Figure 21E shows an example of a wristwatch-type personal information terminal. The personal information terminal 7200 is housed in a casing. Body 7201, display unit 7202, band 7203, buckle 7204, operation buttons 7205 It is equipped with input / output terminals 7206, etc.

[0330] The 7200 mobile information terminal offers mobile phone, email, document viewing and creation, music playback, and internet connectivity. - It can run various applications such as network communication and computer games. ru.

[0331] The display unit 7202 has a curved display surface, and displays are made along the curved display surface. It can do this. In addition, the display unit 7202 is equipped with a touch sensor, allowing you to touch the screen with your finger or stylus. It can be operated by touching it. For example, the icon 72 displayed on the display unit 7202 Touching 07 will launch the application.

[0332] The 7205 control button is used for setting the time, turning the power on and off, and turning wireless communication on and off. It has various functions such as operation, silent mode activation and deactivation, and power saving mode activation and deactivation. This can be done. For example, the operating system built into the mobile information terminal 7200 The stem also allows you to freely configure the function of the control button 7205.

[0333] Furthermore, the personal information terminal 7200 is capable of performing standardized short-range wireless communication. Yes, for example, by communicating with a wireless headset, hands-free operation is possible. You can also make phone calls.

[0334] Furthermore, the portable information terminal 7200 is equipped with an input / output terminal 7206, and connects to other information terminals via a connector. It can directly exchange data via this. It can also be charged via input / output terminal 7206. It is also possible to perform this operation. Note that charging is performed wirelessly without using input / output terminal 7206. That's fine.

[0335] The portable information terminal 7200 has a power storage system according to one aspect of the present invention. The power storage system is It comprises a rechargeable battery and the battery control circuit shown in the previous embodiment.

[0336] 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 acceleration sensors. It is preferable that the following are installed:

[0337] Figure 21F shows an example of an armband-type display device. The display device 7300 has a display unit 730 The present invention has a secondary battery having 4. The 7304 can also be equipped with a touch sensor and can function as a portable information terminal. It's also possible.

[0338] The display unit 7304 has a curved display surface, and displays are made along the curved display surface. Yes, it is possible. Furthermore, the display device 7300 can communicate via standardized short-range wireless communication, etc. The situation can be changed.

[0339] 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 input / output terminals. Furthermore, charging may be performed wirelessly without using input / output terminals.

[0340] By using a secondary battery according to one aspect of the present invention as a secondary battery in everyday electronic devices, a lightweight and long-lasting battery can be achieved. We can provide a variety of products. For example, as everyday electronic devices, electric toothbrushes, electric shavers, etc. Examples include mobile beauty devices, and the rechargeable batteries for these products are designed with ease of handling by the user in mind. What is desired is a rechargeable battery that is stick-shaped, small, lightweight, and has a large capacity.

[0341] Figure 21G is a perspective view of a device also known as a tobacco-containing smoking device (electronic cigarette). In G, the electronic cigarette 7500 includes an atomizer 7501 containing a heating element, and the atomizer The rechargeable battery 7504 that supplies power, and cartridge 7 which includes a liquid supply bottle and sensors. It consists of 502. To enhance safety, it prevents overcharging and over-discharging of the secondary battery 7504. The protection circuit may be electrically connected to the secondary battery 7504. The secondary battery 7 shown in Figure 21G The 504 has an external terminal so that it can be connected to a charging device. The secondary battery 7504 has Since this will be the tip, it is desirable that the total length be short and the weight be light. A secondary battery according to one aspect of the present invention has high capacity and good cycle characteristics, and therefore can be used for a long period of time. This allows us to offer the 7500, a small and lightweight e-cigarette that can be used for extended periods.

[0342] Next, an example of an electronic device equipped with a battery control circuit according to one aspect of the present invention will be described using Figure 22. To do so.

[0343] The Robot 7000 includes a rechargeable battery, light sensor, microphone, camera, speaker, and Spray, various sensors (infrared sensor, ultrasonic sensor, accelerometer, piezoelectric sensor, light) It is equipped with sensors (such as gyro sensors) and a movement mechanism. Secondary robot of Robot 7000 By applying a battery storage system equipped with a battery control circuit according to one aspect of the present invention to a battery, the control of the secondary battery They can provide care and protection, etc.

[0344] The microphone has the function of detecting acoustic signals such as the user's voice and ambient sounds. Furthermore, the speaker has the function of emitting audio signals such as voice and warning sounds. The 7000 analyzes the audio signal input via the microphone and performs the necessary actions. Audio signals can be emitted from the speaker. In the Robot 7000, the microphone It is possible to communicate with the user using a phone and speaker. ru.

[0345] The camera has the function of imaging the area around robot 7000. Also, robot 7000 It has the function of moving using a moving mechanism. Robot 7000 uses a camera to observe its surroundings. By capturing images and analyzing them, it's possible to detect obstacles and other issues while moving.

[0346] Aircraft 7120 is an autonomous aircraft equipped with propellers, cameras, and a secondary battery. To have the ability.

[0347] Furthermore, the secondary battery of the aircraft 7120 is equipped with a battery control circuit according to one aspect of the present invention, and the energy storage system By applying this technology, in addition to weight reduction, it is possible to control and protect the secondary battery, etc.

[0348] The 7140 cleaning robot has a rechargeable battery, a display located on the top, and a side panel. It has multiple cameras, brushes, control buttons, various sensors, etc. Although not shown in the illustration, sweeping The cleaning robot 7140 is equipped with wheels, a suction nozzle, etc. The 40 is self-propelled, can detect dust, and can suck up the dust from a suction port located on its underside. This invention allows for the electrical connection of a battery control cycle to the secondary battery of the cleaning robot 7140. By applying a power storage system with a circuit, the number of components used is reduced, and the secondary battery is micro It can detect abnormalities such as short circuits.

[0349] As an example of a mobile device, we show the electric vehicle 7160. The electric vehicle 7160 uses a secondary battery, Thai It has a steering system, brakes, and a camera. It connects to the secondary battery of the electric vehicle 7160. By applying a battery control circuit according to one aspect of the present invention to an energy storage system, the number of components used can be reduced. Furthermore, it can detect abnormalities such as micro-short circuits in the secondary battery.

[0350] In the above, an electric vehicle was described as an example of a mobile vehicle, but mobile vehicles are electric This is not limited to automobiles. For example, other modes of transport include trains, monorails, ships, and aircraft (helicopters). Other examples include helicopters, unmanned aerial vehicles (drones), airplanes, and rockets. A battery control circuit according to one aspect of the present invention, which is electrically connected to the secondary battery of the mobile device, is installed in the power storage device. By applying the system, the number of components used is reduced, and abnormalities such as micro-shorts in secondary batteries are prevented. It can detect abnormalities.

[0351] A secondary battery equipped with a battery control circuit according to one aspect of the present invention is used in smartphones 7210 and PC 72 It can be incorporated into personal computers (such as the 20) and game consoles (such as the 7240).

[0352] The Smartphone 7210 is an example of a mobile information terminal. It has an microphone, camera, speaker, various sensors, and display unit. Therefore, these peripheral devices are controlled. Electrically connected to the secondary battery of the smartphone 7210. By applying a battery control circuit according to one aspect of the present invention to an energy storage system, the number of components used can be reduced. This reduces the amount of power used and allows for the control and protection of secondary batteries, thereby enhancing safety. ru.

[0353] The PC7220 is an example of a notebook PC. The rechargeable battery of the notebook PC is electrically connected. Applying a battery control circuit according to one aspect of the present invention to an energy storage system, the number of components used is reduced. It can reduce the amount of power used, and also control and protect the secondary battery, thereby enhancing safety. Cut.

[0354] Game console 7240 is an example of a portable game console. Game console 7260 is a home console. This is an example of a game console. The game console 7260 has a controller 7262 that can be connected wirelessly or wired. It is connected. The controller 7262 is equipped with a battery control circuit according to one aspect of the present invention. By applying an electrical system, the number of components used is reduced, and the secondary battery is controlled and protected. This can be done, and safety can be enhanced.

[0355] Figure 23A shows an example of a wearable device. A wearable device has a power source and It uses a rechargeable battery. Furthermore, the user is responsible for water resistance during everyday use or outdoor use. To enhance this, in addition to wired charging where the connector part is exposed, wireless charging is also available. There is a demand for wearable devices that can also be charged.

[0356] For example, it can be mounted on a spectacle-type device 490 as shown in Figure 23A. The vise 490 has a frame 490a and a display unit 490b. The frame has a curved shape. By incorporating a rechargeable battery into the temple of the 490a, it is lightweight and has a good weight balance. This can be used to create a glasses-type device 490 with a long continuous usage time.

[0357] It can also be mounted on a headset-type device 491. 491 comprises at least a microphone section 491a, a flexible pipe 491b, and an earphone. It has a section 491c. A secondary power supply is located inside the flexible pipe 491b or the earphone section 491c. A pond can be constructed.

[0358] Furthermore, it can be mounted on a device 402 that can be directly attached to the body. A secondary battery 402b can be installed inside the thin housing 402a of the 2.

[0359] Furthermore, it can be mounted on a device 403 that can be attached to clothing. A secondary battery 403b can be installed inside the slim housing 403a.

[0360] Furthermore, it can be mounted on a belt-type device 406. The belt-type device 406 is a belt It has a belt section 406a and a wireless power supply and receiving section 406b, and inside the belt section 406a It can be equipped with a secondary battery.

[0361] Furthermore, it can be installed in a wristwatch-type device 405. The wristwatch-type device 405 displays It has a section 405a and a belt section 405b, and the display section 405a or the belt section 405b, A secondary battery can be installed.

[0362] The display unit 405a can display not only the time, but also various other information such as incoming emails and phone calls. It is possible.

[0363] Furthermore, the wristwatch-type device 405 is a wearable device that is worn directly on the wrist. Therefore, it may be equipped with sensors to measure the user's pulse, blood pressure, etc. Furthermore, it is possible to accumulate data related to health and use it to help maintain health.

[0364] A detailed explanation of the wristwatch-type device 405 shown in Figure 23A is provided below.

[0365] Figure 23B shows a perspective view of the wristwatch-type device 405 after it has been removed from the arm.

[0366] A side view is also shown in Figure 23C. Figure 23C shows the internal structure with the secondary battery 913. It indicates a child. The secondary battery 913 is located in a position that overlaps with the display unit 405a, and is small. Furthermore, it is lightweight.

[0367] Furthermore, the wristwatch-type device 405 has a battery control that is electrically connected to a secondary battery 913 inside. It is preferable to have a circuit.

[0368] This embodiment can be appropriately combined with descriptions of other embodiments.

[0369] (Notes regarding the descriptions in this specification, etc.) The above embodiments and a description of each component in those embodiments are provided below.

[0370] The configurations shown in each embodiment can be appropriately combined with the configurations shown in other embodiments to form one of the present inventions. This can be an embodiment. Also, if multiple configuration examples are shown within one embodiment... The configuration examples can be combined as needed.

[0371] Furthermore, the content described in one embodiment (even a part of it) may vary depending on the form of its implementation. Other content (even partial content) described in the tone, and / or one or more other implementations To apply, combine, or replace the content described in the form (even if only a part of it is acceptable), It is possible to do things like this.

[0372] Furthermore, the content described in each embodiment refers to the use of various figures in each embodiment. This refers to the content stated, or the content stated using the text described in the specification.

[0373] Furthermore, a diagram (even a partial one) described in one embodiment may refer to another part of that diagram. Further figures (even partial ones) described in that embodiment, and / or one or more figures. In another embodiment, the diagram (or even just a part of it) described above can be combined by This allows for the creation of even more diagrams.

[0374] Furthermore, in this specification, block diagrams classify components according to their function and treat them as independent of each other. It is shown as a block. However, in actual circuits, the components are arranged according to their function. It is difficult to separate the functions, and when multiple functions are involved in a single circuit, or when the functions span multiple circuits... It is possible that one function may be involved. Therefore, the blocks in the block diagram are described in the specification. The elements are not limited to those explicitly stated, and can be appropriately rephrased depending on the situation.

[0375] Furthermore, in the drawings, the size, layer thickness, or area is shown at an arbitrary size for the sake of explanation. Therefore, it is not necessarily limited to that scale. Furthermore, the drawings are intended to be clear. This is a schematic representation and is not limited to the shapes or values ​​shown in the drawings. For example, Variations in signals, voltages, or currents due to noise, or signals due to timing discrepancies. This can include variations in voltage or current, among other things.

[0376] In this specification and other documents, when describing the connection relationships of transistors, the term "one of the source or drain" is used. The other side of the source and drain is called the "source or drain" (or the first electrode, or the first terminal), and the other side of the source and drain is called the "source or drain" The notation "the other side of the transistor" (or second electrode, or second terminal) is used. The source and drain of a transistor vary depending on its structure or operating conditions. Regarding the terminology for the source and drain of a transistor, the source (drain) terminals and the source (drain) terminals are used. The term "drain electrode" can be appropriately rephrased depending on the context.

[0377] Furthermore, in this specification, the terms "electrode" and "wiring" do not limit the functionality of these components. It is not fixed. For example, "electrode" can be used as part of "wiring". The reverse is also true. Furthermore, the terms "electrode" and "wiring" can refer to multiple "electrodes" and "wiring". This also includes cases where the "lines" are formed as a single unit.

[0378] Furthermore, in this specification, voltage and potential may be used interchangeably as appropriate. Voltage is the reference voltage. This is the potential difference from the potential that is obtained, and for example, if the reference potential is the ground voltage, Voltage can be rephrased as electric potential. Ground potential does not necessarily mean 0V. Not necessarily. Furthermore, potential is relative, and depending on the reference potential, it can affect the wiring, etc. It may change the electrical potential.

[0379] In this specification, the terms "membrane," "layer," etc. may be used in some cases or in some situations. Depending on the context, they can be interchanged. For example, the term "conductive layer" can be replaced with "conductive layer". In some cases, the term can be changed to "electromagnetic film." Alternatively, for example, "insulating film" can be used. In some cases, it may be possible to change the term to "insulating layer."

[0380] In this specification, a switch refers to a conductive state (on state) or a non-conductive state (off state). It refers to a device that has the function of controlling whether or not to allow current to flow (in a certain state). Alternatively, A switch is a device that has the function of selecting and switching the path through which electric current flows.

[0381] In this specification, channel length refers, for example, in a top view of a transistor, to the length of a semiconductor (or the part of the semiconductor through which current flows when the transistor is ON) and the gate The distance between the source and drain in the overlapping region or the region where the channel is formed. It refers to.

[0382] In this specification, channel width refers to, for example, the state when a semiconductor (or transistor) is ON. The region where the part of the semiconductor through which current flows and the gate electrode overlap, or the channel. This refers to the length of the portion where the source and drain face each other in the region where the filter is formed.

[0383] In this specification, when A and B are connected, it means that A and B are directly connected. This includes things that are electrically connected, in addition to objects. Here, A and B are electrically connected Being connected means that there is an object between A and B that has some kind of electrical interaction. This refers to a device that enables the exchange of electrical signals between A and B. [Examples]

[0384] In this embodiment, a method for manufacturing a secondary battery according to one aspect of the present invention and the characteristics of the manufactured secondary battery are described. I will explain.

[0385] [Fabrication of positive electrode active material] The positive electrode active material was prepared.

[0386] First, a first mixture containing magnesium and fluorine was prepared. LiF and MgF2 Weigh the ingredients so that the ratio is LiF:MgF2 = 1:3, and add acetone as the solvent for wet fermentation. The mixture was then mixed and ground. The mixing and grinding were performed using a ball mill with zirconia balls. The process was carried out at 400 rpm for 12 hours. The treated material was collected and used as the first mixture.

[0387] Next, lithium cobaltate was prepared as a composite oxide containing lithium and cobalt. More specifically, we prepared Cellseed C-10N manufactured by Nippon Chemical Industrial Co., Ltd.

[0388] Next, the amount of magnesium atoms in the first mixture relative to the molecular weight of lithium cobalt oxide The ingredients were weighed to a quantity of 0.5 atomic percent and mixed by dry mixing. Zirconia balls were used for mixing. The process was carried out using a ball mill at 150 rpm for 1 hour. The processed material was collected and used for the second mixture. That's what I decided.

[0389] Next, the second mixture is placed in an alumina crucible and heated in an oxygen-filled muffle furnace at 850°C for 60 minutes. The alumina crucible was annealed for 2 hours. During annealing, the crucible was covered. The oxygen flow rate was 10 L. The rate was set to / min. The heating rate was set to 200°C / hr, and the cooling rate was reduced over a period of 10 hours or more. The processed material was used as the positive electrode active material.

[0390] [Fabrication of the positive electrode] Next, a positive electrode was fabricated using the positive electrode active material prepared above. The cathode active material consists of acetylene black (AB) and polyvinylidene fluoride (PVDF). Mix AB and PVDF in a ratio of 95:3:2 (by weight) and use NMP as the solvent to create a slurry. - was prepared. The prepared slurry was coated onto the current collector and the solvent was evaporated. Then, 120 After applying a 179kN / m press at °C, a 1249kN / m press is applied to collect current. A positive electrode active material layer was formed on the body to create the positive electrode P1. The positive electrode P1 is determined by the battery cell used. The amount of positive electrode active material supported was varied. A 20 μm thick aluminum foil was used as the current collector. The positive electrode active material layer was provided on one side of the current collector.

[0391] [Fabrication of the negative electrode] A negative electrode was fabricated using graphite as the negative electrode active material.

[0392] Negative electrodes were fabricated using two types of graphite. The first type had a specific surface area of ​​6.3 m². 2 Using spheroidized natural graphite with an average particle size of 15 μm, along with CMC-Na and SBR Mix graphite:CMC-Na:SBR = 97:1.5:1.5 (by weight ratio) and use as a solvent. A slurry was prepared using water. As a second type, a specific surface area of ​​1.5 m² was used. 2 / g MCM Using B graphite, together with conductive additives, CMC-Na and SBR, the ratio graphite:conductive additive:CMC Mix Na:SBR in a ratio of 96:1:1:2 (by weight), and use water as the solvent to create a slurry. I made it.

[0393] The degree of polymerization of the CMC-Na used was 600 to 800, and it was used as a 1-weight% aqueous solution. The viscosity of the aqueous solution in this case ranged from 300 mPa·s to 500 mPa·s. Also, As a conductive additive, VGCF(registered trademark)-H (manufactured by Showa Denko Corporation), which is a vapor-grown carbon fiber. Fiber diameter 150 nm, specific surface area 13 m² 2 / g) was used.

[0394] Each prepared slurry is coated onto a current collector, dried, and a negative electrode active material layer is formed on the current collector. It was manufactured using 18 μm thick copper foil as the current collector. The negative electrode active material layer was provided on both sides of the current collector. .

[0395] The negative electrode using the first type of graphite is referred to as negative electrode N1, and the negative electrode using the second type of graphite is referred to as negative electrode N2. The amount of negative electrode active material loaded on negative electrodes N1 and N2 is changed depending on the battery cell used. Ta.

[0396] [Manufacturing of secondary batteries] Using the positive and negative electrodes prepared as described above, a secondary battery with a film casing was fabricated. .

[0397] A 50 μm thick cellulose was used as the separator.

[0398] The positive electrode, separator, negative electrode, separator, and positive electrode were stacked in that order. It was provided on one side of the current collector. The two positive electrodes are positioned such that the positive electrode active material faces the negative electrode active material with a separator in between. I placed it.

[0399] Leads were attached to the positive and negative electrodes, respectively.

[0400] A laminate consisting of a positive electrode, a negative electrode, and a separator is sandwiched between two outer casings that are folded in half. The laminated structure was arranged so that one end of the do protrudes from the outside of the outer casing. Next, one side of the outer casing was made into an open section. I left it as is and sealed the other edges.

[0401] The outer film consists of a polypropylene layer, an acid-modified polypropylene layer, and aluminum. A film was used in which a humic acid layer and a nylon layer were laminated in that order. The thickness of the film was approximately 110 μm. The outer surface of the exterior body was made of nylon, and the inner surface was made of polyp The film that would form the outer casing was folded so that each polypropylene layer was positioned accordingly. The thickness of the um layer is approximately 40 μm, the thickness of the nylon layer is approximately 25 μm, and the polypropylene layer is acid-modified. The total thickness of the polypropylene layers was approximately 45 μm.

[0402] Next, under an argon gas atmosphere, the electrolyte was injected through the side that remained open. Ta.

[0403] There are a total of five types of electrolytes (electrolyte Sol_1, Sol_2, Sol_3, Sol_ Prepare 4 and Sol_5), and in each secondary battery, use one of the electrolytes Ta.

[0404] The electrolytes Sol_1 and Sol_2 will be described. The solvent is defined by the structural formula (G11 The EMI-FSA shown in ) was used. In the electrolyte Sol_1, LiFSA (lithium) was used as the electrolyte. Using umbis(fluorosulfonyl)amide, the electrolyte concentration relative to the electrolyte solution is 2. The concentration was set to 15 mol / L. In the electrolyte Sol_2, LiTFSA (lithium bis) was used as the electrolyte. Using (trifluoromethanesulfonyl)amide, the electrolyte concentration relative to the electrolyte solution is 1 The concentration was set to 0.50 mol / L.

[0405] [ka]

[0406] Let's explain the electrolyte Sol_3. The solvent is BMI-FSA, shown in structural formula (G12). LiFSA (lithium bis(fluorosulfonyl)amide) was used as the electrolyte. The electrolyte concentration in the electrolyte solution was set to 1.93 mol / L.

[0407] [ka]

[0408] Let's explain the electrolyte Sol_4. The solvent is P13-FSA, shown in structural formula (G13). LiFSA (lithium bis(fluorosulfonyl)amide) was used as the electrolyte. The electrolyte concentration in the electrolyte solution was set to 1.80 mol / L.

[0409] [ka]

[0410] Let's explain the electrolyte Sol_5. The solvents are ethylene carbonate (EC) and dieth A mixture of hydroxyaluminum carbonate (DEC) in a volume ratio of EC:DEC = 3:7 was used. Lithium hexafluoride phosphate (LiPF6) was used as the electrolyte. Electrolyte relative to electrolyte The concentration was set to 1.00 mol / L.

[0411] The solvent and electrolyte used in each electrolyte e) is shown in Table 1.

[0412] [Table 1]

[0413] Next, under reduced pressure, one side of the outer casing that had been left open was sealed.

[0414] The secondary battery was manufactured using the above process.

[0415] [aging] Next, we performed aging on the secondary battery.

[0416] First, the rechargeable battery is sandwiched between two plates and charged at CC (0.01C, capacity 15mAh / g). Then, the two plates were removed, and one side of the outer casing was cut and opened under an argon atmosphere. Then, the gas was released and resealed. Here, CC represents constant current. Here, the capacity of the secondary battery The value was calculated per unit weight of positive electrode active material. The C rate was calculated based on the conditions of the charge-discharge cycle, with 1C being the optimal value. The calculation was performed accordingly. For a charging voltage of 4.4V in the cycle characteristic evaluation, the current was 190mA. At 4.45V, the capacity is 210mAh / g, and at 4.5V, it is 220mAh / g. It was calculated as follows.

[0417] Next, the rechargeable battery is sandwiched between two plates and charged at CC (0.1C, capacity 120mAh / g). Then, the two plates were removed and kept at 0°C for 24 hours, and then placed under an argon atmosphere. The outer casing was cut along one side to open it, the gas was released, and then it was resealed.

[0418] [Evaluation of charge / discharge characteristics] Next, the secondary battery is sandwiched between two plates, and charging is performed using CCCV (0.1C, initial current 0.01C). The discharge was performed using CC (0.2C, 2.5V). The charging voltage was used to evaluate the cycle characteristics. The charging voltage was adjusted to match the current voltage. Here, CV represents a constant voltage.

[0419] After that, charging was performed using CCCV (0.2C, initial current 0.01C), and discharging was performed using CC (0.2C, 2 The battery was charged and discharged three times at 0.5V. The charging voltage was chosen to evaluate the cycle characteristics. It was adjusted to match the charging voltage.

[0420] [Cycle Characteristics Evaluation 1] Next, the cycle characteristics of the secondary battery were evaluated at 25°C.

[0421] Cells Cel_1 to Cel_7 shown in Table 2 were fabricated as battery cells. The positive electrode used was (P ositive Electrode), Negative Electrode ) and the combination of electrolyte (Electrolyte Solution), and charging The voltage (charge voltage) is shown in Table 2.

[0422] [Table 2]

[0423] In terms of C-rate and the capacity ratio described later, when the charging voltage is 4.4V, the positive electrode capacity is 190 The capacity was set to mAh / g. When the charging voltage was 4.45V, the positive electrode capacity was set to 210mAh / g. When the charging voltage was 4.5V, the positive electrode capacity was set to 220mAh / g.

[0424] The amount of positive electrode active material supported in positive electrode P1 is approximately 6.5 mg / for cells Cel_1 to Cel_4. cm 2 Cells Cel_5 to Cel_7 contain approximately 11 mg / cm³ 2 That's what I decided.

[0425] The area of ​​the positive electrode active material layer at positive electrode P1 is 8.194 cm². 2That's what I decided.

[0426] The amount of negative electrode active material loaded in negative electrode N1 and negative electrode N2 in each battery cell is approximately 7 in terms of capacity ratio. The ratio was adjusted to be between 7% and 83%. Here, the capacity ratio refers to the positive electrode capacity relative to the negative electrode capacity. This value expresses the quantity as a percentage. In calculating the volume ratio, the negative electrode volume is based on the weight of the negative electrode active material. The standard was set at 330 mAh / g. The amount of negative electrode active material supported was determined by the amount provided on both sides of the current collector. The total amount of material supported in the negative electrode active material layer was divided in half to calculate the result.

[0427] Charging is performed using CCCV (0.2C, initial current 0.02C), and discharging is performed using CC (0.2C, 2. The test was conducted at 5V. The capacity of the secondary battery was calculated based on the weight of the positive electrode active material.

[0428] The evaluation results of the cycle characteristics at 25°C are shown in Figures 24A, 24B, and 25.

[0429] Figure 24A shows the cycle characteristics of cells Cel_1 to Cel_4, with the horizontal axis representing the cycle The vertical axis shows the number of units, and the vertical axis shows the discharge capacity, respectively. Figure 24B shows an enlarged view of the vertical axis in Figure 24A. vinegar.

[0430] Figure 25 shows the cycle characteristics of cells Cel_5 to Cel_7.

[0431] Furthermore, the charge and discharge curves of cells Cel_1 to Cel_4 are shown in Figures 26A, 26B, and 27A. These are shown in Figure 27B. The solid line is the curve for the first cycle, and the dotted line is the curve for the 100th cycle. The following shows the respective charge and discharge curves. In each charge and discharge curve, the vertical axis represents the charging or discharging voltage. The horizontal axis shows the capacity.

[0432] From Figures 26A, 26B, 27A, and 27B, all of cells Cel_1 through Cel_4 Even when the charging voltage is set to a very high value of 4.5V, in the first cycle A good charge-discharge curve was obtained. This is because the positive electrode active material of one aspect of the present invention has high charge This suggests that the crystal structure is highly stable even under voltage.

[0433] Furthermore, from Figures 24A and 24B, cells Cel_1 and Cel_ have an ionic liquid as the electrolyte. In models 2 and Cel_3, after 300 cycles, the capacity is 80% or more of the initial discharge capacity. The values ​​were maintained, indicating that it exhibited extremely excellent characteristics.

[0434] Furthermore, as shown in Figure 25, the amount of positive electrode active material and negative electrode active material supported is increased, and black Even with cells using a different type of lead, excellent cycle performance was maintained even when the charging voltage was increased to 4.5V. It was found that the desired characteristics could be obtained.

[0435] Based on the above, in a secondary battery according to one aspect of the present invention, an excellent positive electrode active material is used, and an ionic liquid It was found that significantly superior properties can be obtained by using this as the electrolyte.

[0436] [Cycle Characteristics Evaluation 2] Next, the cycle characteristics of the secondary battery were evaluated at 45°C.

[0437] Cells Cel_11 to Cel_23, shown in Table 3, were fabricated as battery cells. The positive electrode used was... (Positive Electrode), Negative Electrode The combination of (de) and electrolyte (Electrolyte Solution), and The charge voltage is shown in Table 3.

[0438] [Table 3]

[0439] The amount of positive electrode active material supported in positive electrode P1 is approximately 6.5 m³ for cells Cel_11 to Cel_20. g / cm 2 Cells Cel_21 to Cel_23 contain approximately 11 mg / cm³ 2 That's what I decided.

[0440] The area of ​​the positive electrode active material layer at positive electrode P1 is 8.194 cm². 2 That's what I decided.

[0441] The amount of negative electrode active material loaded in negative electrode N1 and negative electrode N2 in each battery cell is approximately 7 in terms of capacity ratio. The percentage was adjusted to be between 7% and 83%.

[0442] Charging is performed using CCCV (0.2C, initial current 0.02C), and discharging is performed using CC (0.2C, 2. The test was conducted at 5V. The capacity of the secondary battery was calculated based on the weight of the positive electrode active material.

[0443] Figure 28A shows the cycle characteristics of cells Cel_11 to Cel_13 at 45°C. Figure 28B shows the cycle characteristics of cells Cel_14 through Cel_16, and cell Cel_17 Figure 29A shows the cycle characteristics of cells Cel_20, and cells Cel_21 through Cel_ The cycle characteristics of the 23 components are shown in Figure 29B.

[0444] From Figures 28A and 28B, in cells using ionic liquid as the electrolyte, the charging voltage is 4.45 The results showed that the decrease in discharge capacity was extremely small even at V. On the other hand, the organic electrolyte In the cells used, a decrease in discharge capacity began to be observed at a charging voltage of 4.45V.

[0445] From Figure 29A, when the charging voltage is set to 4.5V, in a cell using an ionic liquid as the electrolyte, However, a gradual decrease in discharge capacity was observed. On the other hand, as shown in Figures 24A and 24B, at 25°C Furthermore, good characteristics were obtained even when the charging voltage was set to 4.5V. Therefore, By controlling the charging voltage according to the temperature range, the discharge capacity associated with the use of secondary batteries is controlled. This suggests that the decrease in performance can be suppressed, resulting in a long-life secondary battery.

[0446] Furthermore, as shown in Figure 29B, the amount of positive electrode active material and negative electrode active material supported is increased, Even in cells with a different type of graphite, excellent cycle performance was observed at a charging voltage of 4.45V. It was found that the desired characteristics could be obtained.

[0447] [Evaluation of rating characteristics] Next, the rate characteristics were evaluated at 10°C.

[0448] Cells Cel_31 to Cel_33, shown in Table 4, were fabricated as battery cells. The positive electrode used was... (Positive Electrode), Negative Electrode The combination of (de) and electrolyte (Electrolyte Solution), and The charge voltage is shown in Table 4.

[0449] [Table 4]

[0450] The amount of positive electrode active material supported in positive electrode P1 is approximately 6.5 mg / cm³. 2 This was done. Negative electrode activity of negative electrode N1 The amount of material loaded was adjusted so that the volume ratio was approximately between 84% and 87%.

[0451] In the positive electrode, the area of ​​the positive electrode active material layer formed on the current collector is 8.194 cm². 2 That's what I decided.

[0452] Charging is performed using CCCV (0.2C, initial current 0.02C), and discharging is performed using CC (2.5V). The discharge was performed sequentially at discharge rates of 0.1, 0.2, 0.5, and 1 [C]. The pond capacity was calculated based on the weight of the positive electrode active material.

[0453] Figure 30A shows the cycle characteristics of cells Cel_31 to Cel_33 at 10°C. Figures 30B and 31 are shown below.

[0454] From Figures 30A, 30B, and 31, even under relatively low temperature conditions of 10°C, 0. It was found that at a 5C rate, more than 98% of the discharge capacity of 0.1C can be obtained. Furthermore, at a rate of 1C, Cel_31 achieves a discharge capacity of over 97% of that of 0.1C. This resulted in extremely excellent rate characteristics. Furthermore, in the case of Cel_32, the discharge capacity was low. A decline was observed, with the level remaining at approximately 60% of 0.1C. [Explanation of symbols]

[0455] 111: positive electrode, 111a: positive electrode, 115: negative electrode, 115a: negative electrode, 121: positive electrode current collector, 122: Positive electrode active material layer, 123: Separator, 125: Negative electrode current collector, 126: Negative electrode active material layer, 130: electrode assembly, 131: electrode assembly, 211a: positive electrode, 211b: negative electrode, 21 2a: Lead, 212b: Lead, 214: Separator, 250: Secondary battery, 251: External Assembly, 400: secondary battery, 401: positive electrode cap, 402: device, 402a: housing, 402b: secondary battery, 403: device, 403a: housing, 403b: secondary battery, 405 : Wristwatch-type device, 405a: Display unit, 405b: Strap unit, 406: Strap-type device S, 406a: Belt section, 406b: Wireless power supply receiving section, 413: Conductive plate, 414: Conductive plate, 415: Energy storage system, 416: Wiring, 420: Control circuit, 421: Wiring, 42 2: Wiring, 423: Wiring, 424: Conductor, 425: Insulator, 426: Wiring, 490: Eye Mirror-type device, 490a: frame, 490b: display unit, 491: headset-type device S, 491a: microphone section, 491b: flexible pipe, 491c: earphone section, 5 00: Secondary battery, 501: Positive electrode current collector, 502: Positive electrode active material layer, 503: Positive electrode, 504: 505: Negative electrode current collector, 506: Negative electrode active material layer, 507: Separator, 508: Electrolytic Liquid, 509: Outer casing, 510: Positive lead electrode, 511: Negative lead electrode, 513: Secondary Battery, 514: Terminal, 515: Seal, 517: Antenna, 519: Layer, 521: Sealing part , 522: Sealing part, 523: Sealing part, 529: Label, 531: Secondary battery pack, 540 : Circuit board, 551: one side, 552: the other side, 590: control circuit, 590a: circuit system 590b: Circuit system, 601: Positive cap, 602: Battery can, 603: Positive terminal 604: Positive electrode, 605: Separator, 606: Negative electrode, 607: Negative electrode terminal, 608: Insulation Plate, 609: Insulating plate, 611: PTC element, 613: Safety valve mechanism, 730: Charging control circuit , 900: Circuit board, 910: Label, 911: Terminal, 912: Battery control circuit, 913: Secondary battery, 914: Antenna, 915: Seal, 916: Layer, 917: Layer, 918: Antenna Tena, 920: Display device, 921: Sensor, 922: Terminal, 930: Housing, 931: Negative electrode , 932: Positive electrode, 933: Separator, 950: Winding body, 951: Terminal, 952: Terminal, 971: electrode, 972: electrode, 981: film, 982: film, 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, 7000: Robot, 7100: Portable display device, 7101: Enclosure, 7102 : Display unit, 7103: Operation buttons, 7104: Battery, 7120: Aircraft unit, 7140: Sweep Exclusions: Robot, 7160: Electric vehicle, 7200: Portable information terminal, 7201: Enclosure, 720 2: Display unit, 7203: Band, 7204: Buckle, 7205: Operation buttons, 7206 : Input / Output terminals, 7207: Icon, 7210: Smartphone, 7220: PC, 72 40: Game console, 7260: Game console, 7262: Controller, 7300: Display device, 7304: Display unit, 7400: Mobile phone, 7401: Housing, 7402: Display unit, 740 3: Operation buttons, 7404: External connection port, 7405: Speaker, 7406: Microphone, 7407: Rechargeable battery, 7408: Control circuit, 7500: Electronic cigarette, 7501: Atomizer 7504: Secondary battery, 8000: Display device, 8001: Housing, 8002: Display unit, 80 03: Speaker unit, 8004: Rechargeable battery, 8005: Audio input device, 8007: Speaker -Ka, 8008: Display unit, 8009: Portable information terminal, 8010: Charging module, 802 1: Charging device, 8022: Cable, 8024: Energy storage system, 8100: Lighting device, 8 101: Enclosure, 8102: Light source, 8103: Rechargeable battery, 8104: Ceiling, 8105: Side wall 8106: Floor, 8107: Window, 8200: Indoor unit, 8201: Enclosure, 8202: Air outlet 8203: Secondary battery, 8204: Outdoor unit, 8300: Electric refrigerator / freezer, 8301: Enclosure 8302: Door for refrigerator compartment, 8303: Door for freezer compartment, 8304: Rechargeable battery, 8400: Automatic Car, 8401: Headlight, 8406: Electric motor, 8500: Automobile, 8600: Scooter, 8601: Side mirror, 8602: Power storage system, 8603: Turn signal light, 8604: Under-seat storage, 8700: Electric bicycle, 8701: Battery, 8702: Energy storage system TEM, 8703: Display unit, 8704: Control circuit, 9600: Tablet terminal, 9601 : Notebook personal computer, 9625: Switch, 9626: Switch, 962 7: Power switch, 9628: Operation switch, 9629: Fastener, 9630: Housing, 96 30a: enclosure, 9630b: enclosure, 9630B: enclosure, 9631: display unit, 9633: thick Solar cell, 9634: control circuit, 9635: energy storage, 9640: movable part, 9650: keyboard Code section

Claims

1. It comprises a positive electrode, a negative electrode, an electrolyte, and an outer casing. The positive electrode has a positive electrode active material, The positive electrode active material comprises lithium, cobalt, oxygen, magnesium, and fluorine. The negative electrode comprises graphite and a conductive additive. The conductive additive has carbon fibers, The electrolyte has an ionic liquid, The cation of the ionic liquid is selected from one or more of the following: aromatic cations, quaternary ammonium cations, tertiary sulfonium cations, and quaternary phosphonium cations. As the anion of the aforementioned ionic liquid (FSO ２ ) ２ N － or (CF ３ SO ２ ) ２ N － It has, The exterior body has a laminated structure comprising a nylon layer, a metal layer, and a polypropylene layer. The polypropylene layer is a secondary battery having a region in contact with the electrolyte.

2. An electronic device having the secondary battery described in claim 1 and a battery control circuit.

3. In claim 1, The aforementioned secondary battery is curved, An electronic device in which the radius of curvature of the exterior body is 3 mm or more and 30 mm or less.

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