WO2022023865A1 - 二次電池及びその作製方法 - Google Patents

二次電池及びその作製方法 Download PDF

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WO2022023865A1
WO2022023865A1 PCT/IB2021/056482 IB2021056482W WO2022023865A1 WO 2022023865 A1 WO2022023865 A1 WO 2022023865A1 IB 2021056482 W IB2021056482 W IB 2021056482W WO 2022023865 A1 WO2022023865 A1 WO 2022023865A1
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positive electrode
secondary battery
active material
lithium
electrode active
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PCT/IB2021/056482
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English (en)
French (fr)
Japanese (ja)
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斉藤丞
門馬洋平
三上真弓
落合輝明
成田和平
吉谷友輔
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株式会社半導体エネルギー研究所
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Priority to JP2022539783A priority Critical patent/JPWO2022023865A5/ja
Publication of WO2022023865A1 publication Critical patent/WO2022023865A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a secondary battery and a method for manufacturing the secondary battery. Or, it relates to a portable information terminal having a secondary battery, a vehicle, or the like.
  • the uniformity of the present invention relates to a product, a method, or a manufacturing method.
  • the invention relates to a process, machine, manufacture, or composition (composition of matter).
  • One aspect of the present invention relates to a semiconductor device, a display device, a light emitting device, a power storage device, a lighting device, an electronic device, or a method for manufacturing the same.
  • the semiconductor device refers to all devices that can function by utilizing the semiconductor characteristics
  • the electro-optical device, the semiconductor circuit, and the electronic device are all semiconductor devices.
  • a power storage device refers to an element having a power storage function and a device in general.
  • a power storage device also referred to as a secondary battery
  • a lithium ion secondary battery such as a lithium ion secondary battery, a lithium ion capacitor, an electric double layer capacitor, and the like.
  • Lithium-ion secondary batteries which have particularly high output and high energy density, are portable information terminals such as mobile phones, smartphones, or notebook computers, portable music players, digital cameras, medical devices, or hybrid vehicles (HVs), and electric vehicles.
  • HVs hybrid vehicles
  • EVs electric vehicles
  • PSVs plug-in hybrid vehicles
  • Patent Document 1 improvement of the positive electrode active material has been studied in order to improve the cycle characteristics and the capacity of the lithium ion secondary battery (for example, Patent Document 1 and Non-Patent Document 1).
  • the characteristics required for the power storage device include improvement of safety and long-term reliability in various operating environments.
  • One aspect of the present invention is to provide a positive electrode active material having a large charge / discharge capacity.
  • one of the issues is to provide a positive electrode active material having a high charge / discharge voltage.
  • it is an object to provide a positive electrode active material with less deterioration.
  • it is an object to provide a new positive electrode active material.
  • Another issue is to provide a secondary battery having a large charge / discharge capacity.
  • Another issue is to provide a secondary battery having a high charge / discharge voltage.
  • one of the issues is to provide a secondary battery having high safety or reliability.
  • one of the issues is to provide a secondary battery with less deterioration.
  • one of the issues is to provide a secondary battery having a long life.
  • one of the issues is to provide a new secondary battery.
  • one aspect of the present invention is to provide a novel substance, an active material, a power storage device, or a method for producing the same.
  • a lithium oxide When a lithium oxide is used, it is desired to achieve both a positive electrode active material having a high charge / discharge voltage and a positive electrode active material having high safety or reliability. If there is a portion where pure LiCoO 2 is exposed on the particle surface, unevenness may occur, cobalt or oxygen may be desorbed during charging and discharging, the crystal structure may collapse, and deterioration may occur.
  • a material having a layered rock salt type crystal structure such as lithium cobalt oxide (LiCoO 2 ) has a high discharge capacity and is excellent as a positive electrode active material for a secondary battery.
  • the material having a layered rock salt type crystal structure include a composite oxide represented by LiMO 2 .
  • the element M one or more selected from Co and Ni can be mentioned.
  • the element M in addition to one or more selected from Co and Ni, one or more selected from Al and Mg can be mentioned.
  • Lithium cobalt oxide may have a different crystal structure depending on the Li occupancy x of the lithium site.
  • the amount of lithium that can be inserted and removed in the positive electrode active material is indicated by x in the composition formula, for example, x in Li x CoO 2 , or x in Li x MO 2 .
  • Li x CoO 2 in the present specification can be appropriately read as Li x MO 2 .
  • When properly synthesized lithium cobalt oxide before use for the positive electrode satisfies the stoichiometric ratio, it is LiCoO 2 and x 1.
  • discharge completed means a state in which the voltage is 3.0 V or 2.5 V or less with a current of 100 mAh / g or less, for example.
  • discharge completed means a state in which the voltage is 3.0 V or 2.5 V or less with a current of 100 mAh / g or less, for example.
  • a metal oxide is provided as a modifier on a part or all of the surface of the particles of lithium cobalt oxide (LiCoO 2 ). Reliability is improved by providing a modifier at least a part of the particles.
  • the modifier is preferably a material that is electrically or mechanically tougher than the particles of lithium cobalt oxide (LiCoO 2 ).
  • a crystal model (layered crystal structure) of a lithium cobalt oxide film which is a general LCO (LiCoO 2 )
  • LCO LiCoO 2
  • a model in which a part of cobalt is replaced with another metal and oxygen around it is extracted is evaluated.
  • the material of the modifier When the first energy that becomes unstable when oxygen is deficient is calculated from the lithium cobalt oxide film, it is 4.32 eV, and the second energy that becomes unstable when the metal (cobalt) after oxygen deficiency is deficient is It was 7.46 eV.
  • the calculation was performed using various material compositions.
  • the first energy that becomes unstable when oxygen is depleted from the lanthanum oxide is 6.68 eV, which is larger than the value of LCO, and is suitable as a modifier.
  • the first energy that becomes unstable when oxygen is depleted from yttrium oxide is 6.63 eV, which is larger than the value of LCO, and is suitable for a modifier.
  • an oxide containing lanthanum and zirconium may be used as the modifying material, and an oxide containing yttrium and zirconium may be used as the modifying material.
  • the first energy, which becomes unstable when oxygen is depleted from the zirconium oxide, is 6.07 eV, which is larger than the value of LCO, and is suitable for a modifier.
  • the concentration of fluorine in the positive electrode active material provided with the modifying material is higher in the surface layer portion than in the central portion of the positive electrode active material.
  • This concentration distribution of fluorine is caused by the addition of fluorine in two steps in the method for producing a positive electrode active material, that is, after producing particles containing lithium and cobalt.
  • the XPS analysis method, the TOF-SIMS method, or the EDX method is used, and the maximum concentration difference detected in the first region and the second region is more than double. We will call it non-uniform in some cases.
  • the surface layer portion of particles such as an active material is, for example, a region within 50 nm, more preferably within 35 nm, still more preferably within 20 nm, and most preferably within 10 nm from the surface toward the inside.
  • the surface created by cracks and cracks can also be called the surface.
  • the area deeper than the surface layer is called the inside.
  • the grain boundaries are, for example, a portion where particles are fixed to each other, a portion where the crystal orientation changes inside the particles (including the central portion), a portion containing many defects, and a portion where the crystal structure is disturbed. Etc. Grain boundaries can be said to be one of the surface defects.
  • the vicinity of the grain boundary means a region within 10 nm from the grain boundary.
  • the particle is not limited to a spherical shape (the cross-sectional shape is a circle), and the cross-sectional shape of each particle is an ellipse, a rectangle, a trapezoid, a cone, a quadrangle with rounded corners, and an asymmetry.
  • the shape of the individual particles may be irregular.
  • nickel, aluminum, or titanium is further contained in the positive electrode active material, it is preferably obtained by the sol-gel method.
  • the modifying material When lanthanum or yttrium is used as the modifying material, it is preferably obtained by the sol-gel method.
  • the melting point of the lantern is about 920 ° C.
  • the number of atoms of cobalt contained in lithium cobalt oxide may be 1, and the concentration of lantern contained in the metal source may be 0.001 times or more and less than 0.5 times.
  • the concentration of yttrium contained in the metal source may be 0.001 times or more and less than 0.5 times.
  • zirconium when zirconium is used, it is preferably obtained by the sol-gel method. In the case of zirconium, for example, the number of atoms of cobalt contained in lithium cobalt oxide may be 1, and the concentration of zirconium contained in the metal source may be 0.001 times or more and less than 0.5 times.
  • the modifying material refers to a plurality of materials to be adhered to the positive electrode active material particles, and has a function of suppressing deterioration of the positive electrode active material particles such as cobalt elution.
  • An alloy may be formed at a portion where the modifier and the positive electrode active material particles are in contact with each other.
  • the modifier may or may not contribute to the movement of lithium ions in the charging and discharging of the secondary battery. If it contributes, it can be called a positive electrode active material including a modifier.
  • the modifier may have at least a function of suppressing deterioration of the positive electrode active material particles, and may also be referred to as a protective material that protects the particles from a chemical reaction with the electrolytic solution.
  • the positive electrode active material disclosed in the present specification may be said to be a granular material in which child particles (lanthanum oxide, yttrium oxide or zirconium oxide) are coated in a non-uniform state on the surface of the mother particles.
  • One aspect of the present invention is, for example, a NiCo-based oxide represented by LiNi x Co 1 ⁇ x O 2 (0 ⁇ x ⁇ 1) and a lithium composite oxide represented by LiM x Oy. It can also be applied to the NiMn system represented by LiNi x Mn 1 ⁇ x O 2 (0 ⁇ x ⁇ 1).
  • NiComn system also referred to as NCM
  • LiNi x Coy Mn z O 2 x> 0, y > 0, 0.8 ⁇ x + y + z ⁇ 1.2
  • it is preferable that x, y and z satisfy a value of x: y: z 5: 2: 3 or a vicinity thereof.
  • lithium composite oxide having a layered rock salt type crystal structure it can be applied to, for example, Li 2 MnO 3 , Li 2 MnO 3 -LiMeO 2 (Me is Co, Ni, Mn) and the like.
  • positive electrode active material particles with less deterioration can be provided.
  • one aspect of the present invention can provide a method for producing a positive electrode active material.
  • novel positive electrode active material particles can be provided.
  • a novel power storage device can be provided by one aspect of the present invention.
  • FIG. 1A is a photographic diagram showing an electron beam image (SEM), and FIG. 1B is a schematic diagram.
  • FIG. 2 is a diagram illustrating the crystal structure of the positive electrode active material (configuration 1).
  • FIG. 3 is a diagram illustrating the crystal structure of the positive electrode active material (configuration 2).
  • FIG. 4 is a graph showing the calculation results.
  • FIG. 5 is a diagram showing an example of a flow showing one aspect of the present invention.
  • FIG. 6 is a diagram showing an example of a flow showing one aspect of the present invention.
  • 7A to 7D are cross-sectional views illustrating an example of a positive electrode of a secondary battery.
  • 8A is an exploded perspective view of the coin-type secondary battery, FIG.
  • FIG. 8B is a perspective view of the coin-type secondary battery, and FIG. 8C is a sectional perspective view thereof.
  • FIG. 9A shows an example of a cylindrical secondary battery.
  • FIG. 9B shows an example of a cylindrical secondary battery.
  • FIG. 9C shows an example of a plurality of cylindrical secondary batteries.
  • FIG. 9D shows an example of a power storage system having a plurality of cylindrical secondary batteries.
  • 10A and 10B are diagrams for explaining an example of a secondary battery
  • FIG. 10C is a diagram showing the inside of the secondary battery.
  • 11A to 11C are diagrams illustrating an example of a secondary battery.
  • 12A and 12B are views showing the appearance of the secondary battery.
  • 13A to 13C are diagrams illustrating a method for manufacturing a secondary battery.
  • FIG. 14A is a diagram showing the appearance of the battery pack
  • FIG. 14B is a diagram showing a configuration example of the battery pack
  • FIG. 14C is a diagram showing a configuration example of the battery pack.
  • 15A and 15B are diagrams illustrating an example of a secondary battery.
  • 16A to 16C are diagrams illustrating an example of a secondary battery.
  • 17A and 17B are diagrams illustrating an example of a secondary battery.
  • 18A is a perspective view of a battery pack showing one aspect of the present invention
  • FIG. 18B is a block diagram of the battery pack
  • FIG. 18C is a block diagram of a vehicle having a motor.
  • 19A to 19D are diagrams illustrating an example of a transportation vehicle.
  • FIGS. 20A and 20B are diagrams illustrating a power storage device according to an aspect of the present invention.
  • 21A is a diagram showing an electric bicycle
  • FIG. 21B is a diagram showing a secondary battery of the electric bicycle
  • FIG. 21C is a diagram illustrating an electric motorcycle.
  • 22A to 22D are diagrams illustrating an example of an electronic device.
  • 23A shows an example of a wearable device
  • FIG. 23B shows a perspective view of the wristwatch-type device
  • FIG. 23C is a diagram illustrating a side surface of the wristwatch-type device.
  • FIG. 24A is a graph showing the discharge capacity
  • FIG. 24B is a graph showing the maintenance rate of the discharge capacity.
  • FIG. 25A is a graph showing the discharge capacity
  • FIG. 25B is a graph showing the maintenance rate of the discharge capacity.
  • FIG. 26A is a graph showing the discharge capacity
  • FIG. 26B is a graph showing the maintenance rate of the discharge capacity.
  • FIG. 27 is
  • the positive electrode active material of one aspect of the present invention has fluorine. Fluorine can improve the wettability of the surface of the positive electrode active material and homogenize it.
  • the positive electrode active material thus obtained has a crystal structure that does not easily collapse in repeated charging and discharging such that x in Li x CoO 2 becomes 0.24 or less, and the secondary active material using the positive electrode active material having such characteristics is used. Batteries have significantly improved cycle characteristics.
  • the surface unevenness is larger and rougher than the above range, physical cracks or collapse of the crystal structure may occur.
  • the crystal structure collapses the exposed portion of pure LiCoO 2 may be exposed on the surface and the deterioration may be accelerated.
  • lithium oxide a material having a layered rock salt type crystal structure is preferable, and examples thereof include a composite oxide represented by LiMO 2 .
  • the element M one or more selected from Co and Ni can be mentioned.
  • the element M in addition to one or more selected from Co and Ni, one or more selected from Al and Mg can be mentioned.
  • fluorine By including fluorine in the vicinity of the surface, not only fluorine but also magnesium or aluminum can be arranged in the vicinity of the surface at a high concentration. Fluorine is prevented from being diffused outward as a gas by covering it with a lid and heat-treating it, and other aluminum and the like are diffused into a solid substance. Fluorine improves the wettability of the surface of the positive electrode active material and homogenizes it.
  • Composite oxides with lithium, transition metals and oxygen preferably have a layered rock salt type crystal structure with less defects and strain. Therefore, it is preferable that the composite oxide has few impurities. High impurities in composite oxides with lithium, transition metals and oxygen are likely to result in defective or strained crystal structures.
  • the surface of the positive electrode active material In order not to contain impurities, it is preferable to modify the surface of the positive electrode active material by mixing the fluoride, covering it with a lid, and heating it. As for the timing of closing the lid, cover the container before heating and then place it in the heating furnace, or after placing it in the heating furnace, cover the container and cover it, or before the fluoride melts. It is sufficient to cover the lid while heating.
  • the crystal structure of the positive electrode active material shown in the above configuration 1 before and after charging and discharging is shown in FIG.
  • the layered rock salt type composite oxide has a high discharge capacity, has a two-dimensional lithium ion diffusion path, is suitable for a lithium ion insertion / desorption reaction, and is excellent as a positive electrode active material for a secondary battery. Therefore, it is particularly preferable that the inside, which occupies most of the volume of the positive electrode active material, has a layered rock salt type crystal structure.
  • FIG. 2 shows the layered rock salt type crystal structure with R-3m (O3).
  • the surface layer portion of the positive electrode active material 100 of one aspect of the present invention shown in FIG. 1B even if lithium is removed from the positive electrode active material 100 by charging, the layered structure composed of the internal transition metal M and the octahedron of oxygen is broken. It is preferable to have a function of reinforcing so as not to be present. Alternatively, it is preferable that the surface layer portion functions as a barrier film for the positive electrode active material 100. Alternatively, it is preferable that the surface layer portion of the positive electrode active material 100 reinforces the positive electrode active material 100. Reinforcement here means suppressing structural changes in the surface layer portion and the inside of the positive electrode active material 100 such as oxygen desorption, and / or suppressing oxidative decomposition of the electrolyte on the surface of the positive electrode active material 100. To do.
  • the surface layer portion has a crystal structure different from that of the inside.
  • the surface layer portion preferably has a more stable composition and crystal structure at room temperature (25 ° C.) than the inside.
  • at least a part of the surface layer portion of the positive electrode active material 100 according to one aspect of the present invention has a rock salt type crystal structure.
  • the surface layer portion preferably has both a layered rock salt type crystal structure and a rock salt type crystal structure.
  • the surface layer portion preferably has the characteristics of both a layered rock salt type and a rock salt type crystal structure.
  • the surface layer portion is a region where lithium ions are first released during charging, and is a region where the lithium concentration tends to be lower than that inside. Further, it can be said that the atoms on the surface of the positive electrode active material 100 having the surface layer portion are in a state where some bonds are broken. Therefore, it can be said that the surface layer portion tends to be unstable and the deterioration of the crystal structure tends to start. On the other hand, if the surface layer can be made sufficiently stable, even when x in Li x CoO 2 is small, for example, even if x is 0.24 or less, the layered structure consisting of the internal transition metal M and the octahedron of oxygen is made difficult to break. Can be done. Furthermore, it is possible to suppress the displacement of the layer composed of the internal transition metal M and the octahedron of oxygen.
  • the surface layer portion preferably has the additive element A, and more preferably has a plurality of additive elements A. Further, it is preferable that the concentration of one or more selected from the additive element A is higher in the surface layer portion than in the inside. Further, it is preferable that one or more selected from the additive element A contained in the positive electrode active material 100 has a concentration gradient. Further, it is more preferable that the distribution of the positive electrode active material 100 differs depending on the additive element A. For example, it is more preferable that the depth of the concentration peak from the surface differs depending on the additive element A.
  • the concentration peak here means the maximum value of the concentration at 50 nm or less from the surface layer portion or the surface.
  • a part of the additive element A, magnesium, fluorine, titanium, silicon, phosphorus, boron, calcium and the like has a concentration gradient that increases from the inside toward the surface.
  • An element having such a concentration gradient is referred to as an additive element X.
  • another additive element A for example, aluminum, manganese, etc.
  • the concentration peak may be present in the surface layer portion or may be deeper than the surface layer portion.
  • An element having such a concentration gradient is referred to as an additive element Y.
  • magnesium which is one of the additive elements X, is divalent, and magnesium ions are more stable in the lithium site than in the transition metal M site in the layered rock salt type crystal structure, so that they are more likely to enter the lithium site.
  • the presence of magnesium in the lithium site of the surface layer at an appropriate concentration makes it easier to maintain the layered rock salt type crystal structure. It is presumed that this is because the magnesium present in the lithium site functions as a pillar that supports the two CoO layers. Further, the presence of magnesium can suppress the withdrawal of oxygen around magnesium in a state where the occupancy rate x in Li x CoO 2 is, for example, 0.24 or less. Further, it can be expected that the density of the positive electrode active material 100 increases due to the presence of magnesium. Further, when the magnesium concentration in the surface layer portion is high, it can be expected that the corrosion resistance to hydrofluoric acid generated by the decomposition of the electrolytic solution is improved.
  • the amount of magnesium contained in the entire positive electrode active material 100 is an appropriate amount.
  • the ratio of magnesium (Mg / Co) to the sum of the transition metal M contained in the positive electrode active material 100 of one aspect of the present invention is preferably 0.25% or more and 5% or less, and 0.5% or more and 2% or less. More preferably, about 1% is further preferable.
  • the amount of magnesium contained in the entire positive electrode active material 100 here may be a value obtained by performing elemental analysis of the entire positive electrode active material 100 using, for example, GD-MS, ICP-MS, or the like, or the positive electrode activity. It may be based on the value of the composition of the raw materials in the process of producing the substance 100.
  • Fluorine which is one of the additive elements X, is a monovalent anion, and when a part of oxygen is replaced with fluorine in the surface layer portion, the lithium withdrawal energy becomes small. This is because the change in the valence of the cobalt ion due to the desorption of lithium changes from trivalent to tetravalent in the absence of fluorine and from divalent to trivalent in the case of having fluorine, and the redox potentials are different. Therefore, when a part of oxygen is replaced with fluorine in the surface layer portion of the positive electrode active material 100, it can be said that the separation and insertion of lithium ions in the vicinity of fluorine are likely to occur smoothly.
  • the layered rock salt type crystal structure belonging to the space group R-3m, which is possessed by the composite oxide containing the transition metal M such as lithium and cobalt. It has a rock salt-type ion arrangement to be arranged, and a crystal structure capable of two-dimensional diffusion of lithium because the transition metal M and lithium are regularly arranged to form a two-dimensional plane. There may be defects such as cation or anion defects. Strictly speaking, the layered rock salt crystal structure may have a distorted lattice of rock salt crystals.
  • the rock salt type crystal structure has a cubic crystal structure including the space group Fm-3m, and cations and anions are alternately arranged. There may be a cation or anion deficiency.
  • the rock salt type has no distinction between cation sites, but the layered rock salt type has two types of crystalline cation sites, one occupied by lithium and the other occupied by the transition metal M.
  • the laminated structure in which the two-dimensional planes of cations and the two-dimensional planes of anions are arranged alternately is the same for both the rock salt type and the layered rock salt type.
  • the bright spots of the electron beam diffraction image corresponding to the crystal plane forming this quadratic plane when the central spot (transmission spot) is set to the origin 000, the bright spot closest to the central spot is ideal.
  • the rock salt type in the state has, for example, the (111) plane
  • the layered rock salt type has, for example, the (003) plane.
  • the bright spot on the (003) plane of LiCoO 2 is about half the distance of the bright spot on the (111) plane of MgO. Observed. Therefore, when the analysis region has, for example, two phases of rock salt type MgO and layered rock salt type LiCoO 2 , in the electron diffraction image, there is a plane orientation in which strong bright spots and weak bright spots are alternately arranged. do.
  • the bright spots common to the rock salt type and the layered rock salt type have high brightness, and the bright spots generated only by the layered rock salt type have low brightness.
  • the layer observed with high brightness and the layer observed with low brightness are alternately observed.
  • the rock salt type does not have such characteristics because there is no distinction between cation sites.
  • a crystal structure having the characteristics of both rock salt type and layered rock salt type when observed from a specific crystal orientation, layers observed with high brightness and layers observed with low brightness are alternately observed in a cross-sectional STEM image or the like.
  • a metal having an atomic number higher than that of lithium is present in a layer having a lower brightness, that is, a part of the lithium layer.
  • Layered rock salt crystals and anions of rock salt crystals have a cubic close-packed structure (face-centered cubic lattice structure). It is presumed that the anion also has a cubic close-packed structure in the O3'type crystal described later. Therefore, when the layered rock salt type crystal and the rock salt type crystal come into contact with each other, there is a crystal plane in which the directions of the cubic close-packed structure composed of anions are aligned.
  • the anions in the ⁇ 111 ⁇ plane of the cubic crystal structure have a triangular lattice.
  • the layered rock salt type is a space group R-3m and has a rhombohedral structure, but is generally represented by a composite hexagonal lattice to facilitate understanding of the structure, and the layered rock salt type (000l) plane has a hexagonal lattice.
  • the cubic ⁇ 111 ⁇ plane triangular lattice has an atomic arrangement similar to that of the layered rock salt type (000 l) plane hexagonal lattice. It can be said that the orientation of the cubic close-packed structure is aligned when both lattices are consistent.
  • the space group of layered rock salt type crystals and O3'type crystals is R-3m, which is different from the space group Fm-3m of rock salt type crystals (space group of general rock salt type crystals).
  • the mirror index of the crystal plane to be filled is different between the layered rock salt type crystal and the O3'type crystal and the rock salt type crystal.
  • the orientations of the crystals are substantially the same when the orientations of the cubic close-packed structures composed of anions are aligned.
  • TEM Transmission Electron Microscope
  • STEM Sccanning Transmission Electron Microscope, scanning transmission electron microscope
  • HAADF-STEM High Electron Microscope
  • ABF-STEM Annal Bright-Field Scanning Transmission Electron Microscopic, annular bright-field scanning transmission electron microscope
  • FIG. 3 shows changes in the crystal structure of the conventional positive electrode active material.
  • the conventional positive electrode active material shown in FIG. 3 is lithium cobalt oxide (LiCoO 2 ) having no additive element A in particular.
  • LiCoO 2 lithium cobalt oxide
  • changes in the crystal structure of lithium cobalt oxide having no additive element A are described in Non-Patent Documents 1 to 3 and the like.
  • x 1 lithium cobalt oxide in Li x CoO 2 .
  • the CoO 2 layer is a structure in which an octahedral structure in which oxygen is coordinated to cobalt is continuous with a plane in a shared ridge state. This may be referred to as a layer composed of an octahedron of cobalt and oxygen.
  • one CoO layer is present in the unit cell. Therefore, it may be called O1 type or monoclinic O1 type.
  • This structure can be said to be a structure in which CoO 2 structures such as trigonal O1 type and LiCo O 2 structures such as R-3m (O3) are alternately laminated. Therefore, this crystal structure may be referred to as an H1-3 type crystal structure.
  • the H1-3 type crystal structure has twice the number of cobalt atoms per unit cell as the other structures.
  • the c-axis of the H1-3 type crystal structure is shown in a diagram in which the c-axis is halved of the unit cell.
  • the coordinates of cobalt and oxygen in the unit cell are set to Co (0, 0, 0.42150 ⁇ 0.00016), O1 (0, It can be expressed as 0, 0.27671 ⁇ 0.00045) and O2 (0, 0, 0.11535 ⁇ 0.00045).
  • O1 and O2 are oxygen atoms, respectively.
  • Which unit cell should be used to represent the crystal structure of the positive electrode active material can be determined, for example, by Rietveld analysis of XRD. In this case, a unit cell having a small GOF (goodness of fit) value may be adopted.
  • the conventional lithium cobaltate When charging and discharging so that x in Li x CoO 2 becomes 0.24 or less are repeated, the conventional lithium cobaltate has an H1-3 type crystal structure and a discharged state R-3m (O3) structure. And, the change of the crystal structure (that is, the non-equilibrium phase change) is repeated between.
  • these two crystal structures have a large difference in volume.
  • the volume difference between the H1-3 type crystal structure and the discharged R-3m (O3) type crystal structure exceeds 3.5%, typically 3.9% or more. Is.
  • the structure of the H1-3 type crystal structure in which two CoO layers are continuous is likely to be unstable.
  • the conventional crystal structure of lithium cobalt oxide collapses.
  • the collapse of the crystal structure causes deterioration of the cycle characteristics. This is because the collapse of the crystal structure reduces the number of sites where lithium can stably exist, and it becomes difficult to insert and remove lithium.
  • the change in the crystal structure between the discharged state where x in Li x CoO 2 is 1 and the state where x is 0.24 or less is larger than that of the conventional positive electrode active material.
  • the deviation between the two CoO layers in the state where x is 1 and the state where x is 0.24 or less can be reduced.
  • the positive electrode active material shown in the above configuration 1 can have a more stable crystal structure than the conventional positive electrode active material in a state where x in Li x CoO 2 is 0.24 or less. Therefore, the positive electrode active material shown in the above configuration 1 is unlikely to cause a short circuit when x in Li x CoO 2 is maintained in a state of 0.24 or less. In such a case, the safety of the secondary battery is further improved, which is preferable.
  • FIG. 2 shows the crystal structure inside the positive electrode active material 100 when x in Li x CoO 2 is about 1 and 0.2. Since the inside occupies most of the volume of the positive electrode active material 100 and greatly contributes to charging and discharging, it can be said that the displacement of the CoO 2 layer and the change in volume are the most problematic parts.
  • the positive electrode active material 100 has the same crystal structure of R-3m (O3) as the conventional lithium cobalt oxide.
  • the positive electrode active material 100 has a crystal having a different structure when x is 0.24 or less, for example, about 0.2 and about 0.15, so that the conventional lithium cobalt oxide has an H1-3 type crystal structure.
  • x is 0.24 or less, for example, about 0.2 and about 0.15, so that the conventional lithium cobalt oxide has an H1-3 type crystal structure.
  • the O3'type crystal structure sets the coordinates of cobalt and oxygen in the unit cell within the range of Co (0,0,0.5), O (0,0,x), 0.20 ⁇ x ⁇ 0.25. Can be indicated by.
  • ions such as cobalt, nickel and magnesium occupy the oxygen 6 coordination position.
  • Light elements such as lithium may occupy the oxygen 4-coordination position.
  • the difference in volume per cobalt atom of the same number of O3'-type crystal structures from R-3m (O3) in the discharged state is 2.5% or less, more specifically 2.2% or less, typically 1. It is 8%.
  • the change in the crystal structure when the occupancy rate x in Li x CoO 2 is small, that is, when a large amount of lithium is removed, is larger than that of the conventional positive electrode active material. It is suppressed.
  • the change in volume when compared per the same number of cobalt atoms is also suppressed. Therefore, the crystal structure of the positive electrode active material 100 does not easily collapse even if charging and discharging are repeated so that the occupancy rate x becomes 0.24 or less. Therefore, the positive electrode active material 100 suppresses a decrease in charge / discharge capacity in the charge / discharge cycle.
  • the positive electrode active material 100 since more lithium can be stably used than the conventional positive electrode active material, the positive electrode active material 100 has a large discharge capacity per weight and per volume. Therefore, by using the positive electrode active material 100, a secondary battery having a high discharge capacity per weight and per volume can be manufactured.
  • the positive electrode active material 100 may have an O3'type crystal structure when the occupancy rate x in Li x CoO 2 is 0.15 or more and 0.24 or less, and the occupancy rate x is 0.24. It is presumed that it has an O3'type crystal structure even if it exceeds 0.27 or less.
  • the crystal structure is not necessarily limited to the above range of x because it is affected not only by the occupancy rate x in Li x CoO 2 but also by the number of charge / discharge cycles, charge / discharge current, temperature, electrolyte and the like.
  • the occupancy rate x in Li x CoO 2 of the positive electrode active material 100 exceeds 0.1 and is 0.24 or less, the entire inside of the positive electrode active material 100 does not have to have an O3'type crystal structure. It may contain other crystal structures or may be partially amorphous.
  • a state in which the occupancy rate x in Li x CoO 2 is small can be rephrased as a state in which the battery is charged with a high charging voltage.
  • a charging voltage of 4.6 V or higher based on the potential of lithium metal is a high charging voltage.
  • the charging voltage is expressed with reference to the potential of lithium metal.
  • the positive electrode active material 100 can maintain a crystal structure having a symmetry of R-3m (O3) even when charged at a high charging voltage, for example, a voltage of 4.6 V or higher at 25 ° C. In other words, it is preferable. Further, it can be said that it is preferable because an O3'type crystal structure can be obtained when the battery is charged at a higher charging voltage, for example, a voltage of 4.65 V or more and 4.7 V or less at 25 ° C.
  • the positive electrode active material 100 may have an O3'type crystal structure.
  • the voltage of the secondary battery is lower than the above by the potential of graphite.
  • the potential of graphite is about 0.05V to 0.2V with respect to the potential of lithium metal. Therefore, a secondary battery using graphite as the negative electrode active material has the same crystal structure when the voltage is obtained by subtracting the graphite potential from the above voltage.
  • lithium is present in all lithium sites with an equal probability, but the present invention is not limited to this. It may be unevenly present in some lithium sites, or may have symmetry such as monoclinic crystal O1 (Li 0.5 CoO 2 ) shown in FIG.
  • the distribution of lithium can be analyzed, for example, by neutron diffraction.
  • the O3'type crystal structure has lithium at random between layers, but is similar to the CdCl 2 type crystal structure.
  • This crystal structure similar to CdCl type 2 is similar to the crystal structure when lithium nickel oxide is charged to Li 0.06 NiO 2 , but is pure lithium cobalt oxide or a layered rock salt type positive electrode active material containing a large amount of cobalt. It is known that usually does not have a CdCl type 2 crystal structure.
  • the criteria for selecting the modifier is to calculate the value of the energy that becomes unstable based on the procedure shown below, and based on the calculation result, in the present embodiment, the materials of the modifier are lanthanum oxide and yttrium oxide. , Zirconium oxide is used.
  • the resistance to oxygen or metal deficiency is calculated by first-principles calculation for the reference LiCoO 2 . ..
  • the amount of energy destabilized when O-deficiency occurs from the crystal structure of LiCoO 2 was calculated using the first-principles calculation.
  • Table 1 shows the specific calculation conditions for the above-mentioned quantum molecular dynamics calculation.
  • VASP Vienna ab initio simulation package
  • the total number of atoms was 384 when there was no defect in the initial state, 383 when oxygen in the crystal structure was deleted, and 382 when the metal element in the crystal structure was deleted.
  • the specific calculation method of the first energy and the second energy is shown below.
  • ⁇ E is obtained from the difference in generated energy generated when oxygen is extracted from the initial structure based on the unit cell of LiCoO 2 .
  • the lattice and atomic position were optimized using the LiCoO 2 structure with 96 Li atoms, 96 Co atoms, and 192 O atoms as the initial structure model.
  • the crystal structure of this LiCoO 2 was a layered rock salt type structure, and the space group was calculated using the crystal structure of R-3m.
  • the first-principles electronic state calculation package VASP was used.
  • the calculation conditions the conditions shown in Table 1 were used.
  • the first energy that becomes unstable when oxygen close to Co is extracted can be expressed by the following mathematical formula.
  • Etotal (Li 96 Co 96 O 192 ) has energy equivalent to 384 atoms of LiCo O 2
  • Etotal (Li 96 Co 96 O 191 ) has 383 atoms lacking one O element from LiCo O 2 . Minute energy.
  • Etotal (O2) is the energy of one isolated O2 molecule.
  • Etotal Li 96 Co 95 O 191
  • Etotal (Co) is the energy of one isolated Co atom.
  • the first energy which becomes unstable when the oxygen of LiCoO 2 is depleted, was calculated to be 4.32 eV.
  • the second energy that becomes unstable when Co is deficient was calculated to be 7.46 eV.
  • the first energy of the modifier is higher than 4.32 eV, which is the first energy of LiCoO 2 before modification, oxygen deficiency of the entire particle is exhibited. It is thought that the particles will be stronger because it is less likely to occur. Further, if the second energy of the modifier shows a higher value, it can be said that the film is less likely to elute the metal after oxygen deficiency, so that the film is maintained for a longer period of time, and thus the effect of modification on the positive electrode material. However, it is considered that it is difficult to remove due to deterioration due to charging and discharging. Therefore, the modifiers showing higher values of the first energy and the second energy are considered to be preferable.
  • Lanthanum oxide has a first energy of 6.68 eV that becomes unstable when oxygen close to the lanthanum is extracted, and a second energy that becomes unstable when the lanthanum is depleted after oxygen is depleted is 11. It was .32 eV.
  • Yttrium oxide has a first energy of 6.63 eV that becomes unstable when oxygen close to yttrium is extracted, and a second energy that becomes unstable when yttrium is deficient after oxygen is deficient is 18. It was .83 eV.
  • Zirconium oxide has a first energy of 6.07 eV that becomes unstable when oxygen close to zirconium is extracted, and a second energy that becomes unstable when zirconium is depleted after oxygen is depleted is 23. It was .15 eV.
  • lanthanum oxide, yttrium oxide, and zirconium oxide are materials that are less likely to release oxygen and metal elements than LiCoO 2 , and can be said to be suitable as modifiers. Further, a combination thereof, for example, both lanthanum oxide and zirconium oxide may be used as a modifier, or both yttrium oxide and zirconium oxide may be used as a modifier.
  • FIG. 1A shows a photographic diagram of the periphery of the positive electrode active material 100 obtained by an electron beam image (SEM). Further, FIG. 1B shows the positive electrode active material 100 and the modifiers 101a and 101b on the surface thereof.
  • the modifier is smaller than the particles of configuration 1 or 2, and is scattered or scattered on the surface of the particles and arranged in at least one place.
  • the average particle diameter (D50: also referred to as median diameter) is preferably 1 ⁇ m or more and 100 ⁇ m or less, more preferably 2 ⁇ m or more and 40 ⁇ m or less, and further preferably 5 ⁇ m or more and 30 ⁇ m or less.
  • a lithium source and a transition metal M source are prepared as materials for the composite oxide (LiMO 2 ) having lithium, a transition metal M, and oxygen.
  • the composite oxide (LiMO 2 ) may be formed by using the coprecipitation method.
  • lithium source for example, lithium carbonate, lithium fluoride or the like can be used.
  • the transition metal M it is preferable to use a metal capable of forming a layered rock salt type composite oxide belonging to the space group R-3m together with lithium.
  • a metal capable of forming a layered rock salt type composite oxide belonging to the space group R-3m together with lithium for example, at least one of manganese, cobalt and nickel can be used. That is, as the transition metal M source, only cobalt may be used, only nickel may be used, two types of cobalt and manganese, or two types of cobalt and nickel may be used, and cobalt, manganese, and nickel may be used. 3 types may be used.
  • a metal capable of forming a layered rock salt type composite oxide When a metal capable of forming a layered rock salt type composite oxide is used, it is preferable to use a mixing ratio of cobalt, manganese, and nickel within a range in which a layered rock salt type crystal structure can be obtained. Further, aluminum may be added to these transition metals to the extent that a layered rock salt type crystal structure can be obtained.
  • transition metal M source an oxide, a hydroxide, or the like of the above-mentioned metal exemplified as the transition metal M can be used.
  • cobalt source for example, cobalt oxide, cobalt hydroxide and the like can be used.
  • manganese source manganese oxide, manganese hydroxide or the like can be used.
  • nickel source nickel oxide, nickel hydroxide or the like can be used.
  • aluminum source aluminum oxide, aluminum hydroxide, or the like can be used.
  • Step S12 the above-mentioned lithium source and transition metal M source are mixed.
  • Mixing can be done dry or wet.
  • a ball mill, a bead mill or the like can be used for mixing.
  • zirconia balls it is preferable to use zirconia balls as a pulverizing medium, for example.
  • step S13 the materials mixed above are heated.
  • This step may be referred to as first heating or firing to distinguish it from the subsequent heating step.
  • the first heating is to put the material in an alumina crucible, cover it, and heat it in a muffle furnace.
  • the heating is preferably performed at 800 ° C. or higher and lower than 1100 ° C., more preferably 900 ° C. or higher and 1000 ° C. or lower, and further preferably about 950 ° C.
  • it is preferably 800 ° C. or higher and 1000 ° C. or lower.
  • it is preferably 900 ° C. or higher and 1100 ° C. or lower.
  • the temperature is too low, the decomposition and melting of the lithium source and the transition metal M source may be insufficient.
  • the temperature is too high, defects may occur due to causes such as use as the transition metal M, excessive reduction of the metal responsible for the redox reaction, and evaporation of lithium.
  • cobalt is used as the transition metal M, a defect in which cobalt becomes divalent may occur.
  • the heating time can be, for example, 1 hour or more and 100 hours or less, and preferably 2 hours or more and 20 hours or less. Alternatively, it is preferably 1 hour or more and 20 hours or less. Alternatively, it is preferably 2 hours or more and 100 hours or less.
  • the firing is preferably performed in an atmosphere such as dry air where there is little water (for example, a dew point of ⁇ 50 ° C. or lower, more preferably ⁇ 100 ° C. or lower). For example, it is preferable to heat at 1000 ° C. for 10 hours, raise the temperature to 200 ° C./h, and set the flow rate of the dry atmosphere to 10 L / min. The heated material can then be cooled to room temperature (25 ° C.). For example, it is preferable that the temperature lowering time from the specified temperature to room temperature is 10 hours or more and 50 hours or less.
  • cooling to room temperature in step S13 is not essential. If there is no problem in performing the subsequent steps S31 to S33 or S41 to S43, the cooling may be performed at a temperature higher than room temperature.
  • the first heating may be performed by either a continuous system or a batch system.
  • step S14 the material obtained by the first heating is recovered to obtain a composite oxide (LiMO 2 ) having lithium, a transition metal M and oxygen.
  • a composite oxide LiMO 2
  • step S14 a composite oxide having lithium, a transition metal M and oxygen previously synthesized may be used. In this case, steps S11 to S13 can be omitted.
  • lithium cobalt oxide particles (trade name: CellSeed C-10N) manufactured by Nippon Chemical Industrial Co., Ltd. can be used as the pre-synthesized composite oxide.
  • This has an average particle size (D50) of about 12 ⁇ m, and in elemental analysis by glow discharge mass spectrometry (GD-MS), the magnesium concentration and fluorine concentration are 50 ppm wt or less, and the calcium concentration, aluminum concentration and silicon concentration are 100 ppm wt.
  • lithium cobaltate has a nickel concentration of 150 ppm wt or less, a sulfur concentration of 500 ppm wt or less, an arsenic concentration of 1100 ppm wt or less, and other elemental concentrations other than lithium, cobalt and oxygen of 150 ppm wt or less.
  • lithium cobalt oxide particles (trade name: CellSeed C-5H) manufactured by Nippon Chemical Industrial Co., Ltd. can also be used. This is a lithium cobalt oxide having an average particle size (D50) of about 6.5 ⁇ m and an elemental concentration other than lithium, cobalt and oxygen in elemental analysis by GD-MS, which is about the same as or less than C-10N. be.
  • cobalt is used as the metal M, and pre-synthesized lithium cobalt oxide particles (CellSeed C-10N) are used. Assuming that this lithium cobalt oxide is ideal LiCoO 2 , weigh the amount of additive elements (nickel, aluminum, lantern, etc.) to be added in a later step based on the amount of cobalt calculated from the weight to be used. ..
  • a halogen source such as a fluorine source or a chlorine source and a magnesium source are prepared as the material of the mixture 902. It is also preferable to prepare a lithium source.
  • fluorine source examples include lithium fluoride (LiF), magnesium fluoride (MgF 2 ), aluminum fluoride (AlF 3 ), titanium fluoride (TiF 4 ), cobalt fluoride (CoF 2 , CoF 3 ), and fluorine.
  • the fluorine source is not limited to solids, for example, fluorine (F 2 ), carbon fluoride, sulfur fluoride, oxygen fluoride (OF 2 , O 2 F 2 , O 3 F 2 , O 4 F 2 , O 2 F). Etc. may be used to mix the mixture in the atmosphere in the heating step described later. Further, a plurality of fluorine sources may be mixed and used. Among them, lithium fluoride is preferable because it has a relatively low melting point of 848 ° C. and is easily melted in the heat treatment step described later.
  • chlorine source for example, lithium chloride, magnesium chloride or the like can be used.
  • magnesium source for example, magnesium fluoride, magnesium oxide, magnesium hydroxide, magnesium carbonate and the like can be used.
  • lithium fluoride for example, lithium fluoride or lithium carbonate can be used. That is, lithium fluoride can be used both as a lithium source and as a fluorine source. Magnesium fluoride can be used both as a fluorine source and as a magnesium source.
  • lithium fluoride LiF is prepared as a fluorine source
  • magnesium fluoride MgF 2 is prepared as a fluorine source and a magnesium source.
  • LiF: MgF 2 65:35 (molar ratio)
  • the effect of lowering the melting point is highest.
  • the amount of lithium fluoride increases, there is a concern that the amount of lithium becomes excessive and the cycle characteristics deteriorate.
  • the term "neighborhood" means a value larger than 0.9 times and smaller than 1.1 times the value.
  • a solvent is prepared.
  • a ketone such as acetone, an alcohol such as ethanol and isopropanol, an ether such as diethyl ether, dioxane, acetonitrile, N-methyl-2-pyrrolidone (NMP) and the like can be used. It is more preferable to use an aprotic solvent that does not easily react with lithium. In this embodiment, acetone is used.
  • step S22 the material of the above mixture 902 is mixed and pulverized.
  • Mixing can be done dry or wet, but wet is preferred because it can be pulverized to a smaller size.
  • a ball mill, a bead mill or the like can be used for mixing.
  • zirconia balls it is preferable to use zirconia balls as a pulverizing medium, for example. It is preferable that the mixing and pulverizing steps are sufficiently performed to atomize the mixture 902.
  • step S23 the material mixed and pulverized above is recovered to obtain a mixture 902.
  • the D50 (median diameter) is preferably 600 nm or more and 20 ⁇ m or less, and more preferably 1 ⁇ m or more and 10 ⁇ m or less. Alternatively, it is preferably 600 nm or more and 10 ⁇ m or less. Alternatively, it is preferably 1 ⁇ m or more and 20 ⁇ m or less.
  • Such a finely divided mixture 902 tends to uniformly adhere the mixture 902 to the surface of the particles of the composite oxide when mixed with the composite oxide having lithium, transition metal M and oxygen in a later step. .. It is preferable that the mixture 902 is uniformly adhered to the surface of the composite oxide particles because halogen and magnesium are easily distributed in the region near the surface of the composite oxide particles after heating. If there is a region near the surface that does not contain halogen and magnesium, it may be difficult to form the O3'type crystal structure described later in the charged state.
  • step S31 the LiMO 2 obtained in step S14 and the mixture 902 are mixed.
  • the mixing in step S31 is preferably milder than the mixing in step S12 so as not to destroy the particles of the composite oxide.
  • the rotation speed is lower or the time is shorter than the mixing in step S12.
  • the dry type is a condition in which the particles are less likely to be destroyed than the wet type.
  • a ball mill, a bead mill or the like can be used for mixing.
  • zirconia balls it is preferable to use zirconia balls as a pulverizing medium, for example.
  • step S32 the material mixed above is recovered to obtain a first lithium mixture 903.
  • the present embodiment describes a method of adding a mixture of lithium fluoride and magnesium fluoride to lithium cobalt oxide having few impurities (or added elements), one aspect of the present invention is not limited to this. ..
  • a starting material of lithium cobalt oxide to which a magnesium source, a fluorine source, or the like is added and calcined may be used. In this case, since it is not necessary to separate the steps of steps S11 to S14 and the steps of steps S21 to S23, it is simple and highly productive.
  • lithium cobalt oxide to which magnesium and fluorine have been added in advance may be used. If lithium cobalt oxide to which magnesium and fluorine are added is used, the steps up to step S32 can be omitted, which is more convenient.
  • a magnesium source and a fluorine source may be further added to lithium cobalt oxide to which magnesium and fluorine have been added in advance.
  • step S33 the first lithium mixture 903 is heated in an atmosphere containing oxygen.
  • the heating is more preferably a heating having an effect of suppressing sticking so that the particles of the first lithium mixture 903 do not stick to each other.
  • some elemental sources such as fluorine sources and LiF that can be a lithium source, are lighter than oxygen, so the heating may volatilize LiF and reduce LiF in the first lithium mixture 903. Therefore, when heating the first lithium mixture 903, it is preferable to control the partial pressure of fluorine or fluoride in the atmosphere within an appropriate range.
  • this step is the second heating, and may be called annealing to distinguish it from the previous heating step.
  • Examples of the heating having the effect of suppressing sticking include heating while stirring the first lithium mixture 903, heating while vibrating the container containing the first lithium mixture 903, and the like.
  • the temperature of the second heating in step S33 needs to be higher than the temperature at which the reaction between LiMO 2 and the mixture 902 proceeds.
  • the temperature at which the reaction proceeds here may be any temperature at which mutual diffusion of the elements of LiMO 2 and the mixture 902 occurs. Therefore, it may be lower than the melting temperature of these materials. For example, in oxides, solid phase diffusion occurs from 0.757 times the melting temperature T m (Tanman temperature T d ). Therefore, for example, the temperature may be 500 ° C. or higher.
  • the temperature of the second heating is preferably equal to or higher than the co-melting point of the mixture 902.
  • the co-melting point of LiF and MgF 2 is around 742 ° C., so that the temperature in step S33 is preferably 742 ° C. or higher.
  • the temperature of the second heating needs to be lower than the decomposition temperature of LiMO 2 (1130 ° C. in the case of LiCoO 2 ). Further, at a temperature near the decomposition temperature, there is a concern about decomposition of LiMO 2 , although the amount is small. Therefore, the temperature of the second heating is preferably 1130 ° C. or lower, more preferably 1000 ° C. or lower, further preferably 950 ° C. or lower, still more preferably 900 ° C. or lower.
  • the temperature of the second heating is preferably 500 ° C. or higher and 1130 ° C. or lower, more preferably 500 ° C. or higher and 1000 ° C. or lower, further preferably 500 ° C. or higher and 950 ° C. or lower, and further preferably 500 ° C. or higher and 900 ° C. or lower.
  • 742 ° C. or higher and 1130 ° C. or lower are preferable, 742 ° C. or higher and 1000 ° C. or lower are more preferable, 742 ° C. or higher and 950 ° C. or lower are further preferable, and 742 ° C. or higher and 900 ° C. or lower are further preferable.
  • 830 ° C. or higher and 1130 ° C. or lower are preferable, 830 ° C. or higher and 1000 ° C. or lower are more preferable, 830 ° C. or higher and 950 ° C. or lower are further preferable, and 830 ° C. or higher and 900 ° C. or lower are further preferable.
  • some materials for example LiF, which is a fluorine source, function as a flux.
  • the temperature of the second heating can be lowered to below the decomposition temperature of LiMO 2 , for example, 742 ° C or higher and 950 ° C or lower, and additives such as magnesium are distributed in the region near the surface, and the positive electrode has good characteristics.
  • Active material can be produced.
  • LiF is lighter than oxygen
  • LiF in the first lithium mixture 903 decreases.
  • the function as a flux is weakened. Therefore, it is necessary to heat while suppressing the volatilization of LiF.
  • LiF is not used as a fluorine source or the like, Li and F on the surface of LiMO 2 may react with each other to generate LiF and volatilize. Therefore, even if a fluoride having a melting point higher than that of LiF is used, it is necessary to suppress volatilization in the same manner.
  • the first lithium mixture 903 in an atmosphere containing LiF, that is, to heat the first lithium mixture 903 in a state where the partial pressure of LiF in the heating furnace is high. By such heating, the volatilization of LiF in the first lithium mixture 903 can be suppressed.
  • the second heating is preferably performed at an appropriate time.
  • the appropriate second heating time varies depending on conditions such as the temperature of the second heating, the size and composition of the particles of LiMO 2 in step S14. Smaller particles may be more preferred at lower temperatures or shorter times than larger ones.
  • the temperature of the second heating is preferably, for example, 600 ° C. or higher and 950 ° C. or lower.
  • the second heating time is, for example, preferably 3 hours or more, more preferably 10 hours or more, still more preferably 60 hours or more.
  • the temperature of the second heating is preferably 600 ° C. or higher and 950 ° C. or lower, for example.
  • the second heating time is, for example, preferably 1 hour or more and 10 hours or less, and more preferably about 2 hours.
  • the temperature lowering time after the second heating is preferably, for example, 10 hours or more and 50 hours or less.
  • the second heating may be performed by either a continuous system or a batch system.
  • step S34 crushing is performed, and if necessary, mixing is performed. After mixing, it is preferable to collect the powder and sift it.
  • step S35 the material mixed above is recovered to obtain a second lithium mixture 904.
  • an additive element source is prepared.
  • the element possessed by the additive source for example, one or more selected from lanthanum, aluminum, nickel, manganese, titanium, vanadium, iron, chromium, niobium, cobalt, arsenic, zinc, silicon, sulfur, phosphorus and boron should be used. Can be done.
  • FIG. 5 describes an example in which a nickel source is used as an additive source. Nickel may be able to increase capacity per weight and volume. As the nickel source, nickel oxide, nickel hydroxide or the like can be used.
  • a method for mixing these additives for example, a solid phase method, a sol-gel method, a sputtering method, a mechanochemical method, a CVD method and the like can be used. Further, a plurality of methods may be used in combination.
  • the nickel source is mixed in step S41 and then a third lithium mixture 905 is obtained in step S42.
  • Mixing can be done dry or wet.
  • step S43 the third lithium mixture 905 is heated in an atmosphere containing oxygen.
  • the heating in step S43 is called the third heating.
  • the third heating temperature in step S43 is preferably lower than the second heating temperature in step S33.
  • an additive element source is prepared.
  • the element contained in the additive source for example, one or more selected from lanthanum, zirconium, and yttrium can be used.
  • step S61 the third lithium mixture 905 is mixed with a lanthanum source, a zirconium source, or an yttrium source. Mixing can be done dry or wet. At this time, for example, step S61 can be performed by the sol-gel method. When the sol-gel method is used, lanthanum alkoxide is used as the lantern source, and Zr (OC 3H 7 ) 4 is used as the zirconium source.
  • a lanthanum oxide is fixed to a part of the surface of the positive electrode active material 100 as a modifying material by using the sol-gel method.
  • the additive element for forming the modifiers 101a and 101b is one or more selected from lanthanum, yttrium, and zirconium.
  • the sol-gel method using a lantern
  • the solvent used for the sol-gel method is prepared.
  • the number of atoms of cobalt contained in lithium cobalt oxide may be 1, and the concentration of lantern contained in the metal source may be 0.001 times or more and less than 0.5 times.
  • lanthanum alkoxide tri-i-propoxylantan manufactured by High Purity Chemicals, Inc.
  • 2-propanol 2-propanol
  • lithium cobalt oxide particles are further mixed (step S61 in FIG. 5).
  • the required amount of metal alkoxide varies depending on the particle size of lithium cobalt oxide.
  • the mixture of the alcohol solution of the metal alkoxide and the particles of lithium cobalt oxide is stirred in an atmosphere containing water vapor.
  • Stirring can be done, for example, with a magnetic stirrer.
  • the stirring time may be a time sufficient for the water in the atmosphere and the metal alkoxide to cause a hydrolysis and polycondensation reaction, for example, 4 hours, 25 ° C., and a humidity of 90% RH (Relative Humidity). Can be done below.
  • stirring may be performed in an atmosphere where humidity control and temperature control are not performed, for example, in an air atmosphere in a fume hood. In such a case, it is preferable to lengthen the stirring time, for example, 12 hours or more at room temperature.
  • the sol-gel reaction can proceed gently. Further, by reacting the metal alkoxide with water at room temperature, the sol-gel reaction can proceed more gently than in the case of heating at a temperature exceeding the boiling point of the alcohol of the solvent, for example.
  • the reaction time may be controlled by gradually adding water diluted with alcohol, reducing the amount of alcohol in the bath, adding a stabilizer, or the like.
  • the sol-gel reaction By gently advancing the sol-gel reaction, it is possible to form a coating film having a uniform thickness and good quality.
  • the obtained coating film is not always uniform and may be scattered.
  • the modifiers 101a and 101b are intentionally scattered to form convex portions scattered on the surface of the positive electrode active material 100.
  • the precipitate is collected from the mixed solution after the above treatment.
  • filtration, centrifugation, evaporation to dryness, or the like can be applied.
  • the precipitate can be washed with the same alcohol as the solvent in which the metal alkoxide is dissolved.
  • the precipitate may be recovered in the drying step of the next step.
  • the drying step can be, for example, vacuum or ventilation drying at 80 ° C. for 1 hour or more and 4 hours or less.
  • a film may be formed on the first lithium mixture 903 by a sputtering method or a thin-film deposition method.
  • the second lithium mixture 904 can be obtained after the film formation.
  • heating while stirring the stirring ball and the first lithium mixture 903, heating while vibrating the container containing the stirring ball and the first lithium mixture 903, and the like can be mentioned.
  • the material of the stirring ball zirconium oxide, titanium oxide and the like are preferable.
  • the heating by the rotary kiln can be heated while stirring in either the continuous type or the batch type, and is preferable as the sticking suppressing annealing.
  • the continuous type has good productivity and is preferable.
  • the batch type is preferable because the atmosphere can be easily controlled.
  • roller hers kiln When heating with a roller hers kiln, it is preferable to vibrate the container containing the first lithium mixture 903 during heating. Roller kiln is a continuous type, so productivity is good and preferable. In that case, the second lithium mixture 904 can be obtained after stirring.
  • Step S63> Next, the obtained mixture is heated (step S63 in FIG. 5).
  • the holding time within the heating temperature range is preferably 1 hour or more and 80 hours or less, and more preferably 1 hour or more and 20 hours or less in consideration of productivity.
  • the fourth heating temperature is preferably less than 1000 ° C., preferably 700 ° C. or higher and 950 ° C. or lower, and more preferably about 850 ° C.
  • the fourth heating is performed in an atmosphere containing oxygen.
  • the fourth heating temperature is set to 850 ° C. and maintained for 2 hours, the temperature rise is 200 ° C./h, and the oxygen flow rate is 10 L / min.
  • the fourth heating temperature in step S63 is preferably lower than the third heating temperature in step S43.
  • Step S66> the cooled particles are collected. In addition, it is preferable to sift the particles.
  • modifiers 101a and 101b can be produced on the positive electrode active material 100 of one aspect of the present invention and its surface (step S66 in FIG. 5).
  • the production flow shown in FIG. 5 is an example and is not particularly limited.
  • the production flow shown in FIG. 6 may be used. Since FIG. 6 is the same as the production flow of FIG. 5 except for some differences, the same reference numerals are used for the same steps.
  • FIG. 6 shows a production flow in which nickel is used in S24, aluminum is used in S25, and lanthanum and zirconium are mixed by the sol-gel method in S51.
  • a lithium ion secondary battery containing the positive electrode active material according to one aspect of the present invention will be described.
  • the secondary battery has at least an exterior body, a current collector, an active material (positive electrode active material or negative electrode active material), a conductive auxiliary agent, and a binder. It also has an electrolytic solution in which a lithium salt or the like is dissolved.
  • a positive electrode, a negative electrode, and a separator are provided between the positive electrode and the negative electrode.
  • the positive electrode has a positive electrode active material layer and a positive electrode current collector.
  • the positive electrode active material layer preferably has the positive electrode active material shown in the first embodiment, and may further have a binder, a conductive auxiliary agent, or the like.
  • FIG. 7A shows an example of a schematic view of a cross section of a positive electrode.
  • the current collector 550 is a metal foil, and a positive electrode is formed by applying a slurry on the metal foil and drying it. After drying, further pressing may be added.
  • the positive electrode has an active material layer formed on the current collector 550.
  • the slurry is a material liquid used to form an active material layer on the current collector 550, and refers to a material liquid containing at least an active material, a binder and a solvent, and preferably further mixed with a conductive auxiliary agent. ..
  • the slurry may be referred to as an electrode slurry or an active material slurry, a positive electrode slurry may be used when forming a positive electrode active material layer, and a negative electrode slurry may be used when forming a negative electrode active material layer.
  • the conductive auxiliary agent is also called a conductive imparting agent or a conductive material, and a carbon material is used.
  • a conductive imparting agent By adhering the conductive auxiliary agent between the plurality of active materials, the plurality of active materials are electrically connected to each other, and the conductivity is enhanced.
  • adheresion does not only mean that the active material and the conductive auxiliary agent are physically in close contact with each other, but also when a covalent bond occurs, when the active material is bonded by van der Waals force, the active material is used.
  • the concept includes the case where a part of the surface is covered with the conductive auxiliary agent, the case where the conductive auxiliary agent fits into the surface unevenness of the active material, the case where the conductive auxiliary agent is electrically connected even if they are not in contact with each other, and the like.
  • Carbon black is a typical carbon material used as a conductive auxiliary agent.
  • FIG. 7A acetylene black 553 is illustrated as a conductive auxiliary agent.
  • FIG. 7A shows an example in which a second active material 562 having a particle size smaller than that of the particles of the positive electrode active material 100 shown in the first embodiment is mixed. By mixing particles of different sizes, a high-density positive electrode active material layer can be obtained, and the charge / discharge capacity of the secondary battery can be increased.
  • the particles of the positive electrode active material 100 shown in the first embodiment correspond to the active material 561 of FIG. 7A.
  • a binder (resin) is mixed in order to fix the current collector 550 such as a metal foil and the active material. Binders are also called binders.
  • the binder is a polymer material, and if a large amount of binder is contained, the ratio of the active material in the positive electrode decreases, and the discharge capacity of the secondary battery becomes small. Therefore, the amount of binder is mixed to the minimum.
  • the region not filled with the active material 561, the second active material 562, and the acetylene black 553 points to voids or binders.
  • FIG. 7A shows an example in which the active material 561 is illustrated as a sphere, the present invention is not particularly limited and may have various shapes.
  • the cross-sectional shape of the active material 561 may be an ellipse, a rectangle, a trapezoid, a cone, a quadrangle with rounded corners, or an asymmetric shape.
  • FIG. 7B shows an example in which the active material 561 is illustrated as various shapes.
  • FIG. 7B shows an example different from FIG. 7A.
  • graphene 554 is used as the carbon material used as the conductive auxiliary agent.
  • Graphene is a carbon material that is expected to be applied in various fields such as field effect transistors and solar cells using graphene because it has amazing properties electrically, mechanically, or chemically.
  • a positive electrode active material layer having active material 561, graphene 554, and acetylene black 553 is formed on the current collector 550.
  • the weight of the mixed carbon black is 1.5 times or more and 20 times or less, preferably 2 times or more and 9.5 times or less the weight of graphene. It is preferable to do so.
  • the electrode density can be higher than that of the positive electrode using only acetylene black 553 as the conductive auxiliary agent. By increasing the electrode density, the capacity per weight unit can be increased. Specifically, the density of the positive electrode active material layer by weight measurement can be higher than 3.5 g / cc.
  • the positive electrode active material 100 shown in the first embodiment is used for the positive electrode and the mixture of graphene 554 and acetylene black 555 is within the above range, a synergistic effect can be expected for the secondary battery to have a higher capacity. preferable.
  • the electrode density is lower than that of the positive electrode using only graphene as the conductive auxiliary agent, quick charging is possible by setting the mixture of the first carbon material (graphene) and the second carbon material (acetylene black) in the above range. Can be accommodated. Further, when the positive electrode active material 100 shown in the first embodiment is used for the positive electrode and the mixture of graphene 554 and acetylene black 555 is within the above range, the secondary battery becomes more stable and can cope with further rapid charging. A synergistic effect can be expected and is preferable.
  • the energy to be moved increases and the cruising range also decreases.
  • the cruising range can be maintained with almost no change in the total weight of the vehicle equipped with the secondary battery of the same weight.
  • the positive electrode active material 100 shown in the first embodiment As the positive electrode and setting the mixing ratio of acetylene black and graphene to the optimum range, an appropriate gap necessary for high density of electrodes and ion conduction is created. It is possible to obtain an in-vehicle secondary battery having a high energy density and good output characteristics.
  • this configuration is also effective in a portable information terminal, and a secondary battery is provided by using the positive electrode active material 100 shown in the first embodiment as the positive electrode and setting the mixing ratio of acetylene black and graphene to the optimum range. It can be miniaturized and has a high capacity. In addition, by setting the mixing ratio of acetylene black and graphene to the optimum range, it is possible to quickly charge a mobile information terminal.
  • the region not filled with the active material 561, graphene 554, and acetylene black 553 refers to a void or a binder.
  • the voids are necessary for the penetration of the electrolytic solution, but if it is too large, the electrode density will decrease, and if it is too small, the electrolytic solution will not penetrate, and if it remains as a void even after the secondary battery, the energy density will increase. It will drop.
  • the positive electrode active material 100 obtained in the first embodiment As the positive electrode and setting the mixing ratio of acetylene black and graphene to the optimum range, the density of the electrode and the appropriate gap required for ion conduction can be created. Both are possible, and a secondary battery having a high energy density and good output characteristics can be obtained.
  • FIG. 7C illustrates an example of a positive electrode using carbon nanotubes 555 instead of graphene.
  • FIG. 7C shows an example different from FIG. 7B.
  • the carbon nanotube 555 it is possible to prevent the aggregation of carbon black such as acetylene black 555 and enhance the dispersibility.
  • the region not filled with the active material 561, the carbon nanotube 555, and the acetylene black 553 refers to a void or a binder.
  • FIG. 7D is shown as an example of another positive electrode.
  • FIG. 7C shows an example in which carbon nanotubes 555 are used in addition to graphene 554.
  • carbon nanotubes 555 are used in addition to graphene 554.
  • the region not filled with the active material 561, the carbon nanotube 555, the graphene 554, and the acetylene black 555 refers to a void or a binder.
  • a secondary battery can be manufactured by filling with.
  • the above configuration shows an example of a secondary battery using an electrolytic solution, but is not particularly limited.
  • a semi-solid battery or an all-solid-state battery can be manufactured by using the positive electrode active material 100 shown in the first embodiment.
  • the semi-solid battery means a battery having a semi-solid material in at least one of an electrolyte layer, a positive electrode, and a negative electrode.
  • the term semi-solid here does not mean that the ratio of solid materials is 50%.
  • Semi-solid means that it has solid properties such as small volume change, but also has some properties close to liquid such as flexibility. As long as these properties are satisfied, it may be a single material or a plurality of materials. For example, a liquid material may be infiltrated into a porous solid material.
  • the polymer electrolyte secondary battery refers to a secondary battery having a polymer in the electrolyte layer between the positive electrode and the negative electrode.
  • Polymer electrolyte secondary batteries include dry (or intrinsic) polymer electrolyte batteries, and polymer gel electrolyte batteries. Further, the polymer electrolyte secondary battery may be referred to as a semi-solid state battery.
  • the semi-solid-state battery becomes a secondary battery having a large charge / discharge capacity. Further, a semi-solid state battery having a high charge / discharge voltage can be used. Alternatively, a semi-solid state battery with high safety or reliability can be realized.
  • the positive electrode active material described in the first embodiment may be mixed with another positive electrode active material.
  • positive electrode active materials include, for example, an olivine-type crystal structure, a layered rock salt-type crystal structure, or a composite oxide having a spinel-type crystal structure.
  • examples thereof include compounds such as LiFePO 4 , LiFeO 2 , LiNiO 2 , LiMn 2 O 4 , V 2 O 5 , Cr 2 O 5 , and MnO 2 .
  • lithium nickelate LiNiO 2 or LiNi 1-x M x O 2 (0 ⁇ x ⁇ 1) is added to a lithium-containing material having a spinel-type crystal structure containing manganese such as LiMn 2 O 4 as another positive electrode active material.
  • LiMn 2 O 4 LiMn 2 O 4
  • M Co, Al, etc.
  • a lithium manganese composite oxide that can be represented by the composition formula Lia Mn b Mc Od can be used.
  • the element M a metal element selected from other than lithium and manganese, silicon, and phosphorus are preferably used, and nickel is more preferable.
  • the lithium manganese composite oxide refers to an oxide containing at least lithium and manganese, and includes chromium, cobalt, aluminum, nickel, iron, magnesium, molybdenum, zinc, indium, gallium, copper, titanium, niobium, and silicon. And at least one element selected from the group consisting of phosphorus and the like may be contained.
  • ⁇ Binder> As the binder, for example, it is preferable to use a rubber material such as styrene-butadiene rubber (SBR), styrene-isoprene-styrene rubber, acrylonitrile-butadiene rubber, butadiene rubber, and ethylene-propylene-diene copolymer. Further, fluororubber can be used as the binder.
  • SBR styrene-butadiene rubber
  • fluororubber can be used as the binder.
  • a water-soluble polymer for example, a polysaccharide or the like can be used.
  • a polysaccharide such as carboxymethyl cellulose (CMC), methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, or regenerated cellulose, or starch or the like can be used. Further, it is more preferable to use these water-soluble polymers in combination with the above-mentioned rubber material.
  • the binder includes polystyrene, methyl polyacrylate, methyl polymethacrylate (polymethylmethacrylate, PMMA), sodium polyacrylate, polyvinyl alcohol (PVA), polyethylene oxide (PEO), polypropylene oxide, polyimide, polyvinyl chloride.
  • PVA polyvinyl alcohol
  • PEO polyethylene oxide
  • PEO polypropylene oxide
  • polyimide polyvinyl chloride.
  • Polytetrafluoroethylene, polyethylene, polypropylene, polyisobutylene, polyethylene terephthalate, nylon, polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), ethylenepropylene diene polymer, polyvinyl acetate, nitrocellulose and the like are preferably used. ..
  • the binder may be used in combination of a plurality of the above.
  • a material having a particularly excellent viscosity adjusting effect may be used in combination with another material.
  • a rubber material or the like has excellent adhesive strength and elastic strength, but it may be difficult to adjust the viscosity when mixed with a solvent. In such a case, for example, it is preferable to mix with a material having a particularly excellent viscosity adjusting effect.
  • a material having a particularly excellent viscosity adjusting effect for example, a water-soluble polymer may be used.
  • the water-soluble polymer having a particularly excellent viscosity adjusting effect the above-mentioned polysaccharides such as carboxymethyl cellulose (CMC), methyl cellulose, ethyl cellulose, hydroxypropyl cellulose and diacetyl cellulose, cellulose derivatives such as regenerated cellulose, or starch are used. be able to.
  • CMC carboxymethyl cellulose
  • methyl cellulose methyl cellulose
  • ethyl cellulose methyl cellulose
  • hydroxypropyl cellulose hydroxypropyl cellulose
  • diacetyl cellulose cellulose derivatives such as regenerated cellulose, or starch
  • the cellulose derivative such as carboxymethyl cellulose has higher solubility by using, for example, a salt such as a sodium salt or an ammonium salt of carboxymethyl cellulose, and easily exerts an effect as a viscosity adjusting agent.
  • the high solubility can also enhance the dispersibility with the active material or other components when preparing the electrode slurry.
  • the cellulose and the cellulose derivative used as the binder of the electrode include salts thereof.
  • the water-soluble polymer stabilizes its viscosity by dissolving it in water, and can stably disperse an active substance or another material to be combined as a binder, such as styrene-butadiene rubber, in an aqueous solution. Further, since it has a functional group, it is expected that it can be easily stably adsorbed on the surface of the active material. In addition, many cellulose derivatives such as carboxymethyl cellulose have a functional group such as a hydroxyl group or a carboxyl group, and since they have a functional group, the polymers interact with each other and exist widely covering the surface of the active material. There is expected.
  • the immobile membrane is a membrane having no electrical conductivity or a membrane having extremely low electrical conductivity.
  • the battery reaction potential is changed. Decomposition of the electrolytic solution can be suppressed.
  • the passivation membrane suppresses the conductivity of electricity and can conduct lithium ions.
  • a material having high conductivity such as a metal such as stainless steel, gold, platinum, aluminum, and titanium, and an alloy thereof can be used. Further, it is preferable that the material used for the positive electrode current collector does not elute at the potential of the positive electrode. Further, an aluminum alloy to which an element for improving heat resistance such as silicon, titanium, neodymium, scandium, and molybdenum is added can be used. Further, it may be formed of a metal element that reacts with silicon to form silicide.
  • Metallic elements that react with silicon to form silicide include zirconium, titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, nickel and the like.
  • a foil-like shape, a plate-like shape, a sheet-like shape, a net-like shape, a punching metal-like shape, an expanded metal-like shape, or the like can be appropriately used. It is preferable to use a current collector having a thickness of 5 ⁇ m or more and 30 ⁇ m or less.
  • the negative electrode has a negative electrode active material layer and a negative electrode current collector. Further, the negative electrode active material layer may have a negative electrode active material, and may further have a conductive auxiliary agent and a binder.
  • Niobium electrode active material for example, an alloy-based material, a carbon-based material, or the like can be used.
  • an element capable of performing a charge / discharge reaction by an alloying / dealloying reaction with lithium can be used.
  • a material containing at least one of silicon, tin, gallium, aluminum, germanium, lead, antimony, bismuth, silver, zinc, cadmium, indium and the like can be used.
  • Such elements have a larger capacity than carbon, and silicon in particular has a high theoretical capacity of 4200 mAh / g. Therefore, it is preferable to use silicon as the negative electrode active material. Further, a compound having these elements may be used.
  • an element capable of performing a charge / discharge reaction by an alloying / dealloying reaction with lithium, a compound having the element, and the like may be referred to as an alloy-based material.
  • SiO refers to, for example, silicon monoxide.
  • SiO can also be expressed as SiO x .
  • x preferably has a value of 1 or a value close to 1.
  • x is preferably 0.2 or more and 1.5 or less, and preferably 0.3 or more and 1.2 or less.
  • carbon-based material graphite, easily graphitizable carbon (soft carbon), non-graphitizable carbon (hard carbon), carbon nanotubes, graphene, carbon black and the like may be used.
  • Examples of graphite include artificial graphite and natural graphite.
  • Examples of the artificial graphite include mesocarbon microbeads (MCMB), coke-based artificial graphite, pitch-based artificial graphite and the like.
  • MCMB mesocarbon microbeads
  • the artificial graphite spheroidal graphite having a spherical shape can be used.
  • MCMB may have a spherical shape, which is preferable.
  • MCMB is relatively easy to reduce its surface area and may be preferable.
  • Examples of natural graphite include scaly graphite and spheroidized natural graphite.
  • Graphite exhibits a potential as low as lithium metal when lithium ions are inserted into graphite (during the formation of a lithium-graphite intercalation compound) (0.05V or more and 0.3V or less vs. Li / Li + ).
  • the lithium ion secondary battery using graphite can exhibit a high operating voltage.
  • graphite is preferable because it has advantages such as relatively high capacity per unit volume, relatively small volume expansion, low cost, and high safety as compared with lithium metal.
  • titanium dioxide TIM 2
  • lithium titanium oxide Li 4 Ti 5 O 12
  • lithium-graphite interlayer compound Li x C 6
  • niobium pentoxide Nb 2 O 5
  • Oxides such as tungsten (WO 2 ) and molybdenum oxide (MoO 2 ) can be used.
  • Li 2.6 Co 0.4 N 3 shows a large charge / discharge capacity (900 mAh / g, 1890 mAh / cm 3 ) and is preferable.
  • lithium ions are contained in the negative electrode active material, so that it can be combined with materials such as V 2 O 5 and Cr 3 O 8 which do not contain lithium ions as the positive electrode active material, which is preferable. .. Even when a material containing lithium ions is used as the positive electrode active material, a double nitride of lithium and a transition metal can be used as the negative electrode active material by desorbing the lithium ions contained in the positive electrode active material in advance.
  • a material that causes a conversion reaction can also be used as a negative electrode active material.
  • a transition metal oxide that does not form an alloy with lithium such as cobalt oxide (CoO), nickel oxide (NiO), and iron oxide (FeO)
  • Materials that cause a conversion reaction include oxides such as Fe 2 O 3 , CuO, Cu 2 O, RuO 2 , Cr 2 O 3 , sulfides such as CoS 0.89 , NiS, and CuS, and Zn 3 N 2 . , Cu 3 N, Ge 3 N 4 , etc., sulphides such as NiP 2 , FeP 2 , CoP 3 , etc., and fluorides such as FeF 3 , BiF 3 etc. also occur.
  • the same material as the conductive auxiliary agent and the binder that the positive electrode active material layer can have can be used.
  • the negative electrode current collector preferably uses a material that does not alloy with carrier ions such as lithium.
  • a separator is placed between the positive electrode and the negative electrode.
  • the separator include fibers having cellulose such as paper, non-woven fabrics, glass fibers, ceramics, or synthetic fibers using nylon (polyamide), vinylon (polyvinyl alcohol-based fiber), polyester, acrylic, polyolefin, and polyurethane. It is possible to use the one formed by. It is preferable that the separator is processed into a bag shape and arranged so as to wrap either the positive electrode or the negative electrode.
  • the separator may have a multi-layer structure.
  • an organic material film such as polypropylene or polyethylene can be coated with a ceramic material, a fluorine material, a polyamide material, or a mixture thereof.
  • the ceramic material for example, aluminum oxide particles, silicon oxide particles and the like can be used.
  • the fluorine-based material for example, PVDF, polytetrafluoroethylene and the like can be used.
  • the polyamide-based material for example, nylon, aramid (meth-based aramid, para-based aramid) and the like can be used.
  • the oxidation resistance is improved by coating with a ceramic material, deterioration of the separator during charging and discharging is suppressed so that x in Li x CoO 2 becomes 0.24 or less, and the reliability of the secondary battery is improved. Can be made to. Further, when a fluorine-based material is coated, the separator and the electrode are easily brought into close contact with each other, and the output characteristics can be improved. Coating a polyamide-based material, particularly aramid, improves heat resistance and thus can improve the safety of the secondary battery.
  • a mixed material of aluminum oxide and aramid may be coated on both sides of a polypropylene film.
  • the surface of the polypropylene film in contact with the positive electrode may be coated with a mixed material of aluminum oxide and aramid, and the surface in contact with the negative electrode may be coated with a fluorine-based material.
  • the safety of the secondary battery can be maintained even if the thickness of the entire separator is thin, so that the capacity per volume of the secondary battery can be increased.
  • the electrolytic solution has a solvent and an electrolyte.
  • the solvent of the electrolytic solution is preferably an aprotonic organic solvent, for example, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, chloroethylene carbonate, vinylene carbonate, ⁇ -butylolactone, ⁇ -valerolactone, dimethyl carbonate.
  • DMC diethyl carbonate
  • DEC diethyl carbonate
  • EMC ethylmethyl carbonate
  • methyl formate methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, 1,3-dioxane, 1,4 -Use one of dioxane, dimethoxyethane (DME), dimethyl sulfoxide, diethyl ether, methyl diglyme, acetonitrile, benzonitrile, tetrahydrofuran, sulfolane, sulton, etc., or two or more of these in any combination and ratio. be able to.
  • Ionic liquids normally temperature molten salt
  • Ionic liquids consist of cations and anions, including organic cations and anions.
  • Examples of the organic cation used in the electrolytic solution include aliphatic onium cations such as quaternary ammonium cations, tertiary sulfonium cations, and quaternary phosphonium cations, and aromatic cations such as imidazolium cations and pyridinium cations.
  • anions used in the electrolytic solution monovalent amide anions, monovalent methide anions, fluorosulfonic acid anions, perfluoroalkyl sulfonic acid anions, tetrafluoroborate anions, perfluoroalkyl borate anions, and hexafluorophosphate anions. , Or perfluoroalkyl phosphate anion and the like.
  • Examples of the electrolyte to be dissolved in the above solvent include LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , LiAlCl 4 , LiSCN, LiBr, LiI, Li 2 SO 4 , Li 2 B 10 Cl 10 , Li 2 B 12 .
  • One type of lithium salt such as SO 2 ) (CF 3 SO 2 ), LiN (C 2 F 5 SO 2 ) 2 , lithium bis (oxalate) borate (Li (C 2 O 4 ) 2 , LiBOB), or among these Two or more of these can be used in any combination and ratio.
  • the electrolytic solution used in the power storage device it is preferable to use a highly purified electrolytic solution having a small content of granular dust or elements other than the constituent elements of the electrolytic solution (hereinafter, also simply referred to as “impurities”).
  • the weight ratio of impurities to the electrolytic solution is preferably 1% or less, preferably 0.1% or less, and more preferably 0.01% or less.
  • the electrolytic solution includes vinylene carbonate, propane sultone (PS), tert-butylbenzene (TBB), fluoroethylene carbonate (FEC), lithium bis (oxalate) borate (LiBOB), and dinitrile compounds such as succinonitrile and adiponitrile.
  • Additives may be added.
  • the concentration of the additive may be, for example, 0.1 wt% or more and 5 wt% or less with respect to the entire solvent.
  • a polymer gel electrolyte obtained by swelling the polymer with an electrolytic solution may be used.
  • the secondary battery can be made thinner and lighter.
  • silicone gel silicone gel, acrylic gel, acrylonitrile gel, polyethylene oxide gel, polypropylene oxide gel, fluoropolymer gel and the like can be used.
  • a polymer having a polyalkylene oxide structure such as polyethylene oxide (PEO), PVDF, polyacrylonitrile, etc., and a copolymer containing them can be used.
  • PVDF-HFP which is a copolymer of PVDF and hexafluoropropylene (HFP)
  • the polymer to be formed may have a porous shape.
  • a solid electrolyte having an inorganic material such as a sulfide type or an oxide type, or a solid electrolyte having a polymer material such as PEO (polyethylene oxide) type can be used.
  • PEO polyethylene oxide
  • the positive electrode active material 100 obtained in the first embodiment can also be applied to an all-solid-state battery.
  • an all-solid-state battery having high safety and good characteristics can be obtained.
  • a metal material such as aluminum or a resin material can be used.
  • a film-like exterior body can also be used.
  • a metal thin film having excellent flexibility such as aluminum, stainless steel, copper, and nickel is provided on a film made of a material such as polyethylene, polypropylene, polycarbonate, ionomer, and polyamide, and an exterior is further formed on the metal thin film.
  • a film having a three-layer structure provided with an insulating synthetic resin film such as a polyamide resin or a polyester resin can be used as the outer surface of the body.
  • This embodiment can be used in combination with other embodiments.
  • FIG. 8A is an exploded perspective view of a coin-type (single-layer flat type) secondary battery
  • FIG. 8B is an external view
  • FIG. 8C is a cross-sectional view thereof.
  • Coin-type secondary batteries are mainly used in small electronic devices.
  • FIG. 8A in order to make it easy to understand, a schematic diagram is made so that the overlap (vertical relationship and positional relationship) of the members can be understood. Therefore, FIGS. 8A and 8B do not have a completely matching correspondence diagram.
  • the positive electrode 304, the separator 310, the negative electrode 307, the spacer 322, and the washer 312 are overlapped. These are sealed with a negative electrode can 302 and a positive electrode can 301.
  • the gasket for sealing is not shown.
  • the spacer 322 and the washer 312 are used to protect the inside or fix the position inside the can when crimping the positive electrode can 301 and the negative electrode can 302. Stainless steel or an insulating material is used for the spacer 322 and the washer 312.
  • the laminated structure in which the positive electrode active material layer 306 is formed on the positive electrode current collector 305 is referred to as the positive electrode 304.
  • the separator 310 and the ring-shaped insulator 313 are arranged so as to cover the side surface and the upper surface of the positive electrode 304, respectively.
  • the separator 310 has a wider plane area than the positive electrode 304.
  • FIG. 8B is a perspective view of the completed coin-shaped secondary battery.
  • a positive electrode can 301 that also serves as a positive electrode terminal and a negative electrode can 302 that also serves as a negative electrode terminal are insulated and sealed with a gasket 303 that is made of polypropylene or the like.
  • the positive electrode 304 is formed by a positive electrode current collector 305 and a positive electrode active material layer 306 provided in contact with the positive electrode current collector 305.
  • the negative electrode 307 is formed by a negative electrode current collector 308 and a negative electrode active material layer 309 provided in contact with the negative electrode current collector 308.
  • the negative electrode 307 is not limited to the laminated structure, and a lithium metal foil or an alloy foil of lithium and aluminum may be used.
  • the positive electrode 304 and the negative electrode 307 used in the coin-type secondary battery 300 may have the active material layer formed on only one side thereof.
  • the positive electrode can 301 and the negative electrode can 302 a metal such as nickel, aluminum, or titanium having corrosion resistance to an electrolytic solution, or an alloy thereof or an alloy thereof and another metal (for example, stainless steel or the like) may be used. can. Further, in order to prevent corrosion due to an electrolytic solution or the like, it is preferable to coat with nickel, aluminum or the like.
  • the positive electrode can 301 is electrically connected to the positive electrode 304
  • the negative electrode can 302 is electrically connected to the negative electrode 307.
  • the negative electrode 307, the positive electrode 304, and the separator 310 are immersed in an electrolytic solution, and as shown in FIG. 8C, the positive electrode 304, the separator 310, the negative electrode 307, and the negative electrode can 302 are laminated in this order with the positive electrode can 301 facing down, and the positive electrode can A coin-shaped secondary battery 300 is manufactured by crimping the 301 and the negative electrode can 302 via the gasket 303.
  • the secondary battery By using the secondary battery, it is possible to obtain a coin-type secondary battery 300 having a high capacity, a high charge / discharge capacity, and excellent cycle characteristics.
  • the separator 310 may not be required.
  • the cylindrical secondary battery 616 has a positive electrode cap (battery lid) 601 on the upper surface and a battery can (exterior can) 602 on the side surface and the bottom surface.
  • the positive electrode cap 601 and the battery can (exterior can) 602 are insulated by a gasket (insulating packing) 610.
  • FIG. 9B is a diagram schematically showing a cross section of a cylindrical secondary battery.
  • the cylindrical secondary battery shown in FIG. 9B has a positive electrode cap (battery lid) 601 on the upper surface and a battery can (outer can) 602 on the side surface and the bottom surface.
  • These positive electrode caps and the battery can (exterior can) 602 are insulated by a gasket (insulating packing) 610.
  • a battery element in which a band-shaped positive electrode 604 and a negative electrode 606 are wound with a separator 605 sandwiched between them is provided inside the hollow cylindrical battery can 602.
  • the battery element is wound around a central axis.
  • One end of the battery can 602 is closed and the other end is open.
  • a metal such as nickel, aluminum, or titanium having corrosion resistance to an electrolytic solution, or an alloy thereof or an alloy of these and another metal (for example, stainless steel or the like) can be used. ..
  • the battery element in which the positive electrode, the negative electrode, and the separator are wound is sandwiched between a pair of insulating plates 608 and 609 facing each other. Further, a non-aqueous electrolytic solution (not shown) is injected into the inside of the battery can 602 provided with the battery element.
  • the non-aqueous electrolyte solution the same one as that of a coin-type secondary battery can be used.
  • the positive electrode and the negative electrode used in the cylindrical storage battery are wound, it is preferable to form active substances on both sides of the current collector.
  • a cylindrical secondary battery 616 having a high capacity, a high charge / discharge capacity, and excellent cycle characteristics can be obtained.
  • a positive electrode terminal (positive electrode current collecting lead) 603 is connected to the positive electrode 604, and a negative electrode terminal (negative electrode current collecting lead) 607 is connected to the negative electrode 606.
  • a metal material such as aluminum can be used for both the positive electrode terminal 603 and the negative electrode terminal 607.
  • the positive electrode terminal 603 is resistance welded to the safety valve mechanism 613, and the negative electrode terminal 607 is resistance welded to the bottom of the battery can 602.
  • the safety valve mechanism 613 is electrically connected to the positive electrode cap 601 via a PTC element (Positive Temperature Coefficient) 611. The safety valve mechanism 613 disconnects the electrical connection between the positive electrode cap 601 and the positive electrode 604 when the increase in the internal pressure of the battery exceeds a predetermined threshold value.
  • the PTC element 611 is a heat-sensitive resistance element whose resistance increases when the temperature rises, and the amount of current is limited by the increase in resistance to prevent abnormal heat generation.
  • Barium titanate (BaTIO 3 ) -based semiconductor ceramics or the like can be used as the PTC element.
  • FIG. 9C shows an example of the power storage system 615.
  • the power storage system 615 has a plurality of secondary batteries 616.
  • the positive electrode of each secondary battery is in contact with the conductor 624 separated by the insulator 625 and is electrically connected.
  • the conductor 624 is electrically connected to the control circuit 620 via the wiring 623.
  • the negative electrode of each secondary battery is electrically connected to the control circuit 620 via the wiring 626.
  • As the control circuit 620 a charge / discharge control circuit for charging / discharging or a protection circuit for preventing overcharging or overdischarging can be applied.
  • FIG. 9D shows an example of the power storage system 615.
  • the power storage system 615 has a plurality of secondary batteries 616, and the plurality of secondary batteries 616 are sandwiched between the conductive plate 628 and the conductive plate 614.
  • the plurality of secondary batteries 616 are electrically connected to the conductive plate 628 and the conductive plate 614 by wiring 627.
  • the plurality of secondary batteries 616 may be connected in parallel, may be connected in series, or may be connected in parallel and then further connected in series.
  • a plurality of secondary batteries 616 may be connected in parallel and then further connected in series.
  • a temperature control device may be provided between the plurality of secondary batteries 616.
  • the secondary battery 616 When the secondary battery 616 is overheated, it can be cooled by the temperature control device, and when the secondary battery 616 is too cold, it can be heated by the temperature control device. Therefore, the performance of the power storage system 615 is less likely to be affected by the outside air temperature.
  • the power storage system 615 is electrically connected to the control circuit 620 via the wiring 621 and the wiring 622.
  • the wiring 621 is electrically connected to the positive electrode of the plurality of secondary batteries 616 via the conductive plate 628
  • the wiring 622 is electrically connected to the negative electrode of the plurality of secondary batteries 616 via the conductive plate 614.
  • the secondary battery 913 shown in FIG. 10A has a winding body 950 having a terminal 951 and a terminal 952 inside the housing 930.
  • the winding body 950 is immersed in the electrolytic solution inside the housing 930.
  • the terminal 952 is in contact with the housing 930, and the terminal 951 is not in contact with the housing 930 by using an insulating material or the like.
  • the housing 930 is shown separately for convenience, but in reality, the winding body 950 is covered with the housing 930, and the terminals 951 and 952 extend outside the housing 930. It exists.
  • a metal material for example, aluminum or the like
  • a resin material can be used as the housing 930.
  • the housing 930 shown in FIG. 10A may be formed of a plurality of materials.
  • the housing 930a and the housing 930b are bonded to each other, and the winding body 950 is provided in the region surrounded by the housing 930a and the housing 930b.
  • an insulating material such as an organic resin can be used.
  • a material such as an organic resin on the surface on which the antenna is formed it is possible to suppress the shielding of the electric field by the secondary battery 913. If the electric field shielding by the housing 930a is small, an antenna may be provided inside the housing 930a.
  • a metal material can be used as the housing 930b.
  • the wound body 950 has a negative electrode 931, a positive electrode 932, and a separator 933.
  • the wound body 950 is a wound body in which the negative electrode 931 and the positive electrode 932 are overlapped and laminated with the separator 933 interposed therebetween, and the laminated sheet is wound.
  • a plurality of layers of the negative electrode 931, the positive electrode 932, and the separator 933 may be further laminated.
  • the secondary battery 913 having the winding body 950a as shown in FIG. 11 may be used.
  • the winding body 950a shown in FIG. 11A has a negative electrode 931, a positive electrode 932, and a separator 933.
  • the negative electrode 931 has a negative electrode active material layer 931a.
  • the positive electrode 932 has a positive electrode active material layer 932a.
  • a secondary battery 913 having a high capacity, a high charge / discharge capacity, and excellent cycle characteristics can be obtained.
  • the separator 933 has a wider width than the negative electrode active material layer 931a and the positive electrode active material layer 932a, and is wound so as to overlap the negative electrode active material layer 931a and the positive electrode active material layer 932a. Further, it is preferable that the width of the negative electrode active material layer 931a is wider than that of the positive electrode active material layer 932a from the viewpoint of safety. Further, the wound body 950a having such a shape is preferable in terms of safety and productivity.
  • the negative electrode 931 is electrically connected to the terminal 951.
  • the terminal 951 is electrically connected to the terminal 911a.
  • the positive electrode 932 is electrically connected to the terminal 952.
  • the terminal 952 is electrically connected to the terminal 911b.
  • the winding body 950a and the electrolytic solution are covered with the housing 930 to form the secondary battery 913.
  • the housing 930 is provided with a safety valve, an overcurrent protection element, or the like.
  • the safety valve is a valve that opens the inside of the housing 930 at a predetermined internal pressure in order to prevent the battery from exploding.
  • the secondary battery 913 may have a plurality of winding bodies 950a. By using a plurality of winding bodies 950a, it is possible to obtain a secondary battery 913 having a larger charge / discharge capacity.
  • Other elements of the secondary battery 913 shown in FIGS. 11A and 11B can take into account the description of the secondary battery 913 shown in FIGS. 10A-10C.
  • FIGS. 12A and 12B an example of an external view of a laminated secondary battery is shown in FIGS. 12A and 12B.
  • 12A and 12B have a positive electrode 503, a negative electrode 506, a separator 507, an exterior body 509, a positive electrode lead electrode 510, and a negative electrode lead electrode 511.
  • FIG. 13A shows an external view of the positive electrode 503 and the negative electrode 506.
  • the positive electrode 503 has a positive electrode current collector 501, and the positive electrode active material layer 502 is formed on the surface of the positive electrode current collector 501. Further, the positive electrode 503 has a region (hereinafter referred to as a tab region) in which the positive electrode current collector 501 is partially exposed.
  • the negative electrode 506 has a negative electrode current collector 504, and the negative electrode active material layer 505 is formed on the surface of the negative electrode current collector 504. Further, the negative electrode 506 has a region where the negative electrode current collector 504 is partially exposed, that is, a tab region.
  • the area or shape of the tab region of the positive electrode and the negative electrode is not limited to the example shown in FIG. 13A.
  • FIG. 13B shows the negative electrode 506, the separator 507, and the positive electrode 503 laminated.
  • an example in which 5 sets of negative electrodes and 4 sets of positive electrodes are used is shown. It can also be called a laminate consisting of a negative electrode, a separator, and a positive electrode.
  • the tab regions of the positive electrode 503 are bonded to each other, and the positive electrode lead electrode 510 is bonded to the tab region of the positive electrode on the outermost surface.
  • ultrasonic welding may be used.
  • the tab regions of the negative electrode 506 are bonded to each other, and the negative electrode lead electrode 511 is bonded to the tab region of the negative electrode on the outermost surface.
  • the negative electrode 506, the separator 507, and the positive electrode 503 are arranged on the exterior body 509.
  • the exterior body 509 is bent at the portion shown by the broken line. After that, the outer peripheral portion of the exterior body 509 is joined. For example, thermocompression bonding may be used for joining. At this time, a region (hereinafter referred to as an introduction port) that is not joined to a part (or one side) of the exterior body 509 is provided so that the electrolytic solution 508 can be put in later.
  • an introduction port a region that is not joined to a part (or one side) of the exterior body 509 is provided so that the electrolytic solution 508 can be put in later.
  • the electrolytic solution 508 (not shown) is introduced into the inside of the exterior body 509 from the introduction port provided in the exterior body 509.
  • the electrolytic solution 508 is preferably introduced under a reduced pressure atmosphere or an inert atmosphere.
  • the inlet is joined. In this way, the laminated type secondary battery 500 can be manufactured.
  • a secondary battery 500 having a high capacity, a high charge / discharge capacity, and excellent cycle characteristics can be obtained.
  • Example of battery pack An example of a secondary battery pack according to an aspect of the present invention capable of wireless charging using an antenna will be described with reference to FIG.
  • FIG. 14A is a diagram showing the appearance of the secondary battery pack 531 and is a thin rectangular parallelepiped shape (also referred to as a thick flat plate shape).
  • FIG. 14B is a diagram illustrating the configuration of the secondary battery pack 531.
  • the secondary battery pack 531 has a circuit board 540 and a secondary battery 513.
  • a label 529 is affixed to the secondary battery 513.
  • the circuit board 540 is fixed by the seal 515.
  • the secondary battery pack 531 has an antenna 517.
  • the inside of the secondary battery 513 may have a structure having a wound body or a structure having a laminated body.
  • the secondary battery pack 531 has a control circuit 590 on the circuit board 540, for example, as shown in FIG. 14B. Further, the circuit board 540 is electrically connected to the terminal 514. Further, the circuit board 540 is electrically connected to the antenna 517, one 551 of the positive electrode lead and the negative electrode lead of the secondary battery 513, and the other 552 of the positive electrode lead and the negative electrode lead.
  • circuit system 590a provided on the circuit board 540 and a circuit system 590b electrically connected to the circuit board 540 via the terminal 514.
  • the antenna 517 is not limited to a coil shape, and may be, for example, a linear shape or a plate shape. Further, antennas such as a planar antenna, an open surface antenna, a traveling wave antenna, an EH antenna, a magnetic field antenna, and a dielectric antenna may be used. Alternatively, the antenna 517 may be a flat conductor. This flat plate-shaped conductor can function as one of the conductors for electric field coupling. That is, the antenna 517 may function as one of the two conductors of the capacitor. This makes it possible to exchange electric power not only with an electromagnetic field and a magnetic field but also with an electric field.
  • the secondary battery pack 531 has a layer 519 between the antenna 517 and the secondary battery 513.
  • the layer 519 has a function of being able to shield the electromagnetic field generated by the secondary battery 513, for example.
  • a magnetic material can be used as the layer 519.
  • the secondary battery 400 of one aspect of the present invention has a positive electrode 410, a solid electrolyte layer 420 and a negative electrode 430.
  • the positive electrode 410 has a positive electrode current collector 413 and a positive electrode active material layer 414.
  • the positive electrode active material layer 414 has a positive electrode active material 411 and a solid electrolyte 421.
  • the positive electrode active material 411 the positive electrode active material 100 obtained in the first embodiment is used, and the positive electrode active material layer 414 may have a conductive auxiliary agent and a binder.
  • the solid electrolyte layer 420 has a solid electrolyte 421.
  • the solid electrolyte layer 420 is located between the positive electrode 410 and the negative electrode 430, and is a region having neither the positive electrode active material 411 nor the negative electrode active material 431.
  • the negative electrode 430 has a negative electrode current collector 433 and a negative electrode active material layer 434.
  • the negative electrode active material layer 434 has a negative electrode active material 431 and a solid electrolyte 421. Further, the negative electrode active material layer 434 may have a conductive auxiliary agent and a binder.
  • metallic lithium is used for the negative electrode 430
  • the negative electrode 430 without the solid electrolyte 421 can be used as shown in FIG. 15B. It is preferable to use metallic lithium for the negative electrode 430 because the energy density of the secondary battery 400 can be improved.
  • solid electrolyte 421 of the solid electrolyte layer 420 for example, a sulfide-based solid electrolyte, an oxide-based solid electrolyte, a halide-based solid electrolyte, or the like can be used.
  • Sulfide-based solid electrolytes include thiolysicon-based (Li 10 GeP 2 S 12 , Li 3.25 Ge 0.25 P 0.75 S 4 , etc.) and sulfide glass (70Li 2 S / 30P 2 S 5 , 30Li 2 ).
  • Sulfide crystallized glass (Li 7 ) P 3 S 11 , Li 3.25 P 0.95 S 4 etc.) are included.
  • the sulfide-based solid electrolyte has advantages such as having a material having high conductivity, being able to be synthesized at a low temperature, and being relatively soft so that the conductive path can be easily maintained even after charging and discharging.
  • a material having a perovskite-type crystal structure La 2 / 3-x Li 3x TIO 3 , etc.
  • a material having a NASICON-type crystal structure Li 1-Y Al Y Ti 2-Y (PO 4 )) ) 3 etc.
  • Material with garnet type crystal structure Li 7 La 3 Zr 2 O 12 etc.
  • Material with LISION type crystal structure Li 14 ZnGe 4 O 16 etc.
  • LLZO Li 7 La 3 Zr 2 O etc. 12
  • Oxide glass Li 3 PO 4 -Li 4 SiO 4 , 50Li 4 SiO 4 , 50Li 3 BO 3 , etc.
  • Oxide crystallized glass Li 1.07 Al 0.69 Ti 1.46 (PO 4 ) ) 3 , Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 etc.
  • Oxide-based solid electrolytes have the advantage of being stable in the atmosphere.
  • the halide-based solid electrolyte includes LiAlCl 4 , Li 3 InBr 6 , LiF, LiCl, LiBr, LiI and the like. Further, a composite material in which the pores of porous aluminum oxide or porous silica are filled with these halide-based solid electrolytes can also be used as the solid electrolyte.
  • Li 1 + x Al x Ti 2-x (PO 4 ) 3 (0 [x [1) (hereinafter referred to as LATP) having a NASICON type crystal structure is a secondary battery 400 of one aspect of the present invention, which is aluminum and titanium. Since the positive electrode active material used in the above contains an element that may be contained, a synergistic effect can be expected for improving the cycle characteristics, which is preferable. In addition, productivity can be expected to improve by reducing the number of processes.
  • the NASICON type crystal structure is a compound represented by M 2 (XO 4 ) 3 (M: transition metal, X: S, P, As, Mo, W, etc.), and is MO 6
  • M transition metal
  • X S, P, As, Mo, W, etc.
  • MO 6 An octahedron and an XO4 tetrahedron share a vertex and have a three-dimensionally arranged structure.
  • the exterior body of the secondary battery 400 of one aspect of the present invention various materials and shapes can be used, but it is preferable that the exterior body has a function of pressurizing the positive electrode, the solid electrolyte layer and the negative electrode.
  • FIG. 16 is an example of a cell that evaluates the material of an all-solid-state battery.
  • FIG. 16A is a schematic cross-sectional view of the evaluation cell, which has a lower member 761, an upper member 762, and a fixing screw or a wing nut 764 for fixing them, and is used for an electrode by rotating a pressing screw 763.
  • the plate 753 is pressed to fix the evaluation material.
  • An insulator 766 is provided between the lower member 761 made of a stainless steel material and the upper member 762. Further, an O-ring 765 for sealing is provided between the upper member 762 and the holding screw 763.
  • FIG. 16B is an enlarged perspective view of the periphery of the evaluation material.
  • FIG. 16C As an evaluation material, an example of laminating a positive electrode 750a, a solid electrolyte layer 750b, and a negative electrode 750c is shown, and a cross-sectional view is shown in FIG. 16C.
  • the same reference numerals are used for the same parts in FIGS. 16A to 16C.
  • the electrode plate 751 and the lower member 761 electrically connected to the positive electrode 750a correspond to the positive electrode terminals. It can be said that the electrode plate 753 and the upper member 762 electrically connected to the negative electrode 750c correspond to the negative electrode terminals.
  • the electrical resistance and the like can be measured while pressing the evaluation material through the electrode plate 751 and the electrode plate 753.
  • a package having excellent airtightness for the exterior body of the secondary battery according to one aspect of the present invention For example, a ceramic package or a resin package can be used. Further, when sealing the exterior body, it is preferable to shut off the outside air and perform it in a closed atmosphere, for example, in a glove box.
  • FIG. 17A shows a perspective view of a secondary battery according to an aspect of the present invention, which has an exterior body and a shape different from those in FIG.
  • the secondary battery of FIG. 17A has external electrodes 771 and 772, and is sealed with an exterior body having a plurality of package members.
  • FIG. 17B shows an example of a cross section cut by a broken line in FIG. 17A.
  • the laminate having a positive electrode 750a, a solid electrolyte layer 750b, and a negative electrode 750c includes a package member 770a having an electrode layer 773a provided on a flat plate, a frame-shaped package member 770b, and a package member 770c having an electrode layer 773b provided on a flat plate. It has a sealed structure surrounded by. Insulating materials such as resin materials or ceramics can be used for the package members 770a, 770b and 770c.
  • the external electrode 771 is electrically connected to the positive electrode 750a via the electrode layer 773a and functions as a positive electrode terminal. Further, the external electrode 772 is electrically connected to the negative electrode 750c via the electrode layer 773b and functions as a negative electrode terminal.
  • an all-solid-state secondary battery having a high energy density and good output characteristics can be realized.
  • This embodiment can be used in combination with other embodiments as appropriate.
  • FIG. 9D is a cylindrical secondary battery.
  • 18A, 18B, and 18C are used to show an example of application to an electric vehicle (EV).
  • EV electric vehicle
  • the electric vehicle is equipped with a first battery 1301a and 1301b as a main drive secondary battery and a second battery 1311 that supplies electric power to the inverter 1312 that starts the motor 1304.
  • the second battery 1311 is also called a cranking battery (also called a starter battery).
  • the second battery 1311 only needs to have a high output, and a large capacity is not required so much, and the capacity of the second battery 1311 is smaller than that of the first batteries 1301a and 1301b.
  • the internal structure of the first battery 1301a may be the winding type shown in FIG. 10A or FIG. 11C, or the laminated type shown in FIG. 12A or FIG. 12B. Further, as the first battery 1301a, the all-solid-state battery of the fifth embodiment may be used. By using the all-solid-state battery of the fifth embodiment for the first battery 1301a, the capacity can be increased, the safety can be improved, and the size and weight can be reduced.
  • first batteries 1301a and 1301b are connected in parallel, but three or more batteries may be connected in parallel. Further, if the first battery 1301a can store sufficient electric power, the first battery 1301b may not be present.
  • the plurality of secondary batteries may be connected in parallel, may be connected in series, or may be connected in parallel and then further connected in series. Multiple secondary batteries are also called assembled batteries.
  • a service plug or a circuit breaker capable of cutting off a high voltage without using a tool is provided, and the first battery 1301a has. It will be provided.
  • the electric power of the first batteries 1301a and 1301b is mainly used to rotate the motor 1304, but 42V in-vehicle parts (electric power steering 1307, heater 1308, defogger 1309, etc.) via the DCDC circuit 1306. Power to. Even if the rear wheel has a rear motor 1317, the first battery 1301a is used to rotate the rear motor 1317.
  • the second battery 1311 supplies electric power to 14V in-vehicle components (audio 1313, power window 1314, lamps 1315, etc.) via the DCDC circuit 1310.
  • first battery 1301a will be described with reference to FIG. 18A.
  • FIG. 18A shows an example in which nine square secondary batteries 1300 are used as one battery pack 1415. Further, nine square secondary batteries 1300 are connected in series, one electrode is fixed by a fixing portion 1413 made of an insulator, and the other electrode is fixed by a fixing portion 1414 made of an insulator.
  • a fixing portion 1413 made of an insulator In the present embodiment, an example of fixing with the fixing portions 1413 and 1414 is shown, but the configuration may be such that the battery is stored in a battery storage box (also referred to as a housing). Since it is assumed that the vehicle is vibrated or shaken from the outside (road surface or the like), it is preferable that a plurality of secondary batteries are fixed to the fixing portions 1413 and 1414 by a battery accommodating box or the like. Further, one of the electrodes is electrically connected to the control circuit unit 1320 by the wiring 1421. The other electrode is electrically connected to the control circuit unit 1320 by wiring 1422.
  • control circuit unit 1320 may use a memory circuit including a transistor using an oxide semiconductor.
  • a charge control circuit or a battery control system having a memory circuit including a transistor using an oxide semiconductor may be referred to as a BTOS (Battery operating system or Battery oxide semiconductor).
  • a metal oxide that functions as an oxide semiconductor For example, as an oxide, In-M-Zn oxide (element M is aluminum, gallium, yttrium, copper, vanadium, beryllium, boron, titanium, iron, nickel, germanium, zirconium, molybdenum, lanthanum, cerium, neodym, etc. It is preferable to use a metal oxide such as one or more selected from hafnium, tantalum, tungsten, gallium and the like.
  • In-M-Zn oxide element M is aluminum, gallium, yttrium, copper, vanadium, beryllium, boron, titanium, iron, nickel, germanium, zirconium, molybdenum, lanthanum, cerium, neodym, etc.
  • a metal oxide such as one or more selected from hafnium, tantalum, tungsten, gallium and the like.
  • the In-M-Zn oxide that can be applied as an oxide is preferably CAAC-OS (C-Axis Aligned Crystal Oxide Semiconductor) or CAC-OS (Cloud-Aligned Compound Semiconductor).
  • CAAC-OS is an oxide semiconductor having a plurality of crystal regions, the plurality of crystal regions having the c-axis oriented in a specific direction.
  • the specific direction is the thickness direction of the CAAC-OS film, the normal direction of the surface to be formed of the CAAC-OS film, or the normal direction of the surface of the CAAC-OS film.
  • the crystal region is a region having periodicity in the atomic arrangement.
  • the crystal region is also a region in which the lattice arrangement is aligned.
  • the CAAC-OS has a region in which a plurality of crystal regions are connected in the ab plane direction, and the region may have distortion.
  • the strain refers to a region in which a plurality of crystal regions are connected in which the orientation of the lattice arrangement changes between a region in which the lattice arrangement is aligned and a region in which another grid arrangement is aligned. That is, CAAC-OS is an oxide semiconductor that is c-axis oriented and not clearly oriented in the ab plane direction.
  • CAC-OS is, for example, a composition of a material in which elements constituting a metal oxide are unevenly distributed in a size of 0.5 nm or more and 10 nm or less, preferably 1 nm or more and 3 nm or less, or a size close thereto.
  • the metal oxide one or more metal elements are unevenly distributed, and the region having the metal element has a size of 0.5 nm or more and 10 nm or less, preferably 1 nm or more and 3 nm or less, or a size close thereto.
  • the mixed state is also called a mosaic shape or a patch shape.
  • the CAC-OS has a structure in which the material is separated into a first region and a second region to form a mosaic, and the first region is distributed in the film (hereinafter, also referred to as a cloud shape). It is said.). That is, the CAC-OS is a composite metal oxide having a structure in which the first region and the second region are mixed.
  • the atomic number ratios of In, Ga, and Zn with respect to the metal elements constituting CAC-OS in the In-Ga-Zn oxide are expressed as [In], [Ga], and [Zn], respectively.
  • the first region is a region where [In] is larger than [In] in the composition of the CAC-OS film.
  • the second region is a region in which [Ga] is larger than [Ga] in the composition of the CAC-OS film.
  • the first region is a region in which [In] is larger than [In] in the second region and [Ga] is smaller than [Ga] in the second region.
  • the second region is a region in which [Ga] is larger than [Ga] in the first region and [In] is smaller than [In] in the first region.
  • the first region is a region containing indium oxide, indium zinc oxide, or the like as a main component.
  • the second region is a region containing gallium oxide, gallium zinc oxide, or the like as a main component. That is, the first region can be rephrased as a region containing In as a main component. Further, the second region can be rephrased as a region containing Ga as a main component.
  • a region containing In as a main component (No. 1) by EDX mapping acquired by using energy dispersive X-ray spectroscopy (EDX: Energy Dispersive X-ray spectroscopy). It can be confirmed that the region (1 region) and the region containing Ga as a main component (second region) are unevenly distributed and have a mixed structure.
  • CAC-OS When CAC-OS is used for a transistor, the conductivity caused by the first region and the insulating property caused by the second region act in a complementary manner to switch the switching function (On / Off function). Can be added to CAC-OS. That is, the CAC-OS has a conductive function in a part of the material and an insulating function in a part of the material, and has a function as a semiconductor in the whole material. By separating the conductive function and the insulating function, both functions can be maximized. Therefore, by using CAC-OS for the transistor, high on -current (Ion), high field effect mobility ( ⁇ ), and good switching operation can be realized.
  • Ion on -current
  • ⁇ high field effect mobility
  • Oxide semiconductors have various structures, and each has different characteristics.
  • the oxide semiconductor of one aspect of the present invention has two or more of amorphous oxide semiconductor, polycrystalline oxide semiconductor, a-like OS, CAC-OS, nc-OS, and CAAC-OS. You may.
  • the control circuit unit 1320 may be formed by using a unipolar transistor.
  • a transistor using an oxide semiconductor as a semiconductor layer has an operating ambient temperature wider than that of single crystal Si and is -40 ° C or higher and 150 ° C or lower, and its characteristic change is smaller than that of single crystal even when a secondary battery is heated.
  • the off-current of a transistor using an oxide semiconductor is below the lower limit of measurement regardless of the temperature even at 150 ° C., but the off-current characteristics of a single crystal Si transistor are highly temperature-dependent.
  • the off-current of the single crystal Si transistor increases, and the current on / off ratio does not become sufficiently large.
  • the control circuit unit 1320 can improve the safety. Further, by combining the positive electrode active material 100 obtained in the first embodiment and the second embodiment with a secondary battery using the positive electrode, a synergistic effect on safety can be obtained. The secondary battery and the control circuit unit 1320 using the positive electrode active material 100 obtained in the first embodiment and the second embodiment as the positive electrode can greatly contribute to the eradication of accidents such as fires caused by the secondary battery.
  • the control circuit unit 1320 using a memory circuit including a transistor using an oxide semiconductor can also function as an automatic control device for a secondary battery for the causes of instability of 10 items such as micro shorts.
  • Functions that eliminate the causes of instability in 10 items include prevention of overcharging, prevention of overcurrent, overheat control during charging, cell balance with assembled batteries, prevention of overdischarge, fuel gauge, and charging according to temperature.
  • Automatic control of voltage and current amount, control of charge current amount according to the degree of deterioration, detection of abnormal behavior of micro short circuit, prediction of abnormality related to micro short circuit, etc. are mentioned, and the control circuit unit 1320 has at least one function thereof.
  • the automatic control device for the secondary battery can be miniaturized.
  • the micro short circuit refers to a minute short circuit inside the secondary battery, and does not mean that the positive and negative electrodes of the secondary battery are short-circuited and cannot be charged or discharged. It refers to the phenomenon that a short-circuit current flows slightly in the section. Since a large voltage change occurs in a relatively short time and even in a small place, the abnormal voltage value may affect the subsequent estimation.
  • microshorts due to multiple charging and discharging, the uneven distribution of the positive electrode active material causes local current concentration in a part of the positive electrode and a part of the negative electrode, resulting in a separator. It is said that a micro-short circuit occurs due to the occurrence of a part where it does not function or the generation of a side reaction product due to a side reaction.
  • control circuit unit 1320 not only detects the micro short circuit but also detects the terminal voltage of the secondary battery and manages the charge / discharge state of the secondary battery. For example, in order to prevent overcharging, both the output transistor of the charging circuit and the cutoff switch can be turned off almost at the same time.
  • FIG. 18B An example of the block diagram of the battery pack 1415 shown in FIG. 18A is shown in FIG. 18B.
  • the control circuit unit 1320 includes at least a switch for preventing overcharging, a switch unit 1324 including a switch for preventing overdischarging, a control circuit 1322 for controlling the switch unit 1324, and a voltage measuring unit for the first battery 1301a.
  • the control circuit unit 1320 sets the upper limit voltage and the lower limit voltage of the secondary battery to be used, and limits the upper limit of the current from the outside, the upper limit of the output current to the outside, and the like.
  • the range of the lower limit voltage or more and the upper limit voltage or less of the secondary battery is within the voltage range recommended for use, and if it is out of the range, the switch unit 1324 operates and functions as a protection circuit.
  • control circuit unit 1320 can also be called a protection circuit because it controls the switch unit 1324 to prevent over-discharging or over-charging. For example, when the control circuit 1322 detects a voltage that is likely to cause overcharging, the switch of the switch unit 1324 is turned off to cut off the current. Further, a PTC element may be provided in the charge / discharge path to provide a function of cutting off the current in response to an increase in temperature. Further, the control circuit unit 1320 has an external terminal 1325 (+ IN) and an external terminal 1326 ( ⁇ IN).
  • the switch unit 1324 can be configured by combining an n-channel type transistor or a p-channel type transistor.
  • the switch unit 1324 is not limited to a switch having a Si transistor using single crystal silicon, and is not limited to, for example, Ge (germanium), SiGe (silicon germanium), GaAs (gallium arsenide), GaAlAs (gallium aluminum arsenide), and InP (phosphide).
  • the switch unit 1324 may be formed by a power transistor having indium phosphide, SiC (silicon carbide), ZnSe (zinc selenium), GaN (gallium arsenide), GaOx (gallium oxide; x is a real number larger than 0) and the like.
  • the storage element using the OS transistor can be freely arranged by stacking it on a circuit using a Si transistor or the like, integration can be easily performed.
  • the OS transistor can be manufactured by using the same manufacturing apparatus as the Si transistor, it can be manufactured at low cost. That is, it is also possible to stack the control circuit unit 1320 using the OS transistor on the switch unit 1324 and integrate them into one chip. Since the occupied volume of the control circuit unit 1320 can be reduced, the size can be reduced.
  • the first batteries 1301a and 1301b mainly supply electric power to a 42V system (high voltage system) in-vehicle device, and the second battery 1311 supplies electric power to a 14V system (low voltage system) in-vehicle device.
  • the second battery 1311 is often adopted because a lead storage battery is advantageous in terms of cost.
  • Lead-acid batteries have a larger self-discharge than lithium-ion secondary batteries, and have the disadvantage of being easily deteriorated by a phenomenon called sulfation.
  • the second battery 1311 as a lithium ion secondary battery, there is an advantage that it is maintenance-free, but if it is used for a long period of time, for example, after 3 years or more, there is a possibility that an abnormality that cannot be discriminated at the time of manufacture occurs.
  • the second battery 1311 for starting the inverter becomes inoperable, the second battery 1311 is lead-acid in order to prevent the motor from being unable to start even if the first batteries 1301a and 1301b have remaining capacity.
  • power is supplied from the first battery to the second battery, and the battery is charged so as to always maintain a fully charged state.
  • a lithium ion secondary battery is used for both the first battery 1301a and the second battery 1311.
  • the second battery 1311 may use a lead storage battery or an all-solid-state battery or an electric double layer capacitor.
  • the all-solid-state battery of the fifth embodiment may be used.
  • the capacity can be increased, and the size and weight can be reduced.
  • the regenerative energy due to the rotation of the tire 1316 is sent to the motor 1304 via the gear 1305, and is charged from the motor controller 1303 or the battery controller 1302 to the second battery 1311 via the control circuit unit 1321.
  • the first battery 1301a is charged from the battery controller 1302 via the control circuit unit 1320.
  • the first battery 1301b is charged from the battery controller 1302 via the control circuit unit 1320. In order to efficiently charge the regenerative energy, it is desirable that the first batteries 1301a and 1301b can be quickly charged.
  • the battery controller 1302 can set the charging voltage, charging current, and the like of the first batteries 1301a and 1301b.
  • the battery controller 1302 can set charging conditions according to the charging characteristics of the secondary battery to be used and quickly charge the battery.
  • the outlet of the charger or the connection cable of the charger is electrically connected to the battery controller 1302.
  • the electric power supplied from the external charger charges the first batteries 1301a and 1301b via the battery controller 1302.
  • a control circuit may be provided and the function of the battery controller 1302 may not be used, but the first batteries 1301a and 1301b are charged via the control circuit unit 1320 in order to prevent overcharging. Is preferable.
  • the connection cable or the connection cable of the charger is provided with a control circuit.
  • the control circuit unit 1320 may be referred to as an ECU (Electronic Control Unit).
  • the ECU is connected to a CAN (Control Area Area Network) provided in the electric vehicle.
  • CAN is one of the serial communication standards used as an in-vehicle LAN.
  • the ECU also includes a microcomputer. Further, the ECU uses a CPU or a GPU.
  • the external charger installed in the charging stand or the like includes a 100V outlet, a 200V outlet, a three-phase 200V and 50kW, and the like. It is also possible to charge by receiving power supply from an external charging facility by a non-contact power supply method or the like.
  • the secondary battery of the present embodiment described above has a high-density positive electrode by using the positive electrode active material 100 obtained in the first and second embodiments. Furthermore, using graphene as a conductive auxiliary agent, even if the electrode layer is thickened to increase the loading amount, the capacity decrease is suppressed and maintaining high capacity is a synergistic effect of the secondary battery with significantly improved electrical characteristics. realizable. It is particularly effective for a secondary battery used in a vehicle, and provides a vehicle having a long cruising range, specifically, a vehicle having a charge mileage of 500 km or more, without increasing the ratio of the weight of the secondary battery to the total weight of the vehicle. be able to.
  • the secondary battery of the present embodiment described above can increase the operating voltage of the secondary battery by using the positive electrode active material 100 described in the first embodiment, and can be used as the charging voltage increases.
  • the capacity can be increased.
  • the positive electrode active material 100 described in the first embodiment as the positive electrode, it is possible to provide a secondary battery for a vehicle having excellent cycle characteristics.
  • the secondary battery shown in any one of FIGS. 9D, 11C, and 18A is mounted on the vehicle, the next generation such as a hybrid vehicle (HV), an electric vehicle (EV), or a plug-in hybrid vehicle (PHV) is installed.
  • HV hybrid vehicle
  • EV electric vehicle
  • PWD plug-in hybrid vehicle
  • a clean energy vehicle can be realized.
  • agricultural machinery, motorized bicycles including electrically assisted bicycles, motorcycles, electric wheelchairs, electric carts, small or large vessels, submarines, aircraft such as fixed-wing or rotary-wing aircraft, rockets, artificial satellites, space explorers or Secondary batteries can also be mounted on transportation vehicles such as planetary explorers and spacecraft.
  • the secondary battery of one aspect of the present invention can be a high-capacity secondary battery. Therefore, the secondary battery of one aspect of the present invention is suitable for miniaturization and weight reduction, and can be suitably used for a transportation vehicle.
  • the automobile 2001 shown in FIG. 19A is an electric vehicle that uses an electric motor as a power source for traveling. Alternatively, it is a hybrid vehicle in which an electric motor and an engine can be appropriately selected and used as a power source for traveling.
  • an example of the secondary battery shown in the fourth embodiment is installed at one place or a plurality of places.
  • the automobile 2001 shown in FIG. 19A has a battery pack 2200, and the battery pack has a secondary battery module to which a plurality of secondary batteries are connected. Further, it is preferable to have a charge control device that is electrically connected to the secondary battery module.
  • the automobile 2001 can charge the secondary battery of the automobile 2001 by receiving electric power from an external charging facility by a plug-in method, a non-contact power feeding method, or the like.
  • the charging method or the standard of the connector may be appropriately performed by a predetermined method such as CHAdeMO (registered trademark) or a combo.
  • the secondary battery may be a charging station provided in a commercial facility or a household power source.
  • the plug-in technology can charge the power storage device mounted on the automobile 2001 by supplying electric power from the outside. Charging can be performed by converting AC power into DC power via a conversion device such as an ACDC converter.
  • a power receiving device on a vehicle and supply electric power from a ground power transmission device in a non-contact manner to charge the vehicle.
  • this non-contact power supply system by incorporating a power transmission device on the road or the outer wall, charging can be performed not only while the vehicle is stopped but also while the vehicle is running.
  • the non-contact power feeding method may be used to transmit and receive electric power between two vehicles.
  • a solar cell may be provided on the exterior portion of the vehicle to charge the secondary battery when the vehicle is stopped or running.
  • An electromagnetic induction method or a magnetic field resonance method can be used for such non-contact power supply.
  • FIG. 19B shows a large transport vehicle 2002 having a motor controlled by electricity as an example of a transport vehicle.
  • the secondary battery module of the transport vehicle 2002 has, for example, a secondary battery having a nominal voltage of 3.0 V or more and 5.0 V or less as a four-cell unit, and has a maximum voltage of 170 V in which 48 cells are connected in series. Since it has the same functions as in FIG. 19A except that the number of secondary batteries constituting the secondary battery module of the battery pack 2201 is different, the description thereof will be omitted.
  • FIG. 19C shows, as an example, a large transport vehicle 2003 having a motor controlled by electricity.
  • the secondary battery module of the transport vehicle 2003 has, for example, a maximum voltage of 600 V in which 100 or more secondary batteries having a nominal voltage of 3.0 V or more and 5.0 V or less are connected in series. Therefore, a secondary battery having a small variation in characteristics is required.
  • a secondary battery using the positive electrode active material 100 described in the first embodiment as the positive electrode a secondary battery having stable battery characteristics can be manufactured, and mass production can be performed at low cost from the viewpoint of yield. It is possible. Further, since it has the same functions as those in FIG. 19A except that the number of secondary batteries constituting the secondary battery module of the battery pack 2202 is different, the description thereof will be omitted.
  • FIG. 19D shows, as an example, an aircraft 2004 with an engine that burns fuel. Since the aircraft 2004 shown in FIG. 19D has wheels for takeoff and landing, it can be said to be a part of a transportation vehicle, and a plurality of secondary batteries are connected to form a secondary battery module, which is charged with the secondary battery module. It has a battery pack 2203 including a control device.
  • the secondary battery module of the aircraft 2004 has, for example, a maximum voltage of 32V in which eight 4V secondary batteries are connected in series. Since it has the same functions as in FIG. 19A except that the number of secondary batteries constituting the secondary battery module of the battery pack 2203 is different, the description thereof will be omitted.
  • This embodiment can be used in combination with other embodiments as appropriate.
  • the house shown in FIG. 20A has a power storage device 2612 having a secondary battery, which is one aspect of the present invention, and a solar panel 2610.
  • the power storage device 2612 is electrically connected to the solar panel 2610 via wiring 2611 and the like. Further, the power storage device 2612 and the ground-mounted charging device 2604 may be electrically connected.
  • the electric power obtained by the solar panel 2610 can be charged to the power storage device 2612. Further, the electric power stored in the power storage device 2612 can be charged to the secondary battery of the vehicle 2603 via the charging device 2604.
  • the power storage device 2612 is preferably installed in the underfloor space. By installing it in the underfloor space, the space above the floor can be effectively used. Alternatively, the power storage device 2612 may be installed on the floor.
  • the electric power stored in the power storage device 2612 can also supply electric power to other electronic devices in the house. Therefore, even when the power cannot be supplied from the commercial power supply due to a power failure or the like, the electronic device can be used by using the power storage device 2612 according to one aspect of the present invention as an uninterruptible power supply.
  • FIG. 20B shows an example of the power storage device 700 according to one aspect of the present invention.
  • the power storage device 791 according to one aspect of the present invention is installed in the underfloor space portion 796 of the building 799.
  • the power storage device 791 may be provided with the control circuit described in the sixth embodiment, and the power storage device 791 uses a secondary battery using the positive electrode active material 100 obtained in the first and second embodiments as the positive electrode. By using it, a synergistic effect on safety can be obtained.
  • the secondary battery using the control circuit described in the sixth embodiment and the positive electrode active material 100 described in the first embodiment as the positive electrode greatly contributes to the eradication of accidents such as fire by the power storage device 791 having the secondary battery. Can be done.
  • a control device 790 is installed in the power storage device 791, and the control device 790 is connected to a distribution board 703, a power storage controller 705 (also referred to as a control device), a display 706, and a router 709 by wiring. It is electrically connected.
  • Electric power is sent from the commercial power supply 701 to the distribution board 703 via the drop line mounting portion 710. Further, electric power is transmitted to the distribution board 703 from the power storage device 791 and the commercial power supply 701, and the distribution board 703 transfers the transmitted electric power to a general load via an outlet (not shown). It supplies 707 and the power storage system load 708.
  • the general load 707 is, for example, an electric device such as a television or a personal computer
  • the storage system load 708 is, for example, an electric device such as a microwave oven, a refrigerator, or an air conditioner.
  • the power storage controller 705 includes a measurement unit 711, a prediction unit 712, and a planning unit 713.
  • the measuring unit 711 has a function of measuring the amount of electric power consumed by the general load 707 and the power storage system load 708 during one day (for example, from 0:00 to 24:00). Further, the measuring unit 711 may have a function of measuring the electric power of the power storage device 791 and the electric power supplied from the commercial power source 701.
  • the prediction unit 712 is based on the amount of electric power consumed by the general load 707 and the power storage system load 708 during the next day, and the demand consumed by the general load 707 and the power storage system load 708 during the next day. It has a function to predict the amount of electric power.
  • the planning unit 713 has a function of making a charge / discharge plan of the power storage device 791 based on the power demand amount predicted by the prediction unit 712.
  • the amount of electric power consumed by the general load 707 and the power storage system load 708 measured by the measuring unit 711 can be confirmed by the display 706. It can also be confirmed in an electric device such as a television or a personal computer via a router 709. Further, it can be confirmed by a portable electronic terminal such as a smartphone or a tablet via the router 709. Further, the amount of power demand for each time zone (or every hour) predicted by the prediction unit 712 can be confirmed by the display 706, the electric device, and the portable electronic terminal.
  • This embodiment can be used in combination with other embodiments as appropriate.
  • FIG. 21A is an example of an electric bicycle using the power storage device of one aspect of the present invention.
  • One aspect of the power storage device of the present invention can be applied to the electric bicycle 8700 shown in FIG. 21A.
  • the power storage device of one aspect of the present invention includes, for example, a plurality of storage batteries and a protection circuit.
  • the electric bicycle 8700 includes a power storage device 8702.
  • the power storage device 8702 can supply electricity to a motor that assists the driver. Further, the power storage device 8702 is portable, and FIG. 21B shows a state in which the power storage device 8702 is removed from the bicycle. Further, the power storage device 8702 contains a plurality of storage batteries 8701 included in the power storage device of one aspect of the present invention, and the remaining battery level and the like can be displayed on the display unit 8703. Further, the power storage device 8702 has a control circuit 8704 capable of charge control or abnormality detection of the secondary battery shown as an example in the sixth embodiment. The control circuit 8704 is electrically connected to the positive electrode and the negative electrode of the storage battery 8701.
  • control circuit 8704 may be provided with the small solid secondary batteries shown in FIGS. 17A and 17B.
  • the small solid-state secondary battery shown in FIGS. 17A and 17B in the control circuit 8704 power can be supplied to hold the data of the memory circuit of the control circuit 8704 for a long time.
  • the positive electrode active material 100 obtained in the first embodiment and the second embodiment with a secondary battery using the positive electrode, a synergistic effect on safety can be obtained.
  • the secondary battery and the control circuit 8704 using the positive electrode active material 100 obtained in the first embodiment and the second embodiment as the positive electrode can greatly contribute to the eradication of accidents such as fires caused by the secondary battery.
  • FIG. 21C is an example of a two-wheeled vehicle using the power storage device of one aspect of the present invention.
  • the scooter 8600 shown in FIG. 21C includes a power storage device 8602, a side mirror 8601, and a turn signal 8603.
  • the power storage device 8602 can supply electricity to the turn signal 8603.
  • the power storage device 8602 containing a plurality of secondary batteries using the positive electrode active material 100 obtained in the first and second embodiments as the positive electrode can have a high capacity, which can contribute to miniaturization. can.
  • the power storage device 8602 can be stored in the storage under the seat 8604.
  • the power storage device 8602 can be stored in the under-seat storage 8604 even if the under-seat storage 8604 is small.
  • Electronic devices that mount secondary batteries include, for example, television devices (also referred to as televisions or television receivers), monitors for computers, digital cameras, digital video cameras, digital photo frames, mobile phones (mobile phones, mobile phones, etc.).
  • television devices also referred to as televisions or television receivers
  • monitors for computers digital cameras, digital video cameras, digital photo frames, mobile phones (mobile phones, mobile phones, etc.).
  • mobile phone device a portable game machine
  • mobile information terminal a sound reproduction device
  • a large game machine such as a pachinko machine
  • Examples of mobile information terminals include notebook personal computers, tablet terminals, electronic book terminals, and mobile phones.
  • FIG. 22A shows an example of a mobile phone.
  • the mobile phone 2100 includes an operation button 2103, an external connection port 2104, a speaker 2105, a microphone 2106, and the like, in addition to the display unit 2102 incorporated in the housing 2101.
  • the mobile phone 2100 has a secondary battery 2107.
  • the capacity can be increased, and a configuration capable of saving space due to the miniaturization of the housing can be realized. Can be done.
  • the mobile phone 2100 can execute various applications such as mobile phones, e-mails, text viewing and writing, music playback, Internet communication, and computer games.
  • the operation button 2103 can have various functions such as power on / off operation, wireless communication on / off operation, manner mode execution / cancellation, and power saving mode execution / cancellation. ..
  • the function of the operation button 2103 can be freely set by the operating system incorporated in the mobile phone 2100.
  • the mobile phone 2100 can execute short-range wireless communication with communication standards. For example, by communicating with a headset capable of wireless communication, it is possible to make a hands-free call.
  • the mobile phone 2100 is provided with an external connection port 2104, and data can be directly exchanged with another information terminal via a connector. It can also be charged via the external connection port 2104. The charging operation may be performed by wireless power supply without going through the external connection port 2104.
  • the mobile phone 2100 preferably has a sensor.
  • a human body sensor such as a fingerprint sensor, a pulse sensor, or a body temperature sensor, or a touch sensor, a pressure sensor, an acceleration sensor, or the like is preferably mounted.
  • FIG. 22B is an unmanned aerial vehicle 2300 with a plurality of rotors 2302.
  • the unmanned aerial vehicle 2300 is sometimes called a drone.
  • the unmanned aerial vehicle 2300 has a secondary battery 2301, a camera 2303, and an antenna (not shown), which is one aspect of the present invention.
  • the unmanned aerial vehicle 2300 can be remotely controlled via an antenna.
  • the secondary battery using the positive electrode active material 100 obtained in the first embodiment and the second embodiment as the positive electrode has a high energy density and high safety, so that it can be used safely for a long period of time. , Suitable as a secondary battery to be mounted on an unmanned aircraft 2300.
  • FIG. 22C shows an example of a robot.
  • the robot 6400 shown in FIG. 22C includes a secondary battery 6409, an illuminance sensor 6401, a microphone 6402, an upper camera 6403, a speaker 6404, a display unit 6405, a lower camera 6406 and an obstacle sensor 6407, a moving mechanism 6408, an arithmetic unit, and the like.
  • the microphone 6402 has a function of detecting a user's voice, environmental sound, and the like. Further, the speaker 6404 has a function of emitting sound. The robot 6400 can communicate with the user by using the microphone 6402 and the speaker 6404.
  • the display unit 6405 has a function of displaying various information.
  • the robot 6400 can display the information desired by the user on the display unit 6405.
  • the display unit 6405 may be equipped with a touch panel. Further, the display unit 6405 may be a removable information terminal, and by installing it at a fixed position of the robot 6400, it is possible to charge and transfer data.
  • the upper camera 6403 and the lower camera 6406 have a function of photographing the surroundings of the robot 6400. Further, the obstacle sensor 6407 can detect the presence / absence of an obstacle in the traveling direction when the robot 6400 moves forward by using the moving mechanism 6408. The robot 6400 can recognize the surrounding environment and move safely by using the upper camera 6403, the lower camera 6406 and the obstacle sensor 6407.
  • the robot 6400 includes a secondary battery 6409 according to an aspect of the present invention and a semiconductor device or an electronic component in the internal region thereof.
  • the secondary battery using the positive electrode active material 100 obtained in the first embodiment and the second embodiment as the positive electrode has a high energy density and high safety, so that it can be used safely for a long period of time.
  • FIG. 22D shows an example of a cleaning robot.
  • the cleaning robot 6300 has a display unit 6302 arranged on the upper surface of the housing 6301, a plurality of cameras 6303 arranged on the side surface, a brush 6304, an operation button 6305, a secondary battery 6306, various sensors, and the like.
  • the cleaning robot 6300 is provided with tires, suction ports, and the like.
  • the cleaning robot 6300 is self-propelled, can detect dust 6310, and can suck dust from a suction port provided on the lower surface.
  • the cleaning robot 6300 can analyze an image taken by the camera 6303 and determine the presence or absence of an obstacle such as a wall, furniture, or a step. Further, when an object that is likely to be entangled with the brush 6304 such as wiring is detected by image analysis, the rotation of the brush 6304 can be stopped.
  • the cleaning robot 6300 includes a secondary battery 6306 according to an aspect of the present invention and a semiconductor device or an electronic component in the internal region thereof.
  • the secondary battery using the positive electrode active material 100 obtained in the first embodiment and the second embodiment as the positive electrode has a high energy density and high safety, so that it can be used safely for a long period of time. , Suitable as a secondary battery 6306 mounted on the cleaning robot 6300.
  • FIG. 23A shows an example of a wearable device.
  • Wearable devices use a secondary battery as a power source.
  • a wearable device that can perform not only wired charging but also wireless charging with the connector part to be connected exposed is available. It is desired.
  • a secondary battery according to one aspect of the present invention can be mounted on the spectacle-type device 4000 as shown in FIG. 23A.
  • the spectacle-type device 4000 has a frame 4000a and a display unit 4000b.
  • By mounting the secondary battery on the temple portion of the curved frame 4000a it is possible to obtain a spectacle-type device 4000 that is lightweight, has a good weight balance, and has a long continuous use time.
  • the secondary battery using the positive electrode active material 100 obtained in the first embodiment and the second embodiment as the positive electrode has a high energy density, and can realize a configuration that can cope with space saving accompanying the miniaturization of the housing. can.
  • a secondary battery which is one aspect of the present invention, can be mounted on the headset type device 4001.
  • the headset-type device 4001 has at least a microphone unit 4001a, a flexible pipe 4001b, and an earphone unit 4001c.
  • a secondary battery can be provided in the flexible pipe 4001b or in the earphone portion 4001c.
  • the secondary battery using the positive electrode active material 100 obtained in the first embodiment and the second embodiment as the positive electrode has a high energy density, and can realize a configuration that can cope with space saving accompanying the miniaturization of the housing. can.
  • the secondary battery according to one aspect of the present invention can be mounted on the device 4002 that can be directly attached to the body.
  • the secondary battery 4002b can be provided in the thin housing 4002a of the device 4002.
  • the secondary battery using the positive electrode active material 100 obtained in the first embodiment and the second embodiment as the positive electrode has a high energy density, and can realize a configuration that can cope with space saving accompanying the miniaturization of the housing. can.
  • the secondary battery according to one aspect of the present invention can be mounted on the device 4003 that can be attached to clothes.
  • the secondary battery 4003b can be provided in the thin housing 4003a of the device 4003.
  • the secondary battery using the positive electrode active material 100 obtained in the first embodiment and the second embodiment as the positive electrode has a high energy density, and can realize a configuration that can cope with space saving accompanying the miniaturization of the housing. can.
  • a secondary battery which is one aspect of the present invention, can be mounted on the belt-type device 4006.
  • the belt-type device 4006 has a belt portion 4006a and a wireless power supply receiving portion 4006b, and a secondary battery can be mounted in the internal region of the belt portion 4006a.
  • the secondary battery using the positive electrode active material 100 obtained in the first embodiment and the second embodiment as the positive electrode has a high energy density, and can realize a configuration that can cope with space saving accompanying the miniaturization of the housing. can.
  • a secondary battery which is one aspect of the present invention, can be mounted on the wristwatch-type device 4005.
  • the wristwatch-type device 4005 has a display unit 4005a and a belt unit 4005b, and a secondary battery can be provided on the display unit 4005a or the belt unit 4005b.
  • the secondary battery using the positive electrode active material 100 obtained in the first embodiment and the second embodiment as the positive electrode has a high energy density, and can realize a configuration that can cope with space saving accompanying the miniaturization of the housing. can.
  • the display unit 4005a can display not only the time but also various information such as an incoming mail or a telephone call.
  • the wristwatch type device 4005 is a wearable device of a type that is directly wrapped around the wrist, a sensor for measuring the pulse, blood pressure, etc. of the user may be mounted. It is possible to manage the health by accumulating data on the amount of exercise and health of the user.
  • FIG. 23B shows a perspective view of the wristwatch-type device 4005 removed from the arm.
  • FIG. 23C shows a state in which the secondary battery 913 is built in the internal region.
  • the secondary battery 913 is the secondary battery shown in the fourth embodiment.
  • the secondary battery 913 is provided at a position overlapping with the display unit 4005a, can have a high density and a high capacity, is compact, and is lightweight.
  • the wristwatch type device 4005 Since the wristwatch type device 4005 is required to be compact and lightweight, high energy can be obtained by using the positive electrode active material 100 obtained in the first and second embodiments as the positive electrode of the secondary battery 913.
  • a secondary battery 913 having a high density and a small size can be used.
  • This embodiment can be implemented in combination with other embodiments as appropriate.
  • the sample prepared in this example will be described.
  • the positive electrode active material of each sample the positive electrode active material obtained by the method shown in the first embodiment was used.
  • the positive electrode active material lithium cobalt oxide particles (trade name: Cellseed C-10N) manufactured by Nippon Chemical Industrial Co., Ltd. were used as the composite oxide synthesized in advance.
  • Lithium fluoride LiF was prepared as a fluorine source
  • magnesium fluoride MgF 2 was used as a fluorine source and a magnesium source.
  • the first heat treatment was carried out at 850 ° C. for 60 hours under an oxygen atmosphere.
  • LiCoO 2 is used in S14, nickel hydroxide (nickel amount is 0.5 at%) is used as an additive element source of S24, and aluminum alkoxide (aluminum 0.5 at) is used as an additive element source of S51. %) And lanthanum were used to prepare a positive electrode active material by the sol-gel method, and a sample was prepared.
  • FIG. 1A is an electron beam cross-sectional photograph of the produced particles.
  • the solvent in the sol-gel method 10 ml of 2-propanol is used.
  • the conditions of the heat treatment performed by the sol-gel method were heating at 850 ° C. for 2 hours.
  • Acetylene black was used as the conductive auxiliary agent used at the time of sample preparation, and the slurry was mixed to prepare a slurry, and the slurry was applied to an aluminum current collector.
  • a CR2032 type (diameter 20 mm, height 3.2 mm) coin-shaped battery cell was manufactured.
  • Lithium metal was used as the counter electrode.
  • LiPF 6 lithium hexafluoride phosphate
  • DEC diethyl carbonate
  • VC vinylene carbonate
  • Polypropylene having a thickness of 25 ⁇ m was used as the separator.
  • the positive electrode can and the negative electrode are those made of stainless steel (SUS) were used.
  • the charging voltage was 4.7V.
  • the measurement temperature was 25 ° C.
  • Charging was CC / CV (0.5C, 0.05Cut), discharging was CC (0.5C, 2.5Vcut), and a 10-minute rest period was provided before the next charging.
  • 1C was set to 200 mA / g.
  • the discharge rate is a relative ratio of the current at the time of discharge to the battery capacity, and is expressed in the unit C.
  • the current corresponding to 1C is X (A).
  • X (A) When discharged with a current of 2X (A), it is said to be discharged at 2C, and when discharged with a current of X / 5 (A), it is said to be discharged at 0.2C.
  • the charging rate is also the same.
  • When charged with a current of 2X (A) it is said to be charged with 2C, and when charged with a current of X / 5 (A), it is charged with 0.2C. It is said that.
  • Constant current charging refers to, for example, a method of charging with a constant charging rate.
  • Constant voltage charging refers to, for example, a method of charging by keeping the voltage constant when the charging reaches the upper limit voltage.
  • the constant current discharge refers to, for example, a method of discharging with a constant discharge rate.
  • the cycle characteristics of 5 types of samples were measured, 0.25 at% was the best result. It was shown that the 0.25 at% sample was a positive electrode active material in which a decrease in charge / discharge capacity was suppressed even when charging / discharging at a high voltage of 4.7 V was repeated. In addition, the characteristic of 0.5 at% was the most deteriorated. From these results, it is preferable to adjust the lantern concentration so as to be less than 0.5 at%.
  • FIGS. 24A and 24B show the results of preparing a sample using yttrium (Y) instead of the lantern and performing cycle characteristics.
  • Y yttrium
  • the sol-gel method is used, and yttrium alkoxide (tri-i-propoxyittrium manufactured by High Purity Chemicals Co., Ltd.) is used. Both samples were set at 0.25 at%.
  • the vertical axis represents the discharge capacity and the horizontal axis represents the number of cycles.
  • the lantern shows a better value than the yttrium.
  • FIGS. 25A and 25B show the results of similar cycle characteristics with the addition of zirconium (0.25 at%, 0.125 at%, 0.05 at%), respectively.
  • Nickel is 0.5 at% and aluminum is 0.5 at%.
  • zirconium alkoxide such as zirconium isopropoxide can be used.
  • the vertical axis represents the discharge capacity and the horizontal axis represents the number of cycles.
  • the second heat treatment after the sol-gel method was 850 ° C. for 2 hours.
  • FIG. 25B the vertical axis represents the maintenance rate with the maximum discharge capacity set to 100%, and the horizontal axis represents the number of cycles.
  • FIGS. 25A and 25B the characteristics of the sample in which zirconium was 0.25 at% and lanthanum was 0.125 at% were the best. Further, an SEM photograph of the positive electrode active material of this sample is shown in FIG. 27. Lantern and zirconium were detected in the analysis of small particles on the surface of the particles in FIG. 27. The discharge capacity retention rate after 50 cycles showed a good value of 82.4%. The maximum discharge capacity was 219.6 mAh / g.
  • samples are a sample with 0.05 at% zirconium and 0.125 at% lantern, a sample with 0.25 at% zirconium and 0.5 at% lantern, and a sample with 0.25 at% zirconium and lantern.
  • the characteristics of each of the samples having a lantern of 0.05 at% are shown in FIGS. 25A and 25B. Although these samples contain lanthanum and zirconium, they do not form the LLZ known for garnet-type lithium-ion conductors.
  • These positive electrode active material particles have an appearance in which an oxide of zirconium or lanthanum is attached to the surface of the particles.
  • the lantern contained in the positive electrode active material of these samples is contained in an amount smaller than the content of aluminum.
  • the lantern contained in the positive electrode active material of these samples is contained in an amount smaller than the content of nickel.
  • FIGS. 26A and 26B In addition, multiple samples were prepared under different conditions, and similar cycle characteristics were measured. The results are shown in FIGS. 26A and 26B.
  • the vertical axis is the discharge capacity
  • the vertical axis is the maintenance rate of the discharge capacity.
  • FIG. 26A the characteristic of the sample in which zirconium is 0.25 at% and yttrium is 0.025 at% has a maximum discharge capacity exceeding 230 mAh / g. Further, the value of 0.25 at% of the lantern, which is the same sample as in FIGS. 24A and 24B, is displayed as an example.
  • FIGS. 26A and 26B a sample in which zirconium is 0.125 at% and yttrium is 0.125 at%, and a sample in which zirconium is 0.25 at% and yttrium is 0.25 at% are also shown in FIGS. 26A and 26B.
  • nickel is 0.5 at% and aluminum is 0.5 at%.
  • the lanthanum or yttrium contained in these samples is contained in an amount smaller than the content of aluminum.
  • the positive electrode active material of one aspect of the present invention can be repeatedly charged and discharged at a high voltage of 4.7 V for each of the lanthanum sample, yttrium sample, lanthanum and zirconium sample, and yttrium and zirconium sample. It was shown that the decrease in charge / discharge capacity can be suppressed by adjusting each amount.
  • the practitioner may appropriately adjust the amounts of lanthanum, yttrium, and zirconium to prepare a desired positive electrode active material.
  • the charging voltage and the discharging voltage refer to the voltage in the case of counterpolar lithium.
  • the charge / discharge voltage of the secondary battery changes depending on the material used for the negative electrode. For example, since the potential of graphite is about 0.1 V (vs Li / Li + ), the charge / discharge voltage of negative electrode graphite is about 0.1 V lower than that of counterpolar lithium. Further, even when the charging voltage of the secondary battery is, for example, 4.7V or more in the present specification, it is not necessary to have only the discharging voltage of 4.7V or more as the plateau region.

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008226495A (ja) * 2007-03-08 2008-09-25 Agc Seimi Chemical Co Ltd 非水電解質二次電池用リチウム含有複合酸化物粒子及びその製造方法
JP2017007918A (ja) * 2015-06-25 2017-01-12 株式会社豊田自動織機 リチウム複合金属酸化物部及び導電性酸化物部を含有する材料
JP2019003786A (ja) * 2017-06-14 2019-01-10 三星エスディアイ株式会社Samsung SDI Co., Ltd. 正極活物質、非水二次電池、および正極活物質の製造方法
JP2020021742A (ja) * 2017-06-26 2020-02-06 株式会社半導体エネルギー研究所 リチウムイオン二次電池の正極活物質の作製方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008226495A (ja) * 2007-03-08 2008-09-25 Agc Seimi Chemical Co Ltd 非水電解質二次電池用リチウム含有複合酸化物粒子及びその製造方法
JP2017007918A (ja) * 2015-06-25 2017-01-12 株式会社豊田自動織機 リチウム複合金属酸化物部及び導電性酸化物部を含有する材料
JP2019003786A (ja) * 2017-06-14 2019-01-10 三星エスディアイ株式会社Samsung SDI Co., Ltd. 正極活物質、非水二次電池、および正極活物質の製造方法
JP2020021742A (ja) * 2017-06-26 2020-02-06 株式会社半導体エネルギー研究所 リチウムイオン二次電池の正極活物質の作製方法

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