WO2020201916A1 - 正極活物質の作製方法、二次電池の作製方法、二次電池 - Google Patents
正極活物質の作製方法、二次電池の作製方法、二次電池 Download PDFInfo
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- WO2020201916A1 WO2020201916A1 PCT/IB2020/052785 IB2020052785W WO2020201916A1 WO 2020201916 A1 WO2020201916 A1 WO 2020201916A1 IB 2020052785 W IB2020052785 W IB 2020052785W WO 2020201916 A1 WO2020201916 A1 WO 2020201916A1
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- Prior art keywords
- positive electrode
- secondary battery
- active material
- electrode active
- mixture
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- H—ELECTRICITY
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- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
- One aspect of the present invention relates to a product, a method, or a manufacturing method. Alternatively, one aspect of 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 or an electronic device, or a method for manufacturing the same.
- the present invention relates to a positive electrode active material that can be used for a secondary battery, a secondary battery, and an electronic device having the secondary battery.
- the power storage device refers to an element having a power storage function and a device in general.
- a storage battery 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.
- the electronic device refers to all devices having a power storage device, and an electro-optical device having a power storage device, an information terminal device having a power storage device, and the like are all electronic devices.
- Lithium-ion secondary batteries which have particularly high output and high energy density, are mobile information terminals such as mobile phones, smartphones, tablets, or notebook computers, portable music players, digital cameras, medical devices, and next-generation clean energy vehicles (hybrid).
- HVs high output and high energy density
- EVs electric vehicles
- PSVs plug-in hybrid vehicles
- the characteristics required for lithium-ion secondary batteries include further high energy density, improvement of cycle characteristics, safety in various operating environments, and improvement of long-term reliability.
- Patent Document 1 and Patent Document 2 Improvement of the positive electrode active material with the aim of improving the cycle characteristics and increasing the capacity of the lithium ion secondary battery is being studied.
- Patent Documents 1 to 4 Research on the crystal structure of the positive electrode active material has also been conducted.
- X-ray diffraction is one of the methods used for analyzing the crystal structure of the positive electrode active material.
- XRD data can be analyzed by using ICSD (Inorganic Crystal Structure Database) introduced in Non-Patent Document 5.
- One aspect of the present invention is to provide a positive electrode active material for a lithium ion secondary battery having a high capacity and excellent charge / discharge cycle characteristics, and a method for producing the same.
- one of the tasks is to provide a method for producing a positive electrode active material having good productivity.
- one aspect of the present invention is to provide a positive electrode active material in which a decrease in capacity in a charge / discharge cycle is suppressed by using it in a lithium ion secondary battery.
- one aspect of the present invention is to provide a high-capacity secondary battery.
- one aspect of the present invention is to provide a secondary battery having excellent charge / discharge characteristics.
- Another object of the present invention is to provide a positive electrode active material in which elution of transition metals such as cobalt is suppressed even when the state of being charged at a high voltage is maintained for a long time.
- one aspect of the present invention is to provide a secondary battery having high safety or reliability.
- one aspect of the present invention is to provide a novel substance, active material particles, a power storage device, or a method for producing them.
- One aspect of the present invention is a first step of making a first mixture in which a first material, a second material and a third material are mixed, and heating the first mixture to create a second mixture.
- the first material is a halogen compound having an alkali metal
- the second material has magnesium
- the third material is an alkali metal and having a fourth step of making a mixture of A metal oxide having cobalt
- the fourth material has nickel
- the fifth material has aluminum
- the third mixture is heated in the processing chamber of the annealing device.
- the total amount of the third mixture heated in the treatment chamber is 15 g or more
- the heating is carried out in an atmosphere having oxygen
- the heating is carried out. Is carried out in a temperature range of 600 ° C. or higher and 950 ° C. or lower, and in a range of 1 hour or more and 100 hours or less.
- heating is carried out in an atmosphere having oxygen, and in the fourth step, heating is carried out at 600 ° C.
- the temperature of the positive electrode active material is in the temperature range of 950 ° C. or lower and 1 hour or more and 100 hours or less, and the heating temperature in the fourth step is 20 ° C. or more lower than the heating temperature in the second step. It is a manufacturing method.
- the alkali metal is lithium
- the first material is lithium fluoride
- the second material is magnesium fluoride
- the third material is nickel hydroxide and the fourth material is aluminum hydroxide.
- one aspect of the present invention comprises a first step of making a first mixture in which a first material, a second material, a third material and a fourth material are mixed, and a first mixture.
- the second material has a second step of heating to make a second mixture
- the first material is a halogen compound having an alkali metal
- the second material has magnesium and a third material.
- the fourth material is a metal oxide with alkali metals and cobalt
- heating is 600 ° C. or higher and 950. It is carried out in a temperature range of ° C.
- a method for producing a positive electrode active material which has a first peak having a minimum value in the range of 620 ° C. or higher and 920 ° C. or lower in a differential scanning calorific value measurement, and the first peak is a negative peak.
- the alkali metal is lithium
- the first material is lithium fluoride
- the second material is magnesium fluoride
- the third material has nickel, and in the first mixture, a fifth material is mixed in addition to the first material, the second material, the third material and the fourth material.
- the fifth material is preferably a mixture of aluminum.
- the third material is preferably nickel hydroxide.
- the measurement temperature range of the differential scanning calorimetry preferably includes at least a range of 200 ° C. or higher and 850 ° C. or lower.
- the heating atmosphere in the second step has oxygen.
- one aspect of the present invention comprises a first step of making a first mixture in which a first material, a second material, a third material and a fourth material are mixed, and a first mixture.
- a third material having a second step of heating to make a second mixture the first material being a halogen compound having metal A and the second material having magnesium.
- the fourth material is a metal oxide with metal A and cobalt
- the metal A is an alkali metal and the second step.
- the heating is carried out in a temperature range of 600 ° C. or higher and 950 ° C.
- the first material, the second material and the third material are the first material and the second material. 2 ⁇ is 39.5 ° when the material of No. 1 and the third material are mixed, heated in a temperature range of 600 ° C. or higher and 950 ° C. or lower, and in a range of 1 hour or more and 100 hours or less, and analyzed by X-ray diffraction.
- the metal A is lithium
- the first material is lithium fluoride
- the second material is magnesium fluoride
- the third material has nickel, and in the first mixture, a fifth material is mixed in addition to the first material, the second material, the third material and the fourth material.
- the fifth material is preferably a mixture of aluminum.
- the third material is preferably nickel hydroxide.
- a positive electrode active material for a lithium ion secondary battery having a high capacity and excellent charge / discharge cycle characteristics it is possible to provide a method for producing the same. Further, it is possible to provide a method for producing a positive electrode active material having good productivity. Further, by using it in a lithium ion secondary battery, it is possible to provide a positive electrode active material in which a decrease in capacity in a charge / discharge cycle is suppressed. In addition, a high-capacity secondary battery can be provided. Further, it is possible to provide a secondary battery having excellent charge / discharge characteristics.
- 1A, 1B, and 1C are diagrams illustrating a method for inspecting a substance.
- 2A, 2B, and 2C are diagrams illustrating a method for producing a positive electrode active material.
- FIG. 3 is a diagram illustrating a method for producing a positive electrode active material.
- FIG. 4 is a diagram illustrating a method for producing a positive electrode active material.
- 5A, 5B, and 5C are diagrams illustrating a coin-type secondary battery.
- 6A, 6B, 6C, and 6D are diagrams illustrating a cylindrical secondary battery.
- 7A and 7B are diagrams illustrating an example of a secondary battery.
- 8A, 8B, 8C, and 8D are diagrams illustrating an example of a secondary battery.
- FIGS. 9A and 9B are diagrams illustrating an example of a secondary battery.
- FIG. 10 is a diagram illustrating an example of a secondary battery.
- 11A, 11B, and 11C are views for explaining a laminated type secondary battery.
- 12A and 12B are views for explaining a laminated type secondary battery.
- FIG. 13 is a diagram showing the appearance of the secondary battery.
- FIG. 14 is a diagram showing the appearance of the secondary battery.
- 15A, 15B, and 15C are diagrams illustrating a method for manufacturing a secondary battery.
- 16A, 16B1, 16B2, 16C, 16D are diagrams illustrating a bendable secondary battery.
- 17A and 17B are diagrams illustrating a bendable secondary battery.
- 18A, 18B, 18C, 18D, 18E, 18F, 18G, and 18H are diagrams illustrating an example of an electronic device.
- 19A, 19B, and 19C are diagrams illustrating an example of an electronic device.
- FIG. 20 is a diagram illustrating an example of an electronic device.
- 21A, 21B, and 21C are diagrams illustrating an example of a vehicle.
- 22A, 22B, and 22C are diagrams illustrating an example of an electronic device.
- 23A, 23B, and 23C are diagrams showing the evaluation results using DSC.
- 24A and 24B are diagrams showing the evaluation results using DSC.
- FIG. 25 is a diagram showing the evaluation results using DSC.
- FIG. 26 is a diagram showing the cycle characteristics of the secondary battery.
- FIG. 27 is a diagram showing the evaluation result of XRD.
- FIG. 28 is a diagram showing the evaluation result of XRD.
- FIG. 29 is a diagram showing the evaluation result of XRD.
- FIG. 30 is a diagram showing the evaluation result of XRD.
- 31A and 31B are diagrams showing cycle characteristics of a secondary battery at a charging voltage of 4.60 V.
- 32A and 32B are diagrams showing the cycle characteristics of the secondary battery at a charging voltage of 4.62 V.
- 33A and 33B are diagrams showing the cycle characteristics of the secondary battery at a charging voltage of 4.64 V.
- 34A and 34B are diagrams showing the cycle characteristics of the secondary battery at a charging voltage of 4.66V.
- FIG. 35A is a diagram showing the cycle characteristics of the secondary battery using Sample6.
- FIG. 35A is a diagram showing the cycle characteristics of the secondary battery using Sample6.
- FIG. 35B is a diagram showing an initial charge / discharge curve and a 50th charge / discharge curve of a secondary battery using Sample 6 at 50 ° C. and a charging voltage of 4.60 V.
- FIG. 36A is a diagram showing the cycle characteristics of the secondary battery using Sample7.
- FIG. 36B is a diagram showing an initial charge / discharge curve and a 50th charge / discharge curve of a secondary battery using Sample 7 at 50 ° C. and a charging voltage of 4.60 V.
- FIG. 37A is a diagram showing the cycle characteristics of the secondary battery using Sample8.
- FIG. 37B is a diagram showing an initial charge / discharge curve and a 50th charge / discharge curve of a secondary battery using Sample 8 at 50 ° C. and a charging voltage of 4.60 V.
- 38A to 38C are diagrams showing continuous charging characteristics at a voltage of 4.60 V of the secondary battery.
- 39A to 39C are diagrams showing continuous charging characteristics at a voltage of 4.62 V of the secondary battery.
- 40A to 40C are diagrams showing continuous charging characteristics at a voltage of 4.64 V of the secondary battery.
- 41A to 41C are diagrams showing continuous charging characteristics at a voltage of 4.66 V of the secondary battery.
- FIG. 42 is a diagram illustrating the durability time in the continuous charging test.
- 43A and 43B are diagrams showing the evaluation results of XRD.
- 44A and 44B are diagrams showing the evaluation results of XRD.
- the crystal plane and the direction are indicated by the Miller index.
- the notation of crystal plane and direction is to add a superscript bar to the number, but in this specification etc., due to the limitation of application notation, instead of adding a bar above the number,-(minus) before the number. It may be expressed with a sign).
- the individual orientation indicating the direction in the crystal is []
- the aggregate orientation indicating all the equivalent directions is ⁇ >
- the individual plane indicating the crystal plane is ()
- the aggregate plane having equivalent symmetry is ⁇ . Express each with.
- segregation refers to a phenomenon in which a certain element (for example, B) is spatially unevenly distributed in a solid composed of a plurality of elements (for example, A, B, C).
- the surface layer portion of particles such as active material means a region from the surface to about 10 nm.
- 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 layered rock salt type crystal structure of the composite oxide containing lithium and the transition metal has a rock salt type ion arrangement in which cations and anions are alternately arranged, and the transition metal and lithium are present.
- a crystal structure capable of two-dimensional diffusion of lithium because it is regularly arranged to form a two-dimensional plane.
- the layered rock salt crystal structure may have a distorted lattice of rock salt crystals.
- the rock salt type crystal structure means a structure in which cations and anions are alternately arranged. There may be a cation or anion deficiency.
- the pseudo-spinel-type crystal structure of the composite oxide containing lithium and the transition metal is the space group R-3 m, and although it is not a spinel-type crystal structure, ions such as cobalt and magnesium are present.
- a light element such as lithium may occupy the oxygen 4-coordination position, and in this case as well, the ion arrangement has symmetry similar to that of the spinel type.
- the pseudo-spinel type crystal structure has Li randomly between layers, but is similar to the CdCl 2 type crystal structure.
- the crystal structure similar to this CdCl type 2 is similar to the crystal structure when lithium nickel oxide is charged to a charging depth of 0.94 (Li 0.06 NiO 2 ), but simple pure lithium cobalt oxide or cobalt is used. It is known that a layered rock salt type positive electrode active material containing a large amount usually does not have this crystal structure.
- Layered rock salt crystals and anions of rock salt crystals have a cubic closest packed structure (face-centered cubic lattice structure). Pseudo-spinel-type crystals are also presumed to have a cubic close-packed structure with anions. When they come into contact, there is a crystal plane in which the cubic close-packed structure composed of anions is oriented in the same direction.
- the space group of layered rock salt type crystals and pseudo-spinel type crystals is R-3m
- the space group of rock salt type crystals Fm-3m (space group of general rock salt type crystals) and Fd-3m (the simplest symmetry).
- the mirror index of the crystal plane satisfying the above conditions is different between the layered rock salt type crystal and the pseudo spinel type crystal and the rock salt type crystal.
- the orientations of the crystals are substantially the same when the orientations of the cubic closest packed structures composed of anions are aligned. is there.
- the angle formed by the repetition of the bright line and the dark line between the crystals is 5 degrees or less, more preferably 2.5 degrees or less. It can be observed.
- light elements such as oxygen and fluorine may not be clearly observed in the TEM image or the like, but in that case, the alignment of the metal elements can be used to determine the alignment.
- the theoretical capacity of the positive electrode active material means the amount of electricity when all the lithium that can be inserted and removed from the positive electrode active material is desorbed.
- the theoretical capacity of LiCoO 2 is 274 mAh / g
- the theoretical capacity of LiNiO 2 is 274 mAh / g
- the theoretical capacity of LiMn 2 O 4 is 148 mAh / g.
- the charging depth when all the insertable and detachable lithium is inserted is 0, and the charging depth when all the insertable and detachable lithium contained in the positive electrode active material is desorbed is 1. And.
- charging means moving lithium ions from the positive electrode to the negative electrode in the battery and moving electrons from the negative electrode to the positive electrode in an external circuit.
- the release of lithium ions is called charging.
- a positive electrode active material having a charging depth of 0.7 or more and 0.9 or less may be referred to as a positive electrode active material charged at a high voltage.
- discharging means moving lithium ions from the negative electrode to the positive electrode in the battery and moving electrons from the positive electrode to the negative electrode in an external circuit.
- inserting lithium ions is called electric discharge.
- a positive electrode active material having a charging depth of 0.06 or less, or a positive electrode active material in which a capacity of 90% or more of the charging capacity is discharged from a state of being charged at a high voltage is defined as a sufficiently discharged positive electrode active material. ..
- the non-equilibrium phase change means a phenomenon that causes a non-linear change of a physical quantity.
- a non-equilibrium phase change occurs before and after the peak in the dQ / dV curve obtained by differentiating the capacitance (Q) with the voltage (V) (dQ / dV), and the crystal structure changes significantly. ..
- the secondary battery has, for example, a positive electrode and a negative electrode.
- a positive electrode active material As a material constituting the positive electrode, there is a positive electrode active material.
- the positive electrode active material is, for example, a substance that undergoes a reaction that contributes to the charge / discharge capacity.
- the positive electrode active material may contain a substance that does not contribute to the charge / discharge capacity.
- the positive electrode active material of one aspect of the present invention may be expressed as a positive electrode material, a positive electrode material for a secondary battery, or the like. Further, in the present specification and the like, the positive electrode active material according to one aspect of the present invention preferably has a compound. Further, in the present specification and the like, the positive electrode active material according to one aspect of the present invention preferably has a composition. Further, in the present specification and the like, the positive electrode active material according to one aspect of the present invention preferably has a complex.
- the discharge rate is the 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 positive electrode active material of one aspect of the present invention is obtained by mixing a halogen compound having an alkali metal A, a compound having magnesium, and a metal oxide having an alkali metal A and a transition metal, and annealing (heating, heat treatment, etc.). It may be expressed as). Further, in the annealing process, it is preferable to add a compound having a metal M in addition to the above three materials. By adding the compound having the metal M, the structural stability of the positive electrode active material may be improved, and the charging voltage of the secondary battery may be increased. As a result, the energy density increases. In addition, the life of the secondary battery is extended.
- the transition metal is preferably one or more of, for example, cobalt, manganese, nickel and iron. Further, the transition metal contained in the alkali metal A and the metal oxide having the transition metal is preferably an element different from the metal M described later.
- the metal oxide having an alkali metal A and a transition metal has, for example, a layered rock salt type structure. Alternatively, for example, it has a spinel-type structure.
- the metal M is, for example, one or more selected from nickel, aluminum, manganese, titanium, vanadium, iron and chromium, and particularly preferably one or more of nickel and aluminum.
- a eutectic reaction occurs by mixing a halogen compound having an alkali metal A and a compound having magnesium and heating them. Alternatively, the co-melting point decreases. Alternatively, a eutectic reaction occurs. Alternatively, the eutectic point decreases.
- melting can occur at a temperature lower than the melting points of each other, and magnesium can be added to the surface and the inside of the metal oxide having the alkali metal A and the transition metal.
- the alkali metal A is obtained by adding the compound having the metal M in addition to the three materials of the halogen compound having the alkali metal A, the compound having magnesium, and the metal oxide having the alkali metal A and the transition metal.
- the eutectic reaction of the halogen compound and the compound having magnesium may be inhibited.
- the reason why the eutectic reaction is inhibited is that the compound having the metal M reacts with at least one of the compound having magnesium and the halogen compound having alkali metal A at a temperature lower than the temperature at which the eutectic reaction is suggested. To do.
- the susceptibility to the eutectic reaction may vary depending on the atmosphere and pressure of the annealing and the total amount of the material to be annealed with respect to the volume inside the processing chamber of the annealing device.
- the compound having the metal M has a small amount of reaction with the compound having magnesium and the halogen compound having the alkali metal A at a temperature lower than the temperature at which the eutectic reaction is suggested.
- a halogen compound having alkali metal A, a compound having magnesium, and a metal oxide having alkali metal A and a transition metal are mixed. After annealing, a compound having a metal M may be mixed and annealed.
- the reaction between the halogen compound having alkali metal A and the compound having magnesium and the compound having metal M at a temperature lower than the temperature at which the eutectic reaction is suggested can be inspected by the following method.
- the compound having magnesium has been described so far as a substance that causes a eutectic reaction with the halogen compound having the alkali metal A
- a compound having an element X can be used instead of the compound having magnesium.
- elements such as calcium, zirconium, lanthanum, and barium can be used. Further, for example, an element such as copper, potassium, sodium or zinc can be used as the element X.
- magnesium may be contained in addition to the elements shown above. Further, as the element X, two or more of the above-mentioned elements may be used in combination.
- FIG. 1A shows an example in which the reaction between the substance 91 and the substance 92 is inspected by using DSC (Differential scanning calorimetry).
- the substance 91 is a halogen compound having an alkali metal A
- the substance 92 is a compound having an element X.
- step S01 substance 91 and substance 92 are prepared.
- step S02 the substance 91 and the substance 92 are mixed to obtain a mixture 81.
- step S03 the inspection is performed.
- DSC is performed as an inspection.
- the DSC scans the measured temperature and observes changes in the amount of heat.
- This change in calorific value is caused by, for example, an endothermic reaction such as melting or an exothermic reaction such as crystallization.
- the substance 91 and the substance 92 are observed to have a change in the amount of heat suggesting an endothermic reaction at the temperature T (1).
- FIG. 1B shows an example in which the reaction of substance 91, substance 92 and substance 93 is inspected using DSC.
- the substance 93 is a compound having the metal M (1).
- the metal M (1) the description of the metal M can be referred to.
- the temperature T (1) is preferably 620 ° C or higher and 920 ° C or lower, more preferably 700 ° C or higher and 850 ° C or lower, and further preferably 700 ° C or higher and 770 ° C or lower.
- DSC is performed to obtain a temperature-heat flow curve, preferably [temperature T (1) -50 ° C] or more and [temperature T (1) + 50 ° C] or less, more preferably [temperature T (1)).
- a peak suggesting an endothermic reaction is observed at an intensity of 0.3 times or more of the peak intensity I (1) at -30 ° C or higher and [temperature T (1) + 30 ° C] or lower.
- the eutectic reaction is carried out.
- the half width of the observed peak preferably does not exceed 100 ° C, preferably 50 ° C or lower, and more preferably 30 ° C or lower.
- the peak intensity I (1) is preferably calculated by normalizing the compounding ratio of the substance 91 and the substance 92 in the total weight of the mixture.
- the scanning speed of the DSC is, for example, 20 ° C./min. , Preferably, for example, 2 ° C./min. Above 30 ° C./min. The following is preferable.
- the differential waveform of DSC is acquired, and the difference in height between the maximum point and the minimum point observed in the differential waveform is peaked before and after the temperature at which the peak was observed in the temperature-heat flow curve before differentiation. It may be strength.
- the absolute value of the difference between the peak position where the maximum point observed in the differential waveform is observed and the peak position of the temperature-heat flow curve is preferably smaller than 0.5 times the half width of the peak of the temperature-heat flow curve. ..
- the absolute value of the difference between the peak position where the minimum point observed in the differential waveform is observed and the peak position of the temperature-heat flow curve is also preferably smaller than 0.5 times the half-value width of the peak of the temperature-heat flow curve. ..
- FIG. 1C shows an example in which the reaction of substance 91, substance 92, substance 93 and substance 94 is inspected using DSC.
- the substance 94 is a compound having the metal M (2).
- the metal M (2) the description of the metal M can be referred to.
- the metal M (2) preferably contains a metal different from that of the metal M (1).
- the metal oxide 95 may be added for inspection.
- the metal oxide 95 is here a metal oxide having an alkali metal A and a transition metal.
- the temperature T (1) at which the peak is observed may be higher, for example, by about 100 ° C. than when the metal oxide 95 is not added.
- lithium, sodium, potassium or the like may be used as the alkali metal A, and it is particularly preferable to use lithium.
- the metal oxide having the alkali metal A and the transition metal for example, a metal oxide having a layered rock salt type structure may be used. Alternatively, a metal oxide having a structure represented by the space group R-3m may be used.
- lithium cobalt oxide lithium manganate, lithium nickel oxide, lithium cobalt oxide in which part of cobalt is substituted with manganese, and cobalt in which part of cobalt is substituted with nickel.
- Lithium oxide or nickel-manganese-lithium cobalt oxide can be used.
- the ratio Ni / (Co + Ni) of the number of atoms of nickel (Ni) to the sum of the number of atoms of cobalt and nickel (Co + Ni) is 0. It is preferably less than .1 and more preferably 0.075 or less. If the state of being charged at a high voltage is maintained for a long time, the transition metal may be eluted from the positive electrode active material into the electrolytic solution, and the crystal structure may be destroyed. However, by having nickel in the above ratio, elution of the transition metal from the positive electrode active material 100 may be suppressed.
- halogen compound having the alkali metal A examples include lithium fluoride, sodium fluoride, potassium fluoride, lithium chloride, sodium chloride, calcium chloride, and the like. Lithium fluoride is particularly preferable because it easily melts in the annealing step described later.
- a compound having magnesium can be used as the compound having the element X.
- the compound having magnesium include magnesium fluoride, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium chloride, and the like.
- lithium fluoride as the halogen compound having the alkali metal A and magnesium fluoride as the compound having magnesium.
- lithium fluoride By mixing lithium fluoride, it can be melted at a temperature lower than the melting point of magnesium fluoride, and a positive electrode active material is produced by utilizing this eutectic phenomenon.
- a metal hydroxide, an oxide, or the like can be used as the compound having the metal M.
- nickel for example, nickel hydroxide, nickel oxide, or the like can be used.
- metals contained in the metal M is aluminum, for example, aluminum hydroxide, aluminum oxide, or the like can be used.
- manganese for example, manganese hydroxide, manganese oxide, or the like can be used.
- a metal alkoxide may be used as the compound having the metal M.
- aluminum isopropoxide, tetramethoxytitanium, etc. can be used.
- the positive electrode active material of one aspect of the present invention preferably has the metal oxide having the alkali metal A and the transition metal described above.
- the positive electrode active material of one aspect of the present invention has particles, for example, the particles preferably contain the above-mentioned metal oxide having an alkali metal A and a transition metal.
- the positive electrode active material of one aspect of the present invention preferably contains magnesium and metal M. Further, when the positive electrode active material particles of one aspect of the present invention are contained and the particles contain the metal oxide having the alkali metal A and the transition metal described above, the metal oxide is a part of the metal oxide. It has at least one of magnesium and metal M in the region, more specifically in and near the surface of the particles.
- ⁇ XRD> XRD may be performed as the inspection shown in FIG. 1B or FIG. 1C.
- a compound containing, for example, an element X contained in the substance 92 and one or more of the metal elements contained in the substance 93 and / and the substance 94 is suggested in the XRD, both the substance 91 and the substance 92 are used. It is judged that the fusion reaction is significantly inhibited.
- heating is performed in a temperature range of 600 ° C. or higher and 950 ° C. or lower, and in a range of 1 hour or more and 100 hours or less, and then XRD evaluation is performed.
- the metal oxide having the alkali metal A and the transition metal has a rock salt layered structure
- a peak due to the spinel structure is observed in XRD
- a peak is observed in which the substance 91, the substance 92, and at least one of the substance 93 and the substance 94 are mixed, heated, and XRD analyzed, and the eutectic reaction is significantly inhibited. Even in this case, when the substance 91, the substance 92, at least one of the substance 93 and the substance 94, and the metal oxide 95 are further mixed and heated, the peak caused by the metal oxide 95 is reached. Due to the high intensity, the above peak, which is judged to significantly inhibit the fusion reaction, may not be observed.
- 2A, 2B and 2C show an example of a method for producing a positive electrode active material according to one aspect of the present invention using the substance 91, the substance 92, the substance 93, the substance 94 and the metal oxide 95 described in FIG. Is shown.
- step S11 the substance 91, the substance 92, the substance 93, the substance 94 and the metal oxide 95 prepared in step S11 are mixed, annealed in step S34, and the positive electrode active material 100 is obtained in step S36.
- the flow shown in FIG. 2B is followed. It is preferable to use it to obtain the positive electrode active material 100. In particular, when the total amount of the material to be annealed is large, it may be preferable to use the flow shown in FIG. 2B in order to perform the treatment more uniformly. By performing a more uniform treatment, the quality of the obtained positive electrode active material 100 can be improved. Specifically, for example, when the form of the material is powder and the total amount of the powder is 15 g or more, the flow shown in FIG. 2B may be used.
- the surface of the powder may not be sufficiently exposed to the annealing atmosphere by one annealing. In such cases, the eutectic reaction may be more likely to be inhibited. By using the flow of FIG. 2B, the eutectic reaction can be more reliably generated, which is preferable.
- the total amount of material to be annealed may be devised relative to the atmosphere, pressure, and volume of the processing chamber of the annealing apparatus.
- the total amount of the powder is less than, for example, 15 g, the surface of the powder is easily exposed to the annealing atmosphere, and the inhibition of the eutectic reaction may be suppressed.
- annealing may be performed using, for example, a heating furnace.
- the volume of the heating furnace is, for example, 10 L or more, 20 L or more, or 30 L or more.
- the flow shown in FIG. 2B shows a flow in which the substance 93 and the substance 94 are added after the annealing in step S34.
- the substance 91, the substance 92 and the metal oxide 95 prepared in step S11 are mixed and annealed in step S34.
- a substance 93 and a substance 94 are added to the mixture obtained in step S34 and mixed, annealed in step S55, and a positive electrode active material 100 is obtained in step S36.
- the substance 94 significantly inhibits the reaction suggesting the fusion of the substance 91 and the substance 92, and the substance 93 does not significantly inhibit the reaction, for example, the flow shown in FIG. 2C. Can also be used.
- the substance 91, the substance 92, the substance 93 and the metal oxide 95 prepared in step S11 are mixed and annealed in step S34.
- the substance 94 is added to the mixture obtained in step S34 and mixed, annealed in step S55, and the positive electrode active material 100 is obtained in step S36.
- FIG. 2B An example of the manufacturing method shown in FIG. 2B is shown in FIG.
- a metal oxide having an alkali metal and cobalt is used as the metal oxide having the alkali metal A and the transition metal is shown.
- a compound having magnesium is used as the compound having the element X is shown.
- Step S11 of FIG. 3 the material of the mixture 902 is first prepared.
- lithium fluoride LiF is prepared as a halogen compound having an alkali metal A
- magnesium fluoride MgF 2 is prepared as a compound having magnesium.
- Non-Patent Document 4 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 As the solvent, a ketone such as acetone, an alcohol such as ethanol and isopropanol, 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 step S11 of FIG. 3, acetone is used.
- step S12 the material of the above mixture 902 is mixed and pulverized.
- Mixing can be done dry or wet, but wet is preferred as it can be ground into smaller pieces.
- 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 medium, for example. It is preferable that the mixing and pulverization steps are sufficiently performed to pulverize the mixture 902.
- Step S13 the material mixed and pulverized above is recovered, and in step S14, the mixture 902 is obtained.
- D50 is preferably 600 nm or more and 20 ⁇ m or less, and more preferably 1 ⁇ m or more and 10 ⁇ m or less.
- the mixture 902 pulverized in this way 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, a transition metal 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 can be easily distributed on the surface layer of the composite oxide particles after heating. If there is a region on the surface layer that does not contain halogen and magnesium, it may be difficult to form a pseudo-spinel-type crystal structure described later in the charged state.
- the metal oxide 95 is prepared as the metal oxide having the alkali metal A and cobalt.
- the metal oxide 95 can be obtained by firing a mixture of a material having an alkali metal A and a material having cobalt. Alternatively, a metal oxide synthesized in advance may be used.
- step S31 the mixture 902 and the metal oxide 95 are mixed.
- the mixing in step S31 is preferably made under milder conditions than the mixing in step S12 so as not to destroy the particles of the metal oxide 95.
- the number of revolutions is smaller or the time is shorter than the mixing in step S12.
- the dry type is a milder condition 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 medium, for example.
- Step S32 the material mixed above is recovered, and in step S33, the mixture 903 is obtained.
- Step S34> The mixture 903 is then annealed in step S34.
- Annealing is preferably performed at an appropriate temperature and time.
- the appropriate temperature and time vary depending on conditions such as the particle size and composition of the metal oxide 95. Smaller particles may be more preferred at lower temperatures or shorter times than larger particles.
- the annealing temperature is preferably 600 ° C. or higher and 950 ° C. or lower, for example.
- the annealing time is, for example, preferably 3 hours or more, more preferably 10 hours or more, and even more preferably 60 hours or more.
- the annealing temperature is preferably 600 ° C. or higher and 950 ° C. or lower, for example.
- the annealing 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 annealing is preferably 10 hours or more and 50 hours or less, for example.
- the material having a low melting point for example, lithium fluoride, melting point 848 ° C.
- the presence of this molten material causes the melting point of the other material to drop, causing the other material to melt.
- magnesium fluoride melting point 1263 ° C.
- the element contained in the mixture 902 distributed on the surface layer is considered to be solid-solved in the particles of the metal oxide 95.
- magnesium and halogen have higher concentrations in the surface layer and near the grain boundaries than in the inside. As will be described later, when the magnesium concentration in the surface layer portion and the vicinity of the grain boundary is high, the change in the crystal structure can be suppressed more effectively.
- Step S35, Step S36> The material annealed above is then recovered in step S35 and the mixture 904 is obtained in step S36.
- step S41 the metal M source is prepared.
- the metal M is aluminum, for example, the number of cobalt atoms contained in lithium cobalt oxide may be 1, and the molar concentration of aluminum contained in the metal source may be 0.001 times or more and 0.02 times or less.
- the metal M is nickel, for example, the number of cobalt atoms contained in lithium cobalt oxide may be 1, and the molar concentration of nickel contained in the metal source may be 0.001 times or more and 0.02 times or less.
- the metal M is aluminum or nickel, for example, the number of cobalt atoms contained in lithium cobaltate is 1, the molar concentration of aluminum contained in the metal source is 0.001 times or more and 0.02 times or less, and the metal source is The molar concentration of nickel contained may be 0.001 times or more and 0.02 times or less.
- step S42 when wet mixing is performed, the solvent is also prepared in step S41.
- step S41 of FIG. 3 as an example, nickel hydroxide is used as the metal source and acetone is used as the solvent.
- Step S42 The metal source and solvent are then mixed and ground in step S42.
- conditions such as step S12 can be referred to.
- step S43 the metal M source pulverized in step S42 is recovered.
- step S44 a metal M source having a metal different from that of the metal M source prepared in step S41 is prepared.
- the solvent is also prepared in step S44.
- step S44 of FIG. 3 as an example, aluminum hydroxide is prepared as a metal source and acetone is prepared as a solvent.
- Step S45 The metal source and solvent are then mixed and ground in step S45.
- conditions such as step S12 can be referred to.
- step S46 the metal M source pulverized in step 45 is recovered.
- step S53 the mixture 904, the metal M source recovered in step S43, and the metal M source recovered in step S46 are mixed.
- Step S54 The mixture is then recovered in step S54 and the mixture 905 is obtained in step S55.
- step S56 the mixture 905 is annealed.
- the holding time within the specified temperature range is preferably 1 hour or more and 50 hours or less, and more preferably 2 hours or more and 20 hours or less. If the firing time is too short, the crystallinity of the compound having the metal M formed on the surface layer portion may be low. Alternatively, the diffusion of the metal M may be insufficient. Alternatively, organic substances may remain on the surface. However, if the firing time is too long, the diffusion of the metal M may proceed too much and the concentrations in the surface layer portion and the vicinity of the grain boundaries may decrease. In addition, productivity is reduced.
- the specified temperature is preferably 500 ° C. or higher and 1200 ° C. or lower, more preferably 700 ° C. or higher and 920 ° C. or lower, and further preferably 800 ° C. or higher and 900 ° C. or lower. If the specified temperature is too low, the crystallinity of the compound having the metal M formed on the surface layer portion may be low. Alternatively, the diffusion of the metal M may be insufficient. Alternatively, organic substances may remain on the surface.
- the specified temperature is 850 ° C. and the temperature is maintained for 2 hours, the temperature rise is 200 ° C./h, and the oxygen flow rate is 10 L / min.
- the temperature lowering time from the specified temperature to room temperature is 10 hours or more and 50 hours or less.
- the firing temperature in step S56 is preferably lower than the firing temperature in step S34.
- the firing temperature in step S56 is preferably 20 ° C. or higher, 30 ° C. or higher, or 45 ° C. or higher lower than the firing temperature in step S34.
- step S57 the cooled particles are collected. In addition, it is preferable to sift the particles.
- the positive electrode active material 100 is obtained in step S58.
- FIG. 2C an example of the manufacturing method shown in FIG. 2C is shown in FIG.
- a metal oxide having an alkali metal and cobalt is used as the metal oxide having the alkali metal A and the transition metal.
- a compound having magnesium is used as the compound having the element X is shown.
- Step S11 shown in FIG. 4 is different from FIG. 3 in that a gold pole M (1) source is prepared in addition to a halogen compound having an alkali metal A, a compound having magnesium, and a solvent.
- Step S12 to Step S14 a mixture 906 which is a mixture of a halogen compound having an alkali metal A, a compound having magnesium and a gold pole M (1) source is obtained.
- the description in FIG. 3 can be referred to for the conditions and the like in steps S12 to S14.
- step S14 the mixture 906 may be inspected.
- the metal oxide 95 is prepared as the metal oxide having the alkali metal A and cobalt.
- the metal oxide 95 can be obtained by firing a mixture of a material having an alkali metal A and a material having cobalt. Alternatively, a metal oxide synthesized in advance may be used.
- Step S31 to Step S33 Next, through steps S31, S32 and S33, a mixture 907 which is a mixture of the mixture 906 and the metal oxide 95 is obtained.
- steps S31 to S33 the description in FIG. 3 can be referred to.
- step S33 the mixture 907 may be inspected.
- step S34 the mixture 907 is annealed.
- the description in FIG. 3 can be referred to for the annealing conditions and the like.
- Step S35 The annealed powder is then recovered in step S35 to give the mixture 908 in step S36.
- step S47 the metal M (2) source and the solvent are prepared.
- the sol-gel method is applied, and aluminum isopropoxide is used as the metal M (2) source, and isopropanol is used as the solvent.
- step S53 aluminum isopropoxide is dissolved in isopropanol, and the mixture 908 is further mixed.
- the required amount of metal alkoxide varies depending on the particle size of the metal oxide 95. If the particle size (D50) is about 20 ⁇ m, the number of cobalt atoms contained in the metal oxide 95 is set to 1, and the concentration of aluminum contained in aluminum isopropoxide should be 0.001 times or more and 0.02 times or less. Is preferable.
- the mixture 908 is preferably 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 90% humidity RH (Relative Humidity) conditions. Can be done below. Further, 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, the stirring time is preferably longer, for example, 12 hours or more at room temperature.
- the sol-gel reaction can proceed more slowly than when liquid water is added. Further, by reacting the metal alkoxide with water at room temperature, the sol-gel reaction can proceed more slowly than, for example, when heating is performed at a temperature exceeding the boiling point of the solvent alcohol. By slowly advancing the sol-gel reaction, a coating layer having a uniform thickness and good quality can be formed.
- Step S54 The precipitate is then recovered from the mixture in step S54 and the mixture 909 is obtained in step S55.
- a recovery method 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 recovered residue is then dried to give a mixture 909.
- the drying step can be, for example, vacuum or ventilation drying at 80 ° C. for 1 hour or more and 4 hours or less.
- step S56 the mixture 909 is calcined.
- the holding time within the specified temperature range is preferably 1 hour or more and 50 hours or less, and more preferably 2 hours or more and 20 hours or less. If the firing time is too short, the crystallinity of the compound having the metal M (2) formed on the surface layer portion may be low. Alternatively, the diffusion of the metal M (2) may be insufficient. Alternatively, organic substances may remain on the surface. However, if the firing time is too long, the diffusion of the metal M (2) may proceed too much, and the concentrations in the surface layer portion and the vicinity of the crystal grain boundaries may decrease. In addition, productivity is reduced.
- the specified temperature is preferably 500 ° C. or higher and 1200 ° C. or lower, more preferably 700 ° C. or higher and 920 ° C. or lower, and further preferably 800 ° C. or higher and 900 ° C. or lower. If the specified temperature is too low, the crystallinity of the compound having the metal M (2) formed on the surface layer portion may be low. Alternatively, the diffusion of the metal M (2) may be insufficient. Alternatively, organic substances may remain on the surface.
- the specified temperature is 850 ° C. and the temperature is maintained for 2 hours, the temperature rise is 200 ° C./h, and the oxygen flow rate is 10 L / min.
- the temperature lowering time from the specified temperature to room temperature is 10 hours or more and 50 hours or less.
- the firing temperature in step S56 is preferably lower than the firing temperature in step S34.
- step S57 the cooled particles are collected. In addition, it is preferable to sift the particles.
- the positive electrode active material 100 is obtained in step S58.
- the positive electrode active material of one aspect of the present invention includes a halogen compound having an alkali metal A, a compound having magnesium, and a metal oxide having an alkali metal A and a transition metal.
- a halogen compound having an alkali metal A a compound having magnesium
- a metal oxide having an alkali metal A and a transition metal a compound having magnesium
- a metal oxide having an alkali metal A and a transition metal are mixed and annealed (sometimes referred to as heating, heat treatment, etc.). It does not necessarily have to have the metal M. In the absence of the metal M, a single annealing process may be most preferred. If the annealing process is performed only once, the productivity can be improved as compared with the case of multiple annealing processes.
- This embodiment can be used in combination with other embodiments as appropriate.
- ⁇ Positive electrode active material> By using the positive electrode active material of one aspect of the present invention, the capacity of the secondary battery is increased, and the decrease in discharge capacity due to the charge / discharge cycle is suppressed.
- the positive electrode active material preferably has a metal that becomes a carrier ion (hereinafter, element A).
- element A for example, alkali metals such as lithium, sodium and potassium, and Group 2 elements such as calcium, beryllium and magnesium can be used.
- the positive electrode active material carrier ions are desorbed from the positive electrode active material as it is charged. If the desorption of the element A is large, the capacity of the secondary battery is increased due to the large number of ions contributing to the capacity of the secondary battery. On the other hand, if the element A is largely desorbed, the crystal structure of the compound contained in the positive electrode active material is likely to collapse. The collapse of the crystal structure of the positive electrode active material may lead to a decrease in the discharge capacity due to the charge / discharge cycle. When the positive electrode active material of one aspect of the present invention has the element X, the collapse of the crystal structure when the carrier ions are desorbed during charging of the secondary battery may be suppressed.
- the element X For example, a part of the element X is replaced with the position of the element A.
- Elements such as magnesium, calcium, zirconium, lanthanum, and barium can be used as the element X.
- an element such as copper, potassium, sodium or zinc can be used as the element X.
- two or more of the above-mentioned elements may be used in combination.
- the positive electrode active material of one aspect of the present invention preferably has a halogen in addition to the element X. It is preferable to have a halogen such as fluorine and chlorine. When the positive electrode active material of one aspect of the present invention has the halogen, the substitution of element X with the position of element A may be promoted.
- the positive electrode active material of one aspect of the present invention has a metal (hereinafter, element Me) whose valence changes depending on the charging and discharging of the secondary battery.
- the element Me is, for example, a transition metal.
- the positive electrode active material of one aspect of the present invention has, for example, one or more of cobalt, nickel, and manganese as the element Me, and particularly has cobalt.
- the position of the element Me may have an element such as aluminum which does not change in valence and can have the same valence as the element Me, more specifically, for example, a trivalent main group element.
- the element X described above may be substituted at the position of the element Me, for example. When the positive electrode active material of one aspect of the present invention is an oxide, the element X may be substituted at the position of oxygen.
- the positive electrode active material of one aspect of the present invention for example, it is preferable to use a lithium composite oxide having a layered rock salt type crystal structure. More specifically, for example, as a lithium composite oxide having a layered rock salt type crystal structure, a lithium composite oxide having lithium cobalt oxide, lithium nickel oxide, nickel, manganese and cobalt, and a lithium composite oxide having nickel, cobalt and aluminum. , Etc. can be used. Further, these positive electrode active materials are preferably represented by the space group R-3m.
- the crystal structure may collapse when the charging depth is increased.
- the collapse of the crystal structure is, for example, a layer shift. If the collapse of the crystal structure is irreversible, the capacity of the secondary battery may decrease due to repeated charging and discharging.
- the positive electrode active material of one aspect of the present invention can realize excellent cycle characteristics. Further, the positive electrode active material of one aspect of the present invention can have a stable crystal structure in a high voltage charging state. Therefore, the positive electrode active material according to one aspect of the present invention may be less likely to cause a short circuit when the high voltage charged state is maintained. In such a case, safety is further improved, which is preferable.
- the difference in volume between the fully discharged state and the charged state with a high voltage is small when compared with the change in crystal structure and the same number of transition metal atoms.
- Positive electrode active material of an embodiment of the present invention may be represented by the chemical formula AM y O Z (y> 0 , z> 0).
- lithium cobalt oxide may be represented by LiCoO 2 .
- lithium nickelate may be represented by LiNiO 2 .
- the positive electrode active material of one aspect of the present invention having the element X when the charging depth is 0.8 or more, it is represented by the space group R-3m, and although it does not have a spinel-type crystal structure, the element Me (for example, cobalt) , Elements X (eg magnesium), etc. may occupy the oxygen 6 coordination position and the cation arrangement may have symmetry similar to the spinel type.
- This structure is referred to as a pseudo-spinel type crystal structure in the present specification and the like.
- a light element such as lithium may occupy the oxygen 4-coordination position, and in this case as well, the ion arrangement has symmetry similar to that of the spinel type.
- the structure of the positive electrode active material becomes unstable due to the desorption of carrier ions during charging. It can be said that the pseudo-spinel type crystal structure is a structure capable of maintaining high stability despite desorption of carrier ions.
- the charging depth of the present invention is high, by using a positive electrode active material having a pseudo-spinel type structure in the secondary battery, for example, at a voltage of about 4.6 V with respect to the potential of lithium metal, 4.62 V is more preferable. At a voltage of about 4.7 V, the structure of the positive electrode active material is stable, and it is possible to suppress a decrease in capacity due to charging and discharging.
- graphite is used as the negative electrode active material in the secondary battery, for example, the positive electrode activity is performed when the voltage of the secondary battery is 4.3 V or more and 4.5 V or less, more preferably 4.35 V or more and 4.55 V or less.
- the structure of the material is stable, and it is possible to suppress a decrease in capacity due to charging and discharging.
- the pseudo-spinel type crystal structure has Li randomly 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 a charging depth of 0.94 (Li 0.06 NiO 2 ), but contains a large amount of pure lithium cobalt oxide or cobalt. It is known that the layered rock salt type positive electrode active material usually does not have this crystal structure.
- Layered rock salt crystals and anions of rock salt crystals have a cubic closest packed structure (face-centered cubic lattice structure). Pseudo-spinel-type crystals are also presumed to have a cubic close-packed structure with anions. When they come into contact, there is a crystal plane in which the cubic close-packed structure composed of anions is oriented in the same direction.
- the space group of layered rock salt type crystals and pseudo-spinel type crystals is R-3m
- the space group of rock salt type crystals Fm-3m (space group of general rock salt type crystals) and Fd-3m (the simplest symmetry).
- the mirror index of the crystal plane satisfying the above conditions is different between the layered rock salt type crystal and the pseudo spinel type crystal and the rock salt type crystal.
- the orientations of the crystals are substantially the same when the orientations of the cubic closest packed structures composed of anions are aligned. is there.
- the pseudo-spinel 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.
- the difference between the volume of the unit cell at the volume of 0 charge depth and the volume per unit cell of the pseudo-spinel type crystal structure at the charge depth of 0.82 is preferably 2.5% or less. 2.2% or less is more preferable.
- the positive electrode active material of one aspect of the present invention has a pseudo-spinel-type crystal structure when charged at a high voltage, but not all of the particles need to have a pseudo-spinel-type crystal structure. It may contain other crystal structures or may be partially amorphous. However, when Rietveld analysis is performed on the XRD pattern, the pseudo-spinel type crystal structure is preferably 50 wt% or more, more preferably 60 wt% or more, and further preferably 66 wt% or more. When the pseudo-spinel type crystal structure is 50 wt% or more, more preferably 60 wt% or more, still more preferably 66 wt% or more, the positive electrode active material having sufficiently excellent cycle characteristics can be obtained.
- the number of atoms of element X is preferably 0.001 times or more and 0.1 times or less the number of atoms of element Me, more preferably greater than 0.01 and less than 0.04, and even more preferably about 0.02.
- the concentration of the element X shown here may be, for example, a value obtained by elemental analysis of the entire particles of the positive electrode active material using ICP-MS or the like, or a value of the composition of the raw materials in the process of producing the positive electrode active material. May be based on.
- the ratio Ni / (Co + Ni) of the number of nickel atoms (Ni) to the sum of the atomic numbers of cobalt and nickel (Co + Ni) may be less than 0.1. It is preferably 0.075 or less, and more preferably 0.075 or less.
- This embodiment can be used in combination with other embodiments as appropriate.
- the positive electrode has a positive electrode active material layer and a positive electrode current collector.
- the positive electrode active material layer has at least a positive electrode active material. Further, the positive electrode active material layer may contain other substances such as a coating film on the surface of the active material, a conductive auxiliary agent or a binder in addition to the positive electrode active material.
- the positive electrode active material 100 described in the previous embodiment can be used. By using the positive electrode active material 100 described in the previous embodiment, a secondary battery having a high capacity and excellent cycle characteristics can be obtained.
- a carbon material, a metal material, a conductive ceramic material, or the like can be used.
- a fibrous material as a conductive auxiliary agent.
- the content of the conductive auxiliary agent with respect to the total amount of the active material layer is preferably 1 wt% or more and 10 wt% or less, and more preferably 1 wt% or more and 5 wt% or less.
- the conductive auxiliary agent can form a network of electrical conduction in the active material layer.
- the conductive auxiliary agent can maintain the path of electrical conduction between the positive electrode active materials.
- the conductive auxiliary agent for example, natural graphite, artificial graphite such as mesocarbon microbeads, carbon fiber, or the like can be used.
- carbon fibers for example, carbon fibers such as mesophase pitch carbon fibers and isotropic pitch carbon fibers can be used.
- carbon fiber, carbon nanofiber, carbon nanotube, or the like can be used.
- the carbon nanotubes can be produced by, for example, a vapor phase growth method.
- a carbon material such as carbon black (acetylene black (AB) or the like), graphite (graphite) particles, graphene, fullerene or the like can be used.
- metal powders such as copper, nickel, aluminum, silver and gold, metal fibers, conductive ceramic materials and the like can be used.
- a graphene compound may be used as the conductive auxiliary agent.
- Graphene compounds may have excellent electrical properties such as high conductivity and excellent physical properties such as high flexibility and high mechanical strength.
- the graphene compound has a planar shape.
- Graphene compounds enable surface contact with low contact resistance. Further, even if it is thin, the conductivity may be very high, and a conductive path can be efficiently formed in the active material layer with a small amount. Therefore, it is preferable to use the graphene compound as the conductive auxiliary agent because the contact area between the active material and the conductive auxiliary agent can be increased.
- a spray-drying device it is preferable to cover the entire surface of the active material and form a graphene compound as a conductive auxiliary agent as a film. It is also preferable because the electrical resistance may be reduced.
- RGO refers to, for example, a compound obtained by reducing graphene oxide (GO).
- an active material having a small particle size for example, an active material having a particle size of 1 ⁇ m or less
- the specific surface area of the active material is large, and more conductive paths for connecting the active materials are required. Therefore, the amount of the conductive auxiliary agent tends to increase, and the amount of the active material supported tends to decrease relatively.
- the capacity of the secondary battery decreases.
- the graphene compound when a graphene compound is used as the conductive auxiliary agent, the graphene compound can efficiently form a conductive path even in a small amount, so that it is not necessary to reduce the amount of the active material supported, which is particularly preferable.
- graphene or multigraphene may be used as the graphene compound.
- the graphene compound preferably has a sheet-like shape.
- the graphene compound may be in the form of a sheet in which a plurality of multigraphenes or / or a plurality of graphenes are partially overlapped.
- the sheet-shaped graphene compound is dispersed substantially uniformly inside the active material layer.
- the plurality of graphene compounds are preferably formed so as to partially cover the plurality of granular positive electrode active materials or to stick to the surface of the plurality of granular positive electrode active materials, and are in surface contact with each other.
- a network-like graphene compound sheet (hereinafter referred to as graphene compound net or graphene net) can be formed by binding a plurality of graphene compounds to each other.
- the graphene net can also function as a binder for binding the active materials to each other. Therefore, since the amount of the binder can be reduced or not used, the ratio of the active material to the electrode volume and the electrode weight can be improved. That is, the capacity of the secondary battery can be increased.
- graphene oxide as a graphene compound, mix it with an active material to form a layer to be an active material layer, and then reduce it.
- the graphene compound can be dispersed substantially uniformly inside the active material layer. Since the solvent is volatilized and removed from the uniformly dispersed graphene oxide-containing dispersion medium to reduce the graphene oxide, the graphene compounds remaining in the active material layer partially overlap and are dispersed to the extent that they are in surface contact with each other. Can form a three-dimensional conductive path.
- the graphene oxide may be reduced, for example, by heat treatment or by using a reducing agent.
- graphene compounds enable surface contact with low contact resistance, so the amount of granular positive electrode is smaller than that of ordinary conductive auxiliaries.
- the electrical conductivity between the active material and the graphene compound can be improved. Therefore, the ratio of the positive electrode active material in the active material layer can be increased. As a result, the discharge capacity of the secondary battery can be increased.
- a spray-drying device in advance, it is possible to cover the entire surface of the active material to form a graphene compound as a conductive auxiliary agent as a film, and further to form a conductive path between the active materials with the graphene compound. ..
- 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, or ethylene-propylene-diene copolymer.
- SBR styrene-butadiene rubber
- fluororubber can be used as a binder.
- a water-soluble polymer for example, a polysaccharide or the like can be used.
- a polysaccharide for example, cellulose derivatives such as carboxymethyl cellulose (CMC), methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose and regenerated cellulose, starch and 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, polymethyl methacrylate (polymethyl methacrylate, 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 cellulose derivatives such as diacetyl cellulose and regenerated cellulose, and starch are used. be able to.
- CMC carboxymethyl cellulose
- methyl cellulose methyl cellulose
- ethyl cellulose methyl cellulose
- hydroxypropyl cellulose hydroxypropyl cellulose
- cellulose derivatives such as diacetyl cellulose and regenerated cellulose
- the solubility of a cellulose derivative such as carboxymethyl cellulose is increased by using a salt such as a sodium salt or an ammonium salt of carboxymethyl cellulose, and the effect as a viscosity modifier is easily exhibited.
- a salt such as a sodium salt or an ammonium salt of carboxymethyl cellulose
- the cellulose and the cellulose derivative used as the binder of the electrode include salts thereof.
- the water-soluble polymer stabilizes its viscosity by being dissolved in water, and the active material and other materials to be combined as a binder, such as styrene-butadiene rubber, can be stably dispersed in the 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 functional groups such as hydroxyl groups and carboxyl groups, and because they have functional groups, the polymers interact with each other and exist widely covering the surface of the active material. There is expected.
- ⁇ Positive current collector> As the positive electrode current collector, a material having high conductivity such as metals such as stainless steel, gold, platinum, aluminum and titanium, and alloys 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.
- metal elements that react with silicon to form silicide include zirconium, titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, and nickel.
- a foil-like shape, a plate-like shape (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 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. Moreover, you may use the compound which has these elements.
- 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 in the vicinity of 1.
- x is preferably 0.2 or more and 1.5 or less, and more preferably 0.3 or more and 1.2 or less.
- graphite graphitizable carbon (soft carbon), graphitizable carbon (hard carbon), carbon nanotubes, graphene, carbon black, etc. may be used.
- Examples of graphite include artificial graphite and natural graphite.
- Examples of 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 interlayer compound) (0.05 V or more and 0.3 V or less vs. Li / Li + ). As a result, the lithium ion secondary battery can exhibit a high operating voltage. Further, 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 TiO 2
- lithium titanium oxide Li 4 Ti 5 O 12
- lithium-graphite interlayer compound Li x C 6
- niobium pentoxide Nb 2 O 5
- oxidation Oxides such as tungsten (WO 2 ) and molybdenum oxide (MoO 2 ) can be used.
- Li 2.6 Co 0.4 N 3 is preferable because it exhibits a large charge / discharge capacity (900 mAh / g, 1890 mAh / cm 3 ).
- 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 the 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)
- CoO cobalt oxide
- NiO nickel oxide
- FeO iron oxide
- oxides such as Fe 2 O 3 , CuO, Cu 2 O, RuO 2 , Cr 2 O 3 and sulfides such as CoS 0.89 , NiS and CuS, Zn 3 N 2 , Cu 3 N, Ge 3 N 4, etc., sulphides such as NiP 2 , FeP 2 , CoP 3 , and fluorides such as FeF 3 , BiF 3 .
- the same material as the conductive auxiliary agent and binder that the positive electrode active material layer can have can be used.
- the same material as the positive electrode current collector can be used for the negative electrode current collector.
- the negative electrode current collector preferably uses a material that does not alloy with carrier ions such as lithium.
- the electrolyte has a solvent and an electrolyte.
- the solvent of the electrolytic solution is preferably an aproton 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 ethyl methyl 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 them in any combination and ratio. be able to.
- Ionic liquids room temperature molten salt
- Ionic liquids consist of cations and anions, including organic cations and anions.
- organic cation used in the electrolytic solution examples 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.
- organic cation used in the electrolytic solution monovalent amide anion, monovalent methide anion, fluorosulfonic acid anion, perfluoroalkyl sulfonic acid anion, tetrafluoroborate anion, perfluoroalkyl borate anion, hexafluorophosphate anion. , Or perfluoroalkyl phosphate anion and the like.
- the electrolytic solution used for the secondary battery it is preferable to use a highly purified electrolytic solution having a small content of elements other than granular dust and constituent elements of the electrolytic solution (hereinafter, also simply referred to as "impurities").
- impurities a highly purified electrolytic solution having a small content of elements other than granular dust and constituent elements of the electrolytic solution.
- 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.
- Additives may be added.
- concentration of the material to be added 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 acrylic gel, acrylonitrile gel, polyethylene oxide gel, polypropylene oxide gel, fluoropolymer gel and the like can be used.
- polymer for example, a polymer having a polyalkylene oxide structure such as polyethylene oxide (PEO), PVDF, polyacrylonitrile, etc., and a copolymer containing them can be used.
- PEO polyethylene oxide
- 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
- Sulfide-based solid electrolytes include thiosilicon-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 , 30 Li).
- sulfide crystallized glass Li 7 P 3 S 11 , Li 3.25 P 0.95 S 4 etc.
- 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-X Al X Ti 2-X (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.
- Halide-based solid electrolytes include LiAlCl 4 , Li 3 InBr 6 , LiF, LiCl, LiBr, LiI and the like. Further, a composite material in which the pores of porous alumina 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 used as a secondary battery of one aspect of the present invention, that is, aluminum and titanium. Since the positive electrode active material used 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 XO- 4 tetrahedron share a vertex and have a three-dimensionally arranged structure.
- the secondary battery preferably has a separator.
- a separator for example, paper, non-woven fabric, glass fiber, ceramics, or one formed of nylon (polyamide), vinylon (polyvinyl alcohol-based fiber), polyester, acrylic, polyolefin, synthetic fiber using polyurethane or the like is used. Can be done. It is preferable that the separator is processed into an envelope 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 high voltage charging / discharging can be suppressed, and the reliability of the secondary battery can be improved. 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 exterior body of the secondary battery for example, a metal material such as aluminum or a resin material can be used. Further, a film-like exterior body can also be used. As the film, for example, 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.
- FIG. 5A is an external view of a coin-type (single-layer flat type) secondary battery
- FIG. 5B is a cross-sectional view thereof.
- the positive electrode can 301 that also serves as the positive electrode terminal and the negative electrode can 302 that also serves as the 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 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 metals such as nickel, aluminum, and titanium that are corrosion resistant to the electrolytic solution, or alloys thereof or alloys of these and other metals (for example, stainless steel) may be used. it can. Further, in order to prevent corrosion by the electrolytic solution, 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 electrolyte is impregnated with the negative electrode 307, the positive electrode 304, and the separator 310, and as shown in FIG. 5B, 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.
- a coin-shaped secondary battery 300 is manufactured by crimping the 301 and the negative electrode can 302 via the gasket 303.
- the current flow during charging of the secondary battery will be described with reference to FIG. 5C.
- a secondary battery using lithium is regarded as one closed circuit, the movement of lithium ions and the flow of current 78i are in the same direction.
- the anode (anode) and the cathode (cathode) are exchanged by charging and discharging, and the oxidation reaction and the reduction reaction are exchanged. Therefore, an electrode having a high reaction potential is called a positive electrode.
- An electrode having a low reaction potential is called a negative electrode. Therefore, in the present specification, the positive electrode is "positive electrode” or “positive electrode” regardless of whether the battery is being charged, discharged, a reverse pulse current is applied, or a charging current is applied.
- the negative electrode is referred to as "positive electrode” and the negative electrode is referred to as "negative electrode” or "-pole (minus electrode)".
- anode (anode) and cathode (cathode) related to the oxidation reaction and the reduction reaction are used, the charging and discharging are reversed, which may cause confusion. Therefore, the terms anode (anode) and cathode (cathode) are not used herein. If the terms anode (anode) and cathode (cathode) are used, specify whether they are charging or discharging, and also indicate whether they correspond to the positive electrode (positive electrode) or the negative electrode (negative electrode). To do.
- a charger is connected to the two terminals shown in FIG. 5C, and the secondary battery 300 is charged. As the charging of the secondary battery 300 progresses, the potential difference between the electrodes increases.
- FIG. 6B is a diagram schematically showing a cross section of the cylindrical secondary battery 600.
- the cylindrical secondary battery 600 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.
- the positive electrode cap and the battery can (outer can) 602 are insulated by a gasket (insulating packing) 610.
- a battery element in which a strip-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 the center pin.
- 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 between these and another metal (for example, stainless steel or the like) can be used. .. Further, in order to prevent corrosion by the electrolytic solution, it is preferable to coat the battery can 602 with nickel, aluminum or the like.
- 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.
- 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 612, and the negative electrode terminal 607 is resistance welded to the bottom of the battery can 602.
- the safety valve mechanism 612 is electrically connected to the positive electrode cap 601 via a PTC element (Positive Temperature Coefficient) 611.
- the safety valve mechanism 612 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.
- a plurality of secondary batteries 600 may be sandwiched between the conductive plate 613 and the conductive plate 614 to form the module 615.
- the plurality of secondary batteries 600 may be connected in parallel, may be connected in series, or may be connected in parallel and then further connected in series.
- FIG. 6D is a top view of the module 615.
- the conductive plate 613 is shown by a dotted line for clarity.
- the module 615 may have a lead wire 616 that electrically connects a plurality of secondary batteries 600.
- a conductive plate can be superposed on the conducting wire 616.
- the temperature control device 617 may be provided between the plurality of secondary batteries 600. When the secondary battery 600 is overheated, it can be cooled by the temperature control device 617, and when the secondary battery 600 is too cold, it can be heated by the temperature control device 617. Therefore, the performance of the module 615 is less affected by the outside air temperature.
- the heat medium included in the temperature control device 617 preferably has insulating properties and nonflammability.
- FIG. 7A and 7B are views showing an external view of the secondary battery.
- the secondary battery 913 is connected to the antenna 914 and the antenna 915 via the circuit board 900.
- a label 910 is affixed to the secondary battery 913. Further, as shown in FIG. 7B, the secondary battery 913 is connected to the terminal 951 and the terminal 952.
- the circuit board 900 has a terminal 911 and a circuit 912.
- Terminal 911 is connected to terminal 951, terminal 952, antenna 914, antenna 915, and circuit 912.
- a plurality of terminals 911 may be provided, and each of the plurality of terminals 911 may be used as a control signal input terminal, a power supply terminal, or the like.
- the circuit 912 may be provided on the back surface of the circuit board 900.
- the antenna 914 and the antenna 915 are not limited to the coil shape, and may be, for example, a linear shape or a plate shape. Further, antennas such as a flat 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 914 or the antenna 915 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 914 or the antenna 915 may function as one of the two conductors of the capacitor. As a result, electric power can be exchanged not only by an electromagnetic field and a magnetic field but also by an electric field.
- the line width of the antenna 914 is preferably larger than the line width of the antenna 915. As a result, the amount of power received by the antenna 914 can be increased.
- the secondary battery has a layer 916 between the antenna 914 and the antenna 915 and the secondary battery 913.
- the layer 916 has a function capable of shielding the electromagnetic field generated by the secondary battery 913, for example.
- a magnetic material can be used as the layer 916.
- the structure of the secondary battery is not limited to FIG. 7.
- antennas may be provided on each of the pair of facing surfaces of the secondary battery 913 shown in FIGS. 7A and 7B.
- FIG. 8A is an external view showing one of the pair of surfaces
- FIG. 8B is an external view showing the other of the pair of surfaces.
- the description of the secondary battery shown in FIGS. 7A and 7B can be appropriately incorporated.
- the antenna 914 is provided on one side of the pair of surfaces of the secondary battery 913 with the layer 916 interposed therebetween, and as shown in FIG. 8B, the layer 917 is provided on the other side of the pair of surfaces of the secondary battery 913.
- An antenna 918 is provided on the sandwich.
- the layer 917 has a function capable of shielding the electromagnetic field generated by the secondary battery 913, for example.
- a magnetic material can be used as the layer 917.
- the antenna 918 has, for example, a function capable of performing data communication with an external device.
- an antenna having a shape applicable to the antenna 914 can be applied.
- a communication method between the secondary battery and other devices via the antenna 918 a response method that can be used between the secondary battery and other devices such as NFC (Near Field Communication) shall be applied. Can be done.
- the display device 920 may be provided in the secondary battery 913 shown in FIGS. 7A and 7B.
- the display device 920 is electrically connected to the terminal 911. It is not necessary to provide the label 910 on the portion where the display device 920 is provided.
- the description of the secondary battery shown in FIGS. 7A and 7B can be appropriately incorporated.
- the display device 920 may display, for example, an image showing whether or not charging is in progress, an image showing the amount of stored electricity, and the like.
- an electronic paper for example, a liquid crystal display device, an electroluminescence (also referred to as EL) display device, or the like can be used.
- the power consumption of the display device 920 can be reduced by using electronic paper.
- the sensor 921 may be provided in the secondary battery 913 shown in FIGS. 7A and 7B.
- the sensor 921 is electrically connected to the terminal 911 via the terminal 922.
- the description of the secondary battery shown in FIGS. 7A and 7B can be appropriately incorporated.
- the sensor 921 includes, for example, displacement, position, velocity, acceleration, angular velocity, rotation speed, distance, light, liquid, magnetism, temperature, chemical substance, voice, time, hardness, electric field, current, voltage, power, radiation, flow rate. , Humidity, inclination, vibration, odor, or infrared rays may be measured.
- data temperature or the like
- indicating the environment in which the secondary battery is placed can be detected and stored in the memory in the circuit 912.
- the secondary battery 913 shown in FIG. 9A has a winding body 950 in which terminals 951 and 952 are provided inside the housing 930.
- the wound body 950 is impregnated with 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.
- a metal material for example, aluminum
- a resin material can be used as the housing 930.
- the housing 930 shown in FIG. 9A 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.
- an antenna such as an antenna 914 or an antenna 915 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 negative electrode 931 is connected to the terminal 911 shown in FIG. 7 via one of the terminal 951 and the terminal 952.
- the positive electrode 932 is connected to the terminal 911 shown in FIG. 7 via the other of the terminal 951 and the terminal 952.
- the laminated type secondary battery has a flexible structure
- the secondary battery can be bent according to the deformation of the electronic device if it is mounted on an electronic device having at least a part of the flexible portion. it can.
- the laminated type secondary battery 980 will be described with reference to FIG.
- the laminated secondary battery 980 has a wound body 993 shown in FIG. 11A.
- the wound body 993 has a negative electrode 994, a positive electrode 995, and a separator 996. Similar to the winding body 950 described with reference to FIG. 10, the wound body 993 is formed by laminating a negative electrode 994 and a positive electrode 995 on top of each other with a separator 996 interposed therebetween, and winding the laminated sheet.
- the number of layers of the negative electrode 994, the positive electrode 995, and the separator 996 may be appropriately designed according to the required capacity and the element volume.
- the negative electrode 994 is connected to the negative electrode current collector (not shown) via one of the lead electrode 997 and the lead electrode 998
- the positive electrode 995 is connected to the positive electrode current collector (not shown) via the other of the lead electrode 997 and the lead electrode 998. Is connected to.
- the above-mentioned winding body 993 is housed in a space formed by bonding a film 981 as an exterior body and a film 982 having a recess by thermocompression bonding or the like, and is shown in FIG. 11C.
- the secondary battery 980 can be manufactured as described above.
- the wound body 993 has a lead electrode 997 and a lead electrode 998, and is impregnated with an electrolytic solution inside the film 981 and the film 982 having a recess.
- a metal material such as aluminum or a resin material can be used.
- a resin material is used as the material of the film 981 and the film 982 having the recesses, the film 981 and the film 982 having the recesses can be deformed when an external force is applied to produce a flexible storage battery. be able to.
- FIGS. 11B and 11C show an example in which two films are used, a space may be formed by bending one film, and the above-mentioned winding body 993 may be stored in the space.
- a secondary battery 980 having a high capacity and excellent cycle characteristics can be obtained.
- the secondary battery 980 having the wound body in the space formed by the film serving as the exterior body has been described.
- the space formed by the film serving as the exterior body may be formed. It may be a secondary battery having a plurality of strip-shaped positive electrodes, separators and negative electrodes.
- the laminated secondary battery 500 shown in FIG. 12A includes a positive electrode 503 having a positive electrode current collector 501 and a positive electrode active material layer 502, a negative electrode 506 having a negative electrode current collector 504 and a negative electrode active material layer 505, and a separator 507. , The electrolytic solution 508, and the exterior body 509. A separator 507 is installed between the positive electrode 503 and the negative electrode 506 provided in the exterior body 509. Further, the inside of the exterior body 509 is filled with the electrolytic solution 508. As the electrolytic solution 508, the electrolytic solution shown in the second embodiment can be used.
- the positive electrode current collector 501 and the negative electrode current collector 504 also serve as terminals for obtaining electrical contact with the outside. Therefore, a part of the positive electrode current collector 501 and the negative electrode current collector 504 may be arranged so as to be exposed to the outside from the exterior body 509. Further, the positive electrode current collector 501 and the negative electrode current collector 504 are not exposed to the outside from the exterior body 509, and the lead electrode is ultrasonically bonded to the positive electrode current collector 501 or the negative electrode current collector 504 using a lead electrode. It may be allowed to expose the lead electrode to the outside.
- the exterior body 509 has a highly flexible metal such as aluminum, stainless steel, copper, and nickel on a film made of a material such as polyethylene, polypropylene, polycarbonate, ionomer, and polyamide.
- a three-layer structure laminate film in which a thin film is provided and an insulating synthetic resin film such as a polyamide resin or a polyester resin is provided on the metal thin film as the outer surface of the exterior body can be used.
- FIG. 12B an example of the cross-sectional structure of the laminated secondary battery 500 is shown in FIG. 12B.
- FIG. 12A shows an example of being composed of two current collectors for simplicity, it is actually composed of a plurality of electrode layers as shown in FIG. 12B.
- the number of electrode layers is 16 as an example. Even if the number of electrode layers is 16, the secondary battery 500 has flexibility.
- FIG. 12B shows a structure in which the negative electrode current collector 504 has 8 layers and the positive electrode current collector 501 has 8 layers, for a total of 16 layers. Note that FIG. 12B shows a cross section of the negative electrode extraction portion, in which eight layers of negative electrode current collectors 504 are ultrasonically bonded.
- the number of electrode layers is not limited to 16, and may be large or small. When the number of electrode layers is large, a secondary battery having a larger capacity can be used. Further, when the number of electrode layers is small, the thickness can be reduced and a secondary battery having excellent flexibility can be obtained.
- FIGS. 13 and 14 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. 15A 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 and shape of the tab region of the positive electrode and the negative electrode are not limited to the example shown in FIG. 15A.
- FIG. 15B 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.
- the tab regions of the positive electrode 503 are joined to each other, and the positive electrode lead electrode 510 is joined to the tab region of the positive electrode on the outermost surface.
- bonding for example, ultrasonic welding or the like 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 exterior body 509 from the introduction port provided in the exterior body 509.
- the electrolytic solution 508 is preferably introduced in a reduced pressure atmosphere or an inert atmosphere.
- the inlet is joined. In this way, the laminated type secondary battery 500 can be manufactured.
- FIG. 16A shows a schematic top view of the bendable secondary battery 250.
- 16B1, FIG. 16B2, and FIG. 16C are schematic cross-sectional views taken along the cutting lines C1-C2, cutting lines C3-C4, and cutting lines A1-A2 in FIG. 16A, respectively.
- the secondary battery 250 has an exterior body 251 and an electrode laminate 210 housed inside the exterior body 251.
- the electrode laminate 210 has a structure in which at least the positive electrode 211a and the negative electrode 211b are laminated.
- the lead 212a electrically connected to the positive electrode 211a and the lead 212b electrically connected to the negative electrode 211b extend to the outside of the exterior body 251.
- an electrolytic solution (not shown) is sealed in the region surrounded by the exterior body 251.
- FIG. 17A is a perspective view illustrating the stacking order of the positive electrode 211a, the negative electrode 211b, and the separator 214.
- FIG. 17B is a perspective view showing leads 212a and leads 212b in addition to the positive electrode 211a and the negative electrode 211b.
- the secondary battery 250 has a plurality of strip-shaped positive electrodes 211a, a plurality of strip-shaped negative electrodes 211b, and a plurality of separators 214.
- the positive electrode 211a and the negative electrode 211b each have a protruding tab portion and a portion other than the tab.
- a positive electrode active material layer is formed on a portion other than the tab on one surface of the positive electrode 211a, and a negative electrode active material layer is formed on a portion other than the tab on one surface of the negative electrode 211b.
- the positive electrode 211a and the negative electrode 211b are laminated so that the surfaces of the positive electrode 211a where the positive electrode active material layer is not formed and the surfaces of the negative electrode 211b where the negative electrode active material is not formed are in contact with each other.
- a separator 214 is provided between the surface of the positive electrode 211a on which the positive electrode active material is formed and the surface of the negative electrode 211b on which the negative electrode active material is formed.
- the separator 214 is shown by a dotted line for easy viewing.
- the plurality of positive electrodes 211a and the leads 212a are electrically connected at the joint portion 215a. Further, the plurality of negative electrodes 211b and the leads 212b are electrically connected at the joint portion 215b.
- the exterior body 251 has a film-like shape and is bent in two so as to sandwich the positive electrode 211a and the negative electrode 211b.
- the exterior body 251 has a bent portion 261, a pair of sealing portions 262, and a sealing portion 263.
- the pair of seal portions 262 are provided so as to sandwich the positive electrode 211a and the negative electrode 211b, and can also be referred to as a side seal.
- the seal portion 263 has a portion that overlaps with the lead 212a and the lead 212b, and can also be called a top seal.
- the exterior body 251 preferably has a wavy shape in which ridge lines 271 and valley lines 272 are alternately arranged at a portion overlapping the positive electrode 211a and the negative electrode 211b. Further, it is preferable that the seal portion 262 and the seal portion 263 of the exterior body 251 are flat.
- FIG. 16B1 is a cross section cut at a portion overlapping the ridge line 271
- FIG. 16B2 is a cross section cut at a portion overlapping the valley line 272.
- 16B1 and 16B2 both correspond to the cross sections of the secondary battery 250 and the positive electrode 211a and the negative electrode 211b in the width direction.
- the distance between the widthwise ends of the positive electrode 211a and the negative electrode 211b, that is, the ends of the positive electrode 211a and the negative electrode 211b and the seal portion 262 is defined as the distance La.
- the positive electrode 211a and the negative electrode 211b are deformed so as to be displaced from each other in the length direction as described later.
- the distance La is too short, the exterior body 251 may be strongly rubbed against the positive electrode 211a and the negative electrode 211b, and the exterior body 251 may be damaged.
- the metal film of the exterior body 251 is exposed, the metal film may be corroded by the electrolytic solution. Therefore, it is preferable to set the distance La as long as possible.
- the distance La is made too large, the volume of the secondary battery 250 will increase.
- the distance La is 0.8 times or more and 3.0 times or less of the thickness t. It is preferably 0.9 times or more and 2.5 times or less, and more preferably 1.0 times or more and 2.0 times or less.
- the distance between the pair of sealing portions 262 is the distance Lb
- the distance Lb is sufficiently larger than the width of the positive electrode 211a and the negative electrode 211b (here, the width Wb of the negative electrode 211b).
- the difference between the distance Lb between the pair of sealing portions 262 and the width Wb of the negative electrode 211b is 1.6 times or more and 6.0 times or less, preferably 1.8 times the thickness t of the positive electrode 211a and the negative electrode 211b. It is preferable to satisfy 5 times or more and 5.0 times or less, more preferably 2.0 times or more and 4.0 times or less.
- FIG. 16C is a cross section including the lead 212a, which corresponds to a cross section in the length direction of the secondary battery 250, the positive electrode 211a, and the negative electrode 211b.
- the bent portion 261 has a space 273 between the end portions of the positive electrode 211a and the negative electrode 211b in the length direction and the exterior body 251.
- FIG. 16D shows a schematic cross-sectional view when the secondary battery 250 is bent.
- FIG. 16D corresponds to the cross section at the cutting line B1-B2 in FIG. 16A.
- the secondary battery 250 When the secondary battery 250 is bent, a part of the exterior body 251 located outside the bend is stretched, and the other part located inside is deformed so as to shrink. More specifically, the portion located outside the exterior body 251 is deformed so that the amplitude of the wave is small and the period of the wave is large. On the other hand, the portion located inside the exterior body 251 is deformed so that the amplitude of the wave is large and the period of the wave is small.
- the positive electrode 211a and the negative electrode 211b are relatively displaced from each other.
- one end of the laminated positive electrode 211a and the negative electrode 211b on the seal portion 263 side is fixed by the fixing member 217, they are displaced so that the closer to the bent portion 261 is, the larger the deviation amount is.
- the stress applied to the positive electrode 211a and the negative electrode 211b is relaxed, and the positive electrode 211a and the negative electrode 211b themselves do not need to expand or contract.
- the secondary battery 250 can be bent without damaging the positive electrode 211a and the negative electrode 211b.
- the space 273 is provided between the positive electrode 211a and the negative electrode 211b and the exterior body 251 so that the positive electrode 211a and the negative electrode 211b located inside when bent do not come into contact with the exterior body 251 and are relative to each other. You can shift to.
- the secondary battery 250 illustrated in FIGS. 16 and 17 is a battery in which the exterior body is not easily damaged, the positive electrode 211a and the negative electrode 211b are not easily damaged, and the battery characteristics are not easily deteriorated even if the secondary battery 250 is repeatedly bent and stretched.
- the positive electrode active material described in the previous embodiment for the positive electrode 211a of the secondary battery 250 By using the positive electrode active material described in the previous embodiment for the positive electrode 211a of the secondary battery 250, a battery having further excellent cycle characteristics can be obtained.
- FIGS. 18A to 18G show an example of mounting a bendable secondary battery in an electronic device described in a part of the third embodiment.
- Electronic devices to which a bendable secondary battery is applied include, for example, television devices (also called televisions or television receivers), monitors for computers, digital cameras, digital video cameras, digital photo frames, mobile phones. Examples include large game machines (also referred to as mobile phones and mobile phone devices), portable game machines, mobile information terminals, sound reproduction devices, and pachinko machines.
- a rechargeable battery with a flexible shape along the inner or outer wall of a house or building, or along the curved surface of the interior or exterior of an automobile.
- FIG. 18A shows an example of a mobile phone.
- the mobile phone 7400 includes an operation button 7403, an external connection port 7404, a speaker 7405, a microphone 7406, and the like, in addition to the display unit 7402 incorporated in the housing 7401.
- the mobile phone 7400 has a secondary battery 7407.
- the secondary battery of one aspect of the present invention it is possible to provide a lightweight and long-life mobile phone.
- FIG. 18B shows a state in which the mobile phone 7400 is curved.
- the secondary battery 7407 provided inside the mobile phone 7400 is also bent.
- the state of the bent secondary battery 7407 is shown in FIG. 18C.
- the secondary battery 7407 is a thin storage battery.
- the secondary battery 7407 is fixed in a bent state.
- the secondary battery 7407 has a lead electrode electrically connected to the current collector.
- the current collector is a copper foil, which is partially alloyed with gallium to improve the adhesion to the active material layer in contact with the current collector, and the reliability of the secondary battery 7407 in a bent state is improved. It has a high composition.
- FIG. 18D shows an example of a bangle type display device.
- the portable display device 7100 includes a housing 7101, a display unit 7102, an operation button 7103, and a secondary battery 7104.
- FIG. 18E shows the state of the bent secondary battery 7104.
- the housing is deformed and the curvature of a part or the whole of the secondary battery 7104 changes.
- the degree of bending at an arbitrary point of the curve is represented by the value of the radius of the corresponding circle, which is called the radius of curvature, and the reciprocal of the radius of curvature is called the curvature.
- a part or all of the main surface of the housing or the secondary battery 7104 changes within the range of the radius of curvature of 40 mm or more and 150 mm or less. High reliability can be maintained as long as the radius of curvature on the main surface of the secondary battery 7104 is in the range of 40 mm or more and 150 mm or less.
- a lightweight and long-life portable display device can be provided.
- FIG. 18F shows an example of a wristwatch-type mobile information terminal.
- the mobile information terminal 7200 includes a housing 7201, a display unit 7202, a band 7203, a buckle 7204, an operation button 7205, an input / output terminal 7206, and the like.
- the mobile information terminal 7200 can execute various applications such as mobile phone, e-mail, text viewing and creation, music playback, Internet communication, and computer games.
- the display surface of the display unit 7202 is provided to be curved, and display can be performed along the curved display surface. Further, the display unit 7202 is provided with a touch sensor and can be operated by touching the screen with a finger or a stylus. For example, the application can be started by touching the icon 7207 displayed on the display unit 7202.
- the operation button 7205 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 7205 can be freely set by the operating system incorporated in the mobile information terminal 7200.
- the personal digital assistant 7200 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 information terminal 7200 is provided with an input / output terminal 7206, and data can be directly exchanged with another information terminal via a connector. It is also possible to charge via the input / output terminal 7206. The charging operation may be performed by wireless power supply without going through the input / output terminal 7206.
- the display unit 7202 of the portable information terminal 7200 has a secondary battery of one aspect of the present invention.
- a lightweight and long-life portable information terminal can be provided.
- the secondary battery 7104 shown in FIG. 18E can be incorporated in a curved state inside the housing 7201 or in a bendable state inside the band 7203.
- the portable information terminal 7200 has a sensor.
- a human body sensor such as a fingerprint sensor, a pulse sensor, a body temperature sensor, a touch sensor, a pressure sensor, an acceleration sensor, or the like is preferably mounted.
- FIG. 18G shows an example of an armband type display device.
- the display device 7300 has a display unit 7304 and has a secondary battery according to an aspect of the present invention. Further, the display device 7300 can be provided with a touch sensor on the display unit 7304, and can also function as a portable information terminal.
- the display surface of the display unit 7304 is curved, and display can be performed along the curved display surface.
- the display device 7300 can change the display status by communication standard short-range wireless communication or the like.
- the display device 7300 is provided with an input / output terminal, and data can be directly exchanged with another information terminal via a connector. It can also be charged via the input / output terminals.
- the charging operation may be performed by wireless power supply without going through the input / output terminals.
- the secondary battery of one aspect of the present invention as the secondary battery of the display device 7300, a lightweight and long-life display device can be provided.
- the secondary battery of one aspect of the present invention as the secondary battery in the daily electronic device, a lightweight and long-life product can be provided.
- daily electronic devices include electric toothbrushes, electric shavers, electric beauty devices, etc.
- the secondary batteries of these products are compact and lightweight with a stick-shaped shape in consideration of user-friendliness.
- a large-capacity secondary battery is desired.
- FIG. 18H is a perspective view of a device also called a cigarette-accommodating smoking device (electronic cigarette).
- the electronic cigarette 7500 is composed of an atomizer 7501 including a heating element, a secondary battery 7504 for supplying electric power to the atomizer, and a cartridge 7502 including a liquid supply bottle and a sensor.
- a protection circuit for preventing overcharging or overdischarging of the secondary battery 7504 may be electrically connected to the secondary battery 7504.
- the secondary battery 7504 shown in FIG. 18H has an external terminal so that it can be connected to a charging device. Since the secondary battery 7504 becomes the tip portion when it is held, it is desirable that the total length is short and the weight is light. Since the secondary battery of one aspect of the present invention has a high capacity and good cycle characteristics, it is possible to provide a compact and lightweight electronic cigarette 7500 that can be used for a long period of time.
- FIGS. 19A and 19B show an example of a tablet terminal that can be folded in half.
- the tablet terminal 9600 shown in FIGS. 19A and 19B has a housing 9630a, a housing 9630b, a movable unit 9640 connecting the housing 9630a and the housing 9630b, a display unit 9631 having a display unit 9631a and a display unit 9631b, and a switch 9625. , Switch 9626 and switch 9627, fastener 9629, operation switch 9628.
- FIG. 19A shows a state in which the tablet terminal 9600 is opened
- FIG. 19B shows a state in which the tablet terminal 9600 is closed.
- the tablet terminal 9600 has a power storage body 9635 inside the housing 9630a and the housing 9630b.
- the power storage body 9635 passes through the movable portion 9640 and is provided over the housing 9630a and the housing 9630b.
- the display unit 9631 can use all or part of the area as the touch panel area, and can input data by touching an image, characters, an input form, or the like including an icon displayed in the area.
- a keyboard button may be displayed on the entire surface of the display unit 9631a on the housing 9630a side, and information such as characters and images may be displayed on the display unit 9631b on the housing 9630b side.
- the keyboard may be displayed on the display unit 9631b on the housing 9630b side, and information such as characters and images may be displayed on the display unit 9631a on the housing 9630a side.
- the keyboard display switching button on the touch panel may be displayed on the display unit 9631, and the keyboard may be displayed on the display unit 9631 by touching the button with a finger or a stylus.
- the switch 9625 to the switch 9627 may be not only an interface for operating the tablet terminal 9600 but also an interface capable of switching various functions.
- at least one of the switch 9625 to the switch 9627 may function as a switch for switching the power on / off of the tablet terminal 9600.
- at least one of the switch 9625 to the switch 9627 may have a function of switching the display direction such as vertical display or horizontal display, or a function of switching between black and white display and color display.
- at least one of the switch 9625 to the switch 9627 may have a function of adjusting the brightness of the display unit 9631.
- the brightness of the display unit 9631 can be optimized according to the amount of external light during use detected by the optical sensor built in the tablet terminal 9600.
- the tablet terminal may incorporate not only an optical sensor but also another detection device such as a gyro, an acceleration sensor, or other sensor for detecting inclination.
- FIG. 19A shows an example in which the display areas of the display unit 9631a on the housing 9630a side and the display unit 9631b on the housing 9630b side are almost the same, but the display areas of the display unit 9631a and the display unit 9631b are particularly different. It is not limited, and one size and the other size may be different, and the display quality may be different. For example, one may be a display panel capable of displaying a higher definition than the other.
- FIG. 19B shows a state in which the tablet terminal 9600 is closed in half, and the tablet terminal 9600 has a charge / discharge control circuit 9634 including a housing 9630, a solar cell 9633, and a DCDC converter 9636. Further, as the power storage body 9635, the power storage body according to one aspect of the present invention is used.
- the tablet terminal 9600 can be folded in half, it can be folded so that the housing 9630a and the housing 9630b are overlapped when not in use. Since the display unit 9631 can be protected by folding, the durability of the tablet terminal 9600 can be improved. Further, since the power storage body 9635 using the secondary battery of one aspect of the present invention has a high capacity and good cycle characteristics, it is possible to provide a tablet terminal 9600 that can be used for a long time over a long period of time.
- the tablet terminal 9600 shown in FIGS. 19A and 19B displays a function for displaying various information (still image, moving image, text image, etc.), a calendar, a date, a time, and the like on the display unit. It can have a function, a touch input function for touch input operation or editing of information displayed on a display unit, a function for controlling processing by various software (programs), and the like.
- Electric power can be supplied to a touch panel, a display unit, a video signal processing unit, or the like by a solar cell 9633 mounted on the surface of the tablet terminal 9600.
- the solar cell 9633 can be provided on one side or both sides of the housing 9630, and can be configured to efficiently charge the power storage body 9635.
- a lithium ion battery is used as the power storage body 9635, there is an advantage that the size can be reduced.
- FIG. 19C shows the solar cell 9633, the storage body 9635, the DCDC converter 9636, the converter 9637, the switches SW1, SW2 and SW3, and the display unit 9631.
- the storage body 9635, the DCDC converter 9636, the converter 9637, the switches SW1 to SW3 Is the location corresponding to the charge / discharge control circuit 9634 shown in FIG. 19B.
- the electric power generated by the solar cell is stepped up or down by the DCDC converter 9636 so as to be a voltage for charging the storage body 9635. Then, when the electric power from the solar cell 9633 is used for the operation of the display unit 9631, the switch SW1 is turned on, and the converter 9637 boosts or lowers the voltage required for the display unit 9631. Further, when the display is not performed on the display unit 9631, the SW1 may be turned off and the SW2 may be turned on to charge the power storage body 9635.
- the solar cell 9633 is shown as an example of the power generation means, but is not particularly limited, and the storage body 9635 is charged by another power generation means such as a piezoelectric element (piezo element) or a thermoelectric conversion element (Peltier element). It may be.
- a non-contact power transmission module that wirelessly (non-contactly) transmits and receives power for charging, or a configuration in which other charging means are combined may be used.
- FIG. 20 shows an example of another electronic device.
- the display device 8000 is an example of an electronic device using the secondary battery 8004 according to one aspect of the present invention.
- the display device 8000 corresponds to a display device for receiving TV broadcasts, and includes a housing 8001, a display unit 8002, a speaker unit 8003, a secondary battery 8004, and the like.
- the secondary battery 8004 according to one aspect of the present invention is provided inside the housing 8001.
- the display device 8000 can be supplied with electric power from a commercial power source, or can use the electric power stored in the secondary battery 8004. Therefore, even when the power cannot be supplied from the commercial power supply due to a power failure or the like, the display device 8000 can be used by using the secondary battery 8004 according to one aspect of the present invention as an uninterruptible power supply.
- the display unit 8002 includes a light emitting device having a light emitting element such as a liquid crystal display device and an organic EL element in each pixel, an electrophoretic display device, a DMD (Digital Micromirror Device), a PDP (Plasma Display Panel), and a FED (Field Emission Display). ), Etc., a semiconductor display device can be used.
- a light emitting element such as a liquid crystal display device and an organic EL element in each pixel
- an electrophoretic display device such as a liquid crystal display device and an organic EL element in each pixel
- DMD Digital Micromirror Device
- PDP Plasma Display Panel
- FED Field Emission Display
- the display device includes all information display devices such as those for receiving TV broadcasts, those for personal computers, and those for displaying advertisements.
- the stationary lighting device 8100 is an example of an electronic device using the secondary battery 8103 according to one aspect of the present invention.
- the lighting device 8100 includes a housing 8101, a light source 8102, a secondary battery 8103, and the like.
- FIG. 20 illustrates a case where the secondary battery 8103 is provided inside the ceiling 8104 in which the housing 8101 and the light source 8102 are installed, but the secondary battery 8103 is provided inside the housing 8101. It may have been done.
- the lighting device 8100 can be supplied with electric power from a commercial power source, or can use the electric power stored in the secondary battery 8103. Therefore, even when the power cannot be supplied from the commercial power supply due to a power failure or the like, the lighting device 8100 can be used by using the secondary battery 8103 according to one aspect of the present invention as an uninterruptible power supply.
- FIG. 20 illustrates the stationary lighting device 8100 provided on the ceiling 8104
- the secondary battery according to one aspect of the present invention includes, for example, a side wall 8105, a floor 8106, a window 8107, etc. other than the ceiling 8104. It can be used for a stationary lighting device provided in the above, or for a desktop lighting device or the like.
- an artificial light source that artificially obtains light by using electric power can be used.
- an incandescent lamp, a discharge lamp such as a fluorescent lamp, and a light emitting element such as an LED or an organic EL element are examples of the artificial light source.
- the air conditioner having the indoor unit 8200 and the outdoor unit 8204 is an example of an electronic device using the secondary battery 8203 according to one aspect of the present invention.
- the indoor unit 8200 has a housing 8201, an air outlet 8202, a secondary battery 8203, and the like.
- FIG. 20 illustrates the case where the secondary battery 8203 is provided in the indoor unit 8200, the secondary battery 8203 may be provided in the outdoor unit 8204. Alternatively, the secondary battery 8203 may be provided in both the indoor unit 8200 and the outdoor unit 8204.
- the air conditioner can be supplied with electric power from a commercial power source, or can use the electric power stored in the secondary battery 8203.
- the secondary battery 8203 when the secondary battery 8203 is provided in both the indoor unit 8200 and the outdoor unit 8204, the secondary battery 8203 according to one aspect of the present invention is provided even when power cannot be supplied from a commercial power source due to a power failure or the like.
- the power supply as an uninterruptible power supply, the air conditioner can be used.
- FIG. 20 illustrates a separate type air conditioner composed of an indoor unit and an outdoor unit
- the integrated air conditioner having the functions of the indoor unit and the outdoor unit in one housing may be used.
- a secondary battery according to one aspect of the present invention can also be used.
- the electric refrigerator / freezer 8300 is an example of an electronic device using the secondary battery 8304 according to one aspect of the present invention.
- the electric freezer / refrigerator 8300 has a housing 8301, a refrigerator door 8302, a freezer door 8303, a secondary battery 8304, and the like.
- the secondary battery 8304 is provided inside the housing 8301.
- the electric refrigerator / freezer 8300 can be supplied with electric power from a commercial power source, or can use the electric power stored in the secondary battery 8304. Therefore, even when the power cannot be supplied from the commercial power source due to a power failure or the like, the electric refrigerator-freezer 8300 can be used by using the secondary battery 8304 according to one aspect of the present invention as an uninterruptible power supply.
- high-frequency heating devices such as microwave ovens and electronic devices such as electric rice cookers require high electric power in a short time. Therefore, by using the secondary battery according to one aspect of the present invention as an auxiliary power source for assisting the electric power that cannot be covered by the commercial power source, it is possible to prevent the breaker of the commercial power source from being tripped when the electronic device is used. ..
- the power usage rate the ratio of the amount of power actually used (called the power usage rate) to the total amount of power that can be supplied by the commercial power supply source.
- the power usage rate By storing power in the next battery, it is possible to suppress an increase in the power usage rate outside the above time zone.
- the electric freezer / refrigerator 8300 electric power is stored in the secondary battery 8304 at night when the temperature is low and the refrigerating room door 8302 and the freezing room door 8303 are not opened / closed. Then, in the daytime when the temperature rises and the refrigerating room door 8302 and the freezing room door 8303 are opened and closed, the power usage rate in the daytime can be suppressed low by using the secondary battery 8304 as an auxiliary power source.
- the cycle characteristics of the secondary battery can be improved and the reliability can be improved. Further, according to one aspect of the present invention, it is possible to obtain a high-capacity secondary battery, thereby improving the characteristics of the secondary battery, and thus reducing the size and weight of the secondary battery itself. it can. Therefore, by mounting the secondary battery, which is one aspect of the present invention, in the electronic device described in the present embodiment, it is possible to obtain a longer life and lighter electronic device. This embodiment can be implemented in combination with other embodiments as appropriate.
- HV hybrid vehicle
- EV electric vehicle
- PSV plug-in hybrid vehicle
- FIG. 21 illustrates a vehicle using a secondary battery, which is one aspect of the present invention.
- the automobile 8400 shown in FIG. 21A 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. By using one aspect of the present invention, a vehicle having a long cruising range can be realized.
- the automobile 8400 has a secondary battery.
- the modules of the secondary battery shown in FIGS. 6C and 6D may be used side by side with respect to the floor portion in the vehicle.
- a battery pack in which a plurality of secondary batteries shown in FIG. 9 are combined may be installed on the floor portion in the vehicle.
- the secondary battery can not only drive the electric motor 8406, but also supply electric power to a light emitting device such as a headlight 8401 and a room light (not shown).
- the secondary battery can supply electric power to display devices such as speedometers and tachometers of the automobile 8400.
- the secondary battery can supply electric power to a semiconductor device such as a navigation system included in the automobile 8400.
- the automobile 8500 shown in FIG. 21B can be charged by receiving electric power from an external charging facility by a plug-in method, a non-contact power supply method, or the like to the secondary battery of the automobile 8500.
- FIG. 21B shows a state in which the secondary battery 8024 mounted on the automobile 8500 is being charged from the ground-mounted charging device 8021 via the cable 8022.
- the charging method, connector standards, etc. may be appropriately performed by a predetermined method such as CHAdeMO (registered trademark) or combo.
- the charging device 8021 may be a charging station provided in a commercial facility or a household power source.
- the plug-in technology can charge the secondary battery 8024 mounted on the automobile 8500 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 the vehicle and supply 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, it is possible to charge the battery not only while the vehicle is stopped but also while the vehicle is running. Further, electric power may be transmitted and received between vehicles by using this contactless power supply method. Further, 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 to supply power in such a non-contact manner.
- FIG. 21C is an example of a two-wheeled vehicle using the secondary battery of one aspect of the present invention.
- the scooter 8600 shown in FIG. 21C includes a secondary battery 8602, a side mirror 8601, and a turn signal 8603.
- the secondary battery 8602 can supply electricity to the turn signal 8603.
- the scooter 8600 shown in FIG. 21C can store the secondary battery 8602 in the storage under the seat 8604.
- the secondary battery 8602 can be stored in the under-seat storage 8604 even if the under-seat storage 8604 is small.
- the secondary battery 8602 is removable, and when charging, the secondary battery 8602 may be carried indoors, charged, and stored before traveling.
- the cycle characteristics of the secondary battery are improved, and the capacity of the secondary battery can be increased. Therefore, the secondary battery itself can be made smaller and lighter. If the secondary battery itself can be made smaller and lighter, it will contribute to the weight reduction of the vehicle, and thus the cruising range can be improved. Further, the secondary battery mounted on the vehicle can also be used as a power supply source other than the vehicle. In this case, for example, it is possible to avoid using a commercial power source during peak power demand. Avoiding the use of commercial power during peak power demand can contribute to energy savings and reduction of carbon dioxide emissions. Further, if the cycle characteristics are good, the secondary battery can be used for a long period of time, so that the amount of rare metals such as cobalt used can be reduced.
- This embodiment can be implemented in combination with other embodiments as appropriate.
- FIG. 22A shows an example of a wearable device.
- the wearable device uses a secondary battery as a power source. Further, in order to improve the water resistance of water in daily use or outdoor use by the user, a wearable device capable of wireless charging as well as wired charging in which the connector portion to be connected is exposed is desired.
- the spectacle-type device 400 can be mounted on a glasses-type device 400 as shown in FIG. 22A.
- the spectacle-type device 400 has a frame 400a and a display unit 400b.
- By mounting the secondary battery on the temple portion of the curved frame 400a it is possible to obtain a spectacle-type device 400 that is lightweight, has a good weight balance, and has a long continuous use time.
- the headset-type device 401 has at least a microphone unit 401a, a flexible pipe 401b, and an earphone unit 401c.
- a secondary battery can be provided in the flexible pipe 401b or in the earphone portion 401c.
- the secondary battery 402b can be provided in the thin housing 402a of the device 402.
- the secondary battery 403b can be provided in the thin housing 403a of the device 403.
- the belt-type device 406 has a belt portion 406a and a wireless power supply receiving portion 406b, and a secondary battery can be mounted inside the belt portion 406a.
- the wristwatch-type device 405 has a display unit 405a and a belt unit 405b, and a secondary battery can be provided on the display unit 405a or the belt unit 405b.
- the display unit 405a can display not only the time but also various information such as incoming e-mails and telephone calls.
- the wristwatch type device 405 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 accumulate data on the amount of exercise and health of the user and use it to maintain health.
- the wristwatch-type device 405 shown in FIG. 22A will be described in detail below.
- FIG. 22B shows a perspective view of the wristwatch-type device 405 removed from the arm.
- FIG. 22C shows a state in which the secondary battery 913 is built in.
- the secondary battery 913 is provided at a position overlapping the display unit 405a, and is compact and lightweight.
- This embodiment can be implemented in combination with other embodiments as appropriate.
- the substance used for producing the positive electrode active material was inspected by using the inspection by DSC described in the previous embodiment.
- Sample 1 which is a mixture of substance 91 and substance 92, was prepared and inspected.
- Lithium fluoride was used as the substance 91
- magnesium fluoride was used as the substance 92.
- the molar ratio of lithium contained in lithium fluoride was set to be 0.33 times that of magnesium contained in magnesium fluoride.
- DSC was used as the inspection method.
- substances 91 to 94 were inspected using the method shown in FIG. 1C.
- Lithium fluoride was used as the substance 91
- magnesium fluoride was used as the substance 92
- nickel hydroxide was used as the substance 93
- aluminum hydroxide was used as the substance 94.
- a mixture of substance 91, substance 92, substance 93 and substance 94 is referred to as Sample 2.
- the molar ratio of lithium contained in lithium fluoride is 0.33 times that of magnesium contained in magnesium fluoride, nickel contained in nickel hydroxide is 0.5 times, and aluminum contained in aluminum hydroxide is 0.5 times. I made it double.
- DSC was used as the inspection method.
- the temperature (Temperature) -heat flow (Heat Flow) curves by DSC of Sample 1 and Sample 2 are shown in FIG. 23A. From the results of Sample 1, it is considered that a peak suggesting an endothermic reaction was observed near 730 ° C., and a eutectic reaction of lithium fluoride and magnesium fluoride occurred. On the other hand, in Sample 2, a peak suggesting an endothermic reaction is not remarkably observed near 730 ° C. Therefore, either substance 93 or substance 94 may easily inhibit the endothermic reaction.
- FIG. 23B shows the differential waveform of the temperature-heat flow curve of the DSP of Sample 1
- FIG. 23C shows the differential waveform of the temperature-heat flow curve of the DSC of Sample 2.
- Sample 1 a maximum point and a minimum point were observed near 730 ° C. where the peak was observed on the temperature-heat flow curve.
- Sample 2 the peak was not observed remarkably or was extremely weak.
- Sample 3 the mixture of Sample 1 and nickel hydroxide was designated as Sample 3
- Sample 4 the mixture of Sample 1 and aluminum hydroxide was designated as Sample 4.
- DSC was performed for each sample.
- the molar ratio of nickel contained in nickel hydroxide was set to 0.5 times the molar ratio of magnesium contained in magnesium fluoride.
- the molar ratio of aluminum contained in the aluminum hydroxide was set to 0.5 times the molar ratio of magnesium contained in magnesium fluoride.
- the differential waveform of the DSC of Sample 3 is shown in FIG. 24A
- the differential waveform of the DSC of Sample 4 is shown in FIG. 24B, respectively. It can be seen that in Sample 4, the peak suggesting endothermic reaction becomes smaller in the vicinity of 730 ° C. as compared with Sample 3.
- FIG. 25 shows the differential waveform of DSC of Sample 5. It was found that by adding lithium cobalt oxide, the peak suggesting endothermic reaction near 730 ° C observed by DSC shifts to the positive side by about 100 ° C.
- a positive electrode active material was prepared using the manufacturing method described in the previous embodiment, and a secondary battery was manufactured in order to evaluate the characteristics of the positive electrode using the prepared positive electrode active material.
- a positive electrode active material was prepared by using the method shown in FIG. 2B. More specifically, the method shown in FIG. 3 was used. Lithium fluoride was used as the substance 91, and magnesium fluoride was used as the substance 92. For the molar ratio of substance 91 to substance 92, refer to Sample 1. The weight of the powder of the mixture 904 was 30 g.
- a positive electrode active material was prepared by using the method shown in FIG. 2A.
- Lithium fluoride was used as the substance 91
- magnesium fluoride was used as the substance 92
- nickel hydroxide was used as the substance 93
- aluminum hydroxide was used as the substance 94.
- the molar ratio of the substance 91 to the substance 92 refer to Sample 1 so that the molar ratio of nickel possessed by nickel hydroxide is 0.5 times the molar ratio of magnesium possessed by magnesium fluoride, and aluminum hydroxide is used.
- the molar ratio of aluminum possessed was adjusted to be 0.5 times the molar ratio of magnesium possessed by magnesium fluoride.
- the sum of the weights of the powders of the substance 91 to the substance 94 was 30 g for Cell 2 and 2.4 g for Cell 3.
- CR2032 type coin-type secondary batteries were produced as Cell 1, Cell 2, and Cell 3.
- Lithium metal was used for the opposite electrode.
- LiPF 6 lithium hexafluorophosphate
- EC ethylene carbonate
- DEC diethyl carbonate
- VC vinylene carbonate
- Polypropylene with a thickness of 25 ⁇ m was used for the separator.
- the positive electrode can and the negative electrode can those made of stainless steel (SUS) were used.
- the substance used for producing the positive electrode active material was inspected by using the XRD inspection described in the previous embodiment.
- the sample 2, sample 3 and sample 4 produced in the previous example were each subjected to a heat treatment at 850 ° C. under an oxygen atmosphere, and then evaluated by XRD.
- the spectrum of XRD is shown in FIGS. 27, 28, 29 and 30.
- the vertical axis of FIGS. 27 to 30 shows the intensity of the spectrum (INTERNSITY), and the horizontal axis shows 2 ⁇ .
- the graphs of FIGS. 27 to 30 have different ranges of 2 ⁇ shown on the horizontal axis.
- Bruker's D8ADVANCE was used as the XRD measurement.
- the X-ray output is 40 kV, 40 mA
- the scanning angle is in the range of 15 ° to 90 °
- the measurement interval is 0.01 °
- the scanning speed is 0.5 sec / step
- the sample is at 15 rpm. It was measured while rotating.
- the obtained XRD pattern was obtained from DIFFRAC. Background removal and K ⁇ 2 removal were performed using EVA (XRD data analysis software manufactured by Bruker).
- Table 1 shows the peak position (peak position), half width (half width), and peak intensity (peak intensity) of the main peaks based on the obtained XRD results of Sample 2.
- the peak position is the maximum value of the peak.
- an intensity of about 37 was observed at a position of 37.03 °.
- 2 ⁇ may correspond to MgAl (2-x) Ni x O 4 (x is 0 or more and 2 or less) having a spinel type structure such as 19.08 °, 31.44 °, 59.60 °, etc.
- a peak was observed.
- these peaks had peak intensities of 0.05 times, 0.04 times, and 0.06 times, respectively, as compared with the peak of 40.43 °.
- FIGS. 43A, 43B, 44A and 44B The spectra of XRD are shown in FIGS. 43A, 43B, 44A and 44B.
- the vertical axis of FIGS. 43A, 43B, 44A and 44B shows the intensity of the spectrum (INTENSITY), and the horizontal axis shows 2 ⁇ .
- the graphs of FIGS. 43A, 43B, 44A and 44B have different ranges of 2 ⁇ shown on the horizontal axis.
- Bruker's D8ADVANCE was used as the XRD measurement.
- the X-ray output is 40 kV, 40 mA
- the scanning angle is in the range of 15 ° to 90 °
- the measurement interval is 0.01 °
- the scanning speed is 5 sec / step
- the sample is rotated at 15 rpm. While measuring.
- the obtained XRD pattern was obtained from DIFFRAC. Background removal and K ⁇ 2 removal were performed using EVA (XRD data analysis software manufactured by Bruker).
- Table 2 shows the peak position (peak position), full width at half maximum (half width), and peak intensity (peak intensity) of the main peaks.
- the peak position is the maximum value of the peak.
- the peak suggested to be due to the spinel-type structure suggested by the XRD of Sample 2 was not clearly observed.
- the peak caused by the metal oxide 95 is strong, and it may be difficult to observe the peak suggested to be caused by the spinel-type structure.
- a positive electrode active material is produced using the method shown in FIG. 2B, more specifically, the method shown in FIG. 3, and its initial charge / discharge characteristics, high voltage cycle characteristics, high temperature cycle characteristics, and continuous charging characteristics are exhibited. evaluated.
- the positive electrode active material produced in such a manner was designated as Sample 6.
- the first annealing (FIG. 3S34) was performed at 900 ° C. for 20 hours, and the second annealing (FIG. 3S56) was performed at 850 ° C. for 10 hours, both in an oxygen atmosphere (oxygen gas flow rate 10 L / min).
- Magnesium fluoride and lithium fluoride were added to lithium cobalt oxide, and the positive electrode active material annealed once was designated as Sample 7.
- the number of atoms of cobalt contained in lithium cobalt oxide is 1, the molar concentration of magnesium is 0.005.
- Annealing was carried out at 900 ° C. for 20 hours in an oxygen atmosphere (purging the inside of the heating furnace with oxygen gas before annealing).
- Lithium cobalt oxide which was not annealed with the addition of other elements, was designated as Sample 8 (comparative example).
- a coin cell was prepared using the positive electrode active materials of Sample 6 to Sample 8.
- the mixing ratio of the positive electrode active material, the conductive auxiliary agent and the binder, the electrolyte, the electrolytic solution, the separator, the positive electrode can and the negative electrode can were the same as in Example 2.
- FIG. 31A shows the cycle characteristics at 25 ° C. and a charging voltage of 4.60 V.
- FIG. 31B shows the cycle characteristics at 45 ° C. and a charging voltage of 4.60 V.
- FIG. 32A shows the cycle characteristics at 25 ° C. and a charging voltage of 4.62 V.
- FIG. 32B shows the cycle characteristics at 45 ° C. and a charging voltage of 4.62 V.
- FIG. 33A shows the cycle characteristics at 25 ° C. and a charging voltage of 4.64 V.
- FIG. 33B shows the cycle characteristics at 45 ° C. and a charging voltage of 4.64 V.
- FIG. 34A shows the cycle characteristics at 25 ° C. and a charging voltage of 4.66 V.
- FIG. 34B shows the cycle characteristics at 45 ° C. and a charging voltage of 4.66 V.
- Table 3 shows the initial charge capacity and the initial discharge capacity at 25 ° C. or 45 ° C. at each charging voltage. It is the volume per weight of the active material, and the unit is mAh / g.
- Sample 6 and Sample 7 showed very good cycle characteristics as compared with Sample 8 which was not added and annealed with other elements. At 25 ° C. and a charging voltage of 4.6 V, there was no significant difference between Sample 6 and Sample 7, but the cycle characteristics of Sample 6 tended to be better as the temperature and voltage increased.
- FIG. 35A shows the cycle characteristics of each temperature of Sample 6.
- FIG. 35B shows the initial charge / discharge curve and the 50th charge / discharge curve at 50 ° C. and a charging voltage of 4.60 V.
- FIG. 36A shows the cycle characteristics of each temperature of Sample 7.
- FIG. 36B shows the initial charge / discharge curve and the 50th charge / discharge curve at 50 ° C. and a charging voltage of 4.60 V.
- FIG. 37A shows the cycle characteristics of each temperature of Sample 8.
- FIG. 37B shows the initial charge / discharge curve and the 50th charge / discharge curve at 50 ° C. and a charging voltage of 4.60 V.
- the initial discharge capacity is 220.0 mA / g
- the discharge capacity at the 50th cycle is 204.0 mA / g
- the reduction rate of the discharge capacity is as good as 8% or less.
- Met At a charging voltage of 4.6 V and 50 ° C., the initial discharge capacity was 223.1 mA / g
- the discharge capacity at the 50th cycle was 191.9 mA / g
- the rate of decrease in the discharge capacity was as good as 14% or less.
- the rate of decrease is a number representing the amount of decrease in the capacity in the desired cycle from the discharge capacity in the first cycle, where the discharge capacity in the first cycle is 100%.
- the continuous charging test is a test in which a secondary battery is continuously charged at a constant voltage for a long time to evaluate the stability and safety of the battery.
- the first charge / discharge was performed at CCCV (38 mA / g, 4.5 V, termination current 4 mA / g) and discharge at CC (38 mA / g, termination voltage 3.0 V) at 25 ° C.
- Continuous charging was performed at CCCV (96 mA / g, 4.60 V, 4.62 V, 4.64 V or 4.66 V), 60 ° C. The measurement of the test was up to 250 hours.
- FIG. 38A to 38C are the results of the voltage of 4.60V, the horizontal axis shows the charging time, and the vertical axis shows the voltage or current.
- FIG. 38A shows the results of the continuous charging test of Sample 6
- FIG. 38B shows the results of Simple 7
- FIG. 38C shows the results of the continuous charging test of Sample 8.
- FIG. 39A to 39C are the results of the voltage of 4.62V, the horizontal axis represents the charging time, and the vertical axis represents the voltage or current. Similarly, FIG. 39A shows the results of the continuous charging test of Sample 6, FIG. 39B shows the results of the sample 7, and FIG. 39C shows the results of the continuous charging test of Sample 8.
- FIG. 40A to 40C are the results of the voltage of 4.64V, the horizontal axis shows the charging time, and the vertical axis shows the voltage or current. Similarly, FIG. 40A shows the results of the continuous charging test of Sample 6, FIG. 40B shows the results of Simple 7, and FIG. 40C shows the results of the continuous charging test of Sample 8.
- FIG. 41A to 41C are the results of the voltage of 4.66V, the horizontal axis represents the charging time, and the vertical axis represents the voltage or current. Similarly, FIG. 41A shows the results of the continuous charging test of Sample 6, FIG. 41B shows the results of the sample 7, and FIG. 41C shows the results of the continuous charging test of Sample 8.
- Sample 8 as a comparative example showed relatively stable continuous charging characteristics at 4.6 V, whereas it was considered to be due to a short circuit within 200 hours at 4.62 V or higher. The current rise was observed.
- Sample 6 showed stable continuous charging characteristics as the voltage increased, and it was clarified that the safety was extremely high even under the high temperature of 60 ° C. and the high voltage of 4.62V or more.
- the durability time of the secondary battery was determined from FIGS. 38 to 41.
- the endurance time will be described with reference to FIG. 42.
- the horizontal axis of FIG. 42 shows the charging time, and the vertical axis shows the voltage or current.
- the endurance time TE is obtained by subtracting the CC charge completion time T F from the short circuit time T S.
- Short time T S is the approximate straight line L1 of the period during which maintains a stable low current after CV charging initiation, an approximate straight line L2 period current rise seen to be due to short circuit is occurring, the time and the intersection P of did.
- Table 4 shows the durability times of Samples 6 to 8. The unit is time.
- the endurance time of Sample 6 exceeded 200 hours under all conditions.
- the endurance time exceeded 250 hours at charging voltages of 4.62V, 4.64V and 4.66V, indicating that safety is extremely high even at high temperatures and high voltages.
Abstract
Description
図2A、図2B、図2Cは、正極活物質の作製方法を説明する図である。
図3は、正極活物質の作製方法を説明する図である。
図4は、正極活物質の作製方法を説明する図である。
図5A、図5B、図5Cは、コイン型二次電池を説明する図である。
図6A、図6B、図6C、図6Dは、円筒型二次電池を説明する図である。
図7A、図7Bは、二次電池の例を説明する図である。
図8A、図8B、図8C、図8Dは、二次電池の例を説明する図である。
図9A、図9Bは、二次電池の例を説明する図である。
図10は、二次電池の例を説明する図である。
図11A、図11B、図11Cは、ラミネート型の二次電池を説明する図である。
図12A、図12Bは、ラミネート型の二次電池を説明する図である。
図13は、二次電池の外観を示す図である。
図14は、二次電池の外観を示す図である。
図15A、図15B、図15Cは、二次電池の作製方法を説明する図である。
図16A、図16B1、図16B2、図16C、図16Dは、曲げることのできる二次電池を説明する図である。
図17A、図17Bは、曲げることのできる二次電池を説明する図である。
図18A、図18B、図18C、図18D、図18E、図18F、図18G、図18Hは、電子機器の一例を説明する図である。
図19A、図19B、図19Cは、電子機器の一例を説明する図である。
図20は、電子機器の一例を説明する図である。
図21A、図21B、図21Cは、車両の一例を説明する図である。
図22A、図22B、図22Cは、電子機器の一例を説明する図である。
図23A、図23B、図23Cは、DSCを用いた評価結果を示す図である。
図24A、図24Bは、DSCを用いた評価結果を示す図である。
図25は、DSCを用いた評価結果を示す図である。
図26は、二次電池のサイクル特性を示す図である。
図27は、XRDの評価結果を示す図である。
図28は、XRDの評価結果を示す図である。
図29は、XRDの評価結果を示す図である。
図30は、XRDの評価結果を示す図である。
図31Aおよび図31Bは二次電池の充電電圧4.60Vにおけるサイクル特性を示す図である。
図32Aおよび図32Bは、二次電池の充電電圧4.62Vにおけるサイクル特性を示す図である。
図33Aおよび図33Bは、二次電池の充電電圧4.64Vにおけるサイクル特性を示す図である。
図34Aおよび図34Bは、二次電池の充電電圧4.66Vにおけるサイクル特性を示す図である。
図35AはSample6を用いた二次電池のサイクル特性を示す図である。図35BはSample6を用いた二次電池の50℃、充電電圧4.60Vにおける初回充放電曲線と50回目の充放電曲線を示す図である。
図36AはSample7を用いた二次電池のサイクル特性を示す図である。図36BはSample7を用いた二次電池の50℃、充電電圧4.60Vにおける初回充放電曲線と50回目の充放電曲線を示す図である。
図37AはSample8を用いた二次電池のサイクル特性を示す図である。図37BはSample8を用いた二次電池の50℃、充電電圧4.60Vにおける初回充放電曲線と50回目の充放電曲線を示す図である。
図38A乃至図38Cは二次電池の電圧4.60Vにおける連続充電特性を示す図である。
図39A乃至図39Cは二次電池の電圧4.62Vにおける連続充電特性を示す図である。
図40A乃至図40Cは二次電池の電圧4.64Vにおける連続充電特性を示す図である。
図41A乃至図41Cは二次電池の電圧4.66Vにおける連続充電特性を示す図である。
図42は連続充電試験における耐久時間について説明する図である。
図43Aおよび図43Bは、XRDの評価結果を示す図である。
図44Aおよび図44Bは、XRDの評価結果を示す図である。
本実施の形態では、本発明の一態様の正極活物質の作製方法等について説明する。
図1Aには物質91と物質92の反応を、DSC(示差走査熱量測定:Differential scanning calorimetry)を用いて検査する例を示す。ここでは、物質91はアルカリ金属Aを有するハロゲン化合物であり、物質92は元素Xを有する化合物である。
図1Bあるいは図1Cに示す検査としてXRDを行ってもよい。XRDにおいて例えば、物質92に含まれる元素Xと、物質93または/および物質94に含まれる金属元素の一以上と、を含む化合物の存在が示唆される場合には、物質91と物質92の共融反応が顕著に阻害されると判断する。なお、検査においてはまず、600℃以上950℃以下の温度範囲、かつ1時間以上100時間以下の範囲で加熱を行い、その後、XRD評価を行う。
図2A、図2Bおよび図2Cには、図1で述べた物質91、物質92、物質93、物質94および金属酸化物95を用いて本発明の一態様の正極活物質を作製する方法の一例を示す。
図2Bに示す作製方法の一例を図3に示す。図3に示す作製方法においては、アルカリ金属Aおよび遷移金属を有する金属酸化物として、アルカリ金属およびコバルトを有する金属酸化物を用いる場合の例を示す。また、元素Xを有する化合物として、マグネシウムを有する化合物を用いる場合の例を示す。
図3のステップS11に示すように、まず混合物902の材料を準備する。図3では、アルカリ金属Aを有するハロゲン化合物としてフッ化リチウムLiFを用意し、マグネシウムを有する化合物としてフッ化マグネシウムMgF2を用意することとする。フッ化リチウムLiFとフッ化マグネシウムMgF2は、LiF:MgF2=65:35(モル比)程度で混合すると混合物の融点を下げる効果が最も高くなる(非特許文献4)。一方、フッ化リチウムが多くなると、リチウムが過剰になりすぎサイクル特性が悪化する懸念がある。そのため、フッ化リチウムLiFとフッ化マグネシウムMgF2のモル比は、LiF:MgF2=x:1(0≦x≦1.9)であることが好ましく、LiF:MgF2=x:1(0.1≦x≦0.5)がより好ましく、LiF:MgF2=x:1(x=0.33近傍)がさらに好ましい。なお本明細書等において近傍とは、その値の0.9倍より大きく1.1倍より小さい値とする。
次にステップS12において、上記の混合物902の材料を混合および粉砕する。混合は乾式または湿式で行うことができるが、湿式はより小さく粉砕することができるため好ましい。混合には例えばボールミル、ビーズミル等を用いることができる。ボールミルを用いる場合は、例えばメディアとしてジルコニアボールを用いることが好ましい。この混合および粉砕工程を十分に行い、混合物902を微粉化することが好ましい。
ステップS13において、上記で混合、粉砕した材料を回収し、ステップS14において、混合物902を得る。
次にステップS25において、アルカリ金属Aおよびコバルトを有する金属酸化物として、金属酸化物95を準備する。金属酸化物95は、アルカリ金属Aを有する材料とコバルトを有する材料の混合物を焼成して得ることができる。あるいはあらかじめ、合成された金属酸化物を用いてもよい。
次にステップS31において、混合物902と、金属酸化物95と、を混合する。金属酸化物95のコバルトの原子数TMと、混合物902が有するマグネシウムの原子数MgMix1との比は、TM:MgMix1=1:y(0.005≦y≦0.05)であることが好ましく、TM:MgMix1=1:y(0.007≦y≦0.04)であることがより好ましく、TM:MgMix1=1:0.02程度がさらに好ましい。
次にステップS32において、上記で混合した材料を回収し、ステップS33において混合物903を得る。
次にステップS34において、混合物903をアニールする。
次にステップS35において、上記でアニールした材料を回収し、ステップS36において、混合物904を得る。
次にステップS41において、金属M源を準備する。金属Mがアルミニウムの場合には例えば、コバルト酸リチウムが有するコバルトの原子数を1とし、金属源が有するアルミニウムのモル濃度が0.001倍以上0.02倍以下となればよい。金属Mがニッケルの場合には例えば、コバルト酸リチウムが有するコバルトの原子数を1とし、金属源が有するニッケルのモル濃度が0.001倍以上0.02倍以下となればよい。金属Mがアルミニウムおよびニッケルの場合には例えば、コバルト酸リチウムが有するコバルトの原子数を1とし、金属源が有するアルミニウムのモル濃度が0.001倍以上0.02倍以下、かつ、金属源が有するニッケルのモル濃度が0.001倍以上0.02倍以下となればよい。
次にステップS42において、金属源および溶媒を混合および粉砕する。混合および粉砕については、ステップS12等の条件を参照することができる。
次にステップS43において、ステップS42で粉砕した金属M源を回収する。
次にステップS44において、ステップS41で準備された金属M源が有する金属と異なる金属を有する金属M源を準備する。後のステップS45において、湿式で混合を行う場合には、ステップS44において溶媒も準備する。図3のステップS44では一例として、金属源として水酸化アルミニウムを準備し、溶媒としてアセトンを準備する。
次にステップS45において、金属源および溶媒を混合および粉砕する。混合および粉砕については、ステップS12等の条件を参照することができる。
次にステップS46において、ステップ45で粉砕した金属M源を回収する。
次にステップS53において、混合物904、ステップS43で回収された金属M源およびステップS46で回収された金属M源を混合する。
次にステップS54において、混合物を回収し、ステップS55において混合物905を得る。
次にステップS56において、混合物905のアニールを行う。アニール時間は、規定温度の範囲内での保持時間を1時間以上50時間以下とすることが好ましく、2時間以上20時間以下がより好ましい。焼成時間が短すぎると表層部に形成される金属Mを有する化合物の結晶性が低い場合がある。あるいは、金属Mの拡散が不充分となる場合がある。あるいは有機物が表面に残存する場合がある。しかし焼成時間が長すぎると、金属Mの拡散が進みすぎて表層部および結晶粒界近傍の濃度が低くなる恐れがある。また、生産性が低下する。
次にステップS57において、冷却された粒子を回収する。さらに、粒子をふるいにかけることが好ましい。上記の工程で、ステップS58において正極活物質100を得る。
次に、図2Cに示す作製方法の一例を図4に示す。図4に示す作製方法においては、アルカリ金属Aおよび遷移金属を有する金属酸化物として、アルカリ金属およびコバルトを有する金属酸化物を用いる場合の例を示す。また、元素Xを有する化合物として、マグネシウムを有する化合物を用いる場合の例を示す。
図4に示すステップS11は、アルカリ金属Aを有するハロゲン化合物、マグネシウムを有する化合物および溶媒に加えて、金極M(1)源を準備する点が、図3と異なる。
次に、ステップS12、ステップS13およびステップS14を経て、アルカリ金属Aを有するハロゲン化合物、マグネシウムを有する化合物および金極M(1)源の混合物である混合物906を得る。ステップS12乃至ステップS14の条件等については図3の記載を参照することができる。
次にステップS25において、アルカリ金属Aおよびコバルトを有する金属酸化物として、金属酸化物95を準備する。金属酸化物95は、アルカリ金属Aを有する材料とコバルトを有する材料の混合物を焼成して得ることができる。あるいはあらかじめ、合成された金属酸化物を用いてもよい。
次に、ステップS31、ステップS32およびステップS33を経て、混合物906と金属酸化物95の混合物である混合物907を得る。ステップS31乃至ステップS33の条件等については図3の記載を参照することができる。
次にステップS34において、混合物907のアニールを行う。アニールの条件等については図3の記載を参照することができる。
次にステップS35においてアニールされた粉体を回収し、ステップS36において混合物908を得る。
次にステップS47において、金属M(2)源および溶媒を準備する。ここでは一例として、ゾルゲル法を適用し、金属M(2)源としてアルミニウムイソプロポキシドを、溶媒としてイソプロパノールを用いる例を示す。
次にステップS53において、アルミニウムイソプロポキシドをイソプロパノールに溶解させ、さらに混合物908を混合する。金属酸化物95の粒径によって、金属アルコキシドの必要量は異なる。粒径(D50)が20μm程度ならば、金属酸化物95が有するコバルトの原子数を1とし、アルミニウムイソプロポキシドが有するアルミニウムの濃度が0.001倍以上0.02倍以下となるよう加えることが好ましい。混合物908は、水蒸気を含む雰囲気下で撹拌されることが好ましい。撹拌はたとえばマグネチックスターラーで行うことができる。撹拌時間は、雰囲気中の水と金属アルコキシドが加水分解および重縮合反応を起こすのに十分な時間であればよく、例えば4時間、25℃、湿度90%RH(Relative Humidity、相対湿度)の条件下で行うことができる。また、湿度制御、および温度制御がされていない雰囲気下、例えばドラフトチャンバー内の大気雰囲気下において攪拌を行ってもよい。そのような場合には攪拌時間をより長くすることが好ましく、例えば室温において12時間以上、とすればよい。
次にステップS54において、混合液から沈殿物を回収し、ステップS55において混合物909を得る。回収方法としては、ろ過、遠心分離、蒸発乾固等を適用することができる。沈殿物は金属アルコキシドを溶解させた溶媒と同じアルコールで洗浄することができる。その後、回収した残渣を乾燥し、混合物909を得る。乾燥工程は例えば、80℃で1時間以上4時間以下、真空または通風乾燥することができる。
次にステップS56において、混合物909を焼成する。焼成時間は、規定温度の範囲内での保持時間を1時間以上50時間以下とすることが好ましく、2時間以上20時間以下がより好ましい。焼成時間が短すぎると表層部に形成される金属M(2)を有する化合物の結晶性が低い場合がある。あるいは、金属M(2)の拡散が不充分となる場合がある。あるいは有機物が表面に残存する場合がある。しかし焼成時間が長すぎると、金属M(2)の拡散が進みすぎて表層部および結晶粒界近傍の濃度が低くなる恐れがある。また、生産性が低下する。
次にステップS57において、冷却された粒子を回収する。さらに、粒子をふるいにかけることが好ましい。上記の工程で、ステップS58において正極活物質100を得る。
本実施の形態では、本発明の一態様の正極活物質について説明する。
本発明の一態様の正極活物質を用いることにより、二次電池の容量を高め、かつ、充放電サイクルに伴う放電容量の低下を抑制する。
正極活物質は、キャリアイオンとなる金属(以降、元素A)を有することが好ましい。元素Aとして例えばリチウム、ナトリウム、カリウム等のアルカリ金属、およびカルシウム、ベリリウム、マグネシウム等の第2族の元素を用いることができる。
本実施の形態では、先の実施の形態で説明した正極活物質100を有する二次電池に用いることのできる材料の例について説明する。本実施の形態では、正極、負極および電解液が、外装体に包まれている二次電池を例にとって説明する。
正極は、正極活物質層および正極集電体を有する。
正極活物質層は、少なくとも正極活物質を有する。また、正極活物質層は、正極活物質に加えて、活物質表面の被膜、導電助剤またはバインダなどの他の物質を含んでもよい。
正極集電体としては、ステンレス、金、白金、アルミニウム、チタン等の金属、及びこれらの合金など、導電性が高い材料をもちいることができる。また正極集電体に用いる材料は、正極の電位で溶出しないことが好ましい。また、シリコン、チタン、ネオジム、スカンジウム、モリブデンなどの耐熱性を向上させる元素が添加されたアルミニウム合金を用いることができる。また、シリコンと反応してシリサイドを形成する金属元素で形成してもよい。シリコンと反応してシリサイドを形成する金属元素としては、ジルコニウム、チタン、ハフニウム、バナジウム、ニオブ、タンタル、クロム、モリブデン、タングステン、コバルト、ニッケル等がある。集電体は、箔状、板状(シート状)、網状、パンチングメタル状、エキスパンドメタル状等の形状を適宜用いることができる。集電体は、厚みが5μm以上30μm以下のものを用いるとよい。
負極は、負極活物質層および負極集電体を有する。また、負極活物質層は、導電助剤およびバインダを有していてもよい。
負極活物質としては、例えば合金系材料や炭素系材料等を用いることができる。
負極集電体には、正極集電体と同様の材料を用いることができる。なお負極集電体は、リチウム等のキャリアイオンと合金化しない材料を用いることが好ましい。
電解液は、溶媒と電解質を有する。電解液の溶媒としては、非プロトン性有機溶媒が好ましく、例えば、エチレンカーボネート(EC)、プロピレンカーボネート(PC)、ブチレンカーボネート、クロロエチレンカーボネート、ビニレンカーボネート、γ−ブチロラクトン、γ−バレロラクトン、ジメチルカーボネート(DMC)、ジエチルカーボネート(DEC)、エチルメチルカーボネート(EMC)、ギ酸メチル、酢酸メチル、酢酸エチル、プロピオン酸メチル、プロピオン酸エチル、プロピオン酸プロピル、酪酸メチル、1,3−ジオキサン、1,4−ジオキサン、ジメトキシエタン(DME)、ジメチルスルホキシド、ジエチルエーテル、メチルジグライム、アセトニトリル、ベンゾニトリル、テトラヒドロフラン、スルホラン、スルトン等の1種、又はこれらのうちの2種以上を任意の組み合わせおよび比率で用いることができる。
また二次電池は、セパレータを有することが好ましい。セパレータとしては、例えば、紙、不織布、ガラス繊維、セラミックス、或いはナイロン(ポリアミド)、ビニロン(ポリビニルアルコール系繊維)、ポリエステル、アクリル、ポリオレフィン、ポリウレタンを用いた合成繊維等で形成されたものを用いることができる。セパレータはエンベロープ状に加工し、正極または負極のいずれか一方を包むように配置することが好ましい。
二次電池が有する外装体としては、例えばアルミニウムなどの金属材料や樹脂材料を用いることができる。また、フィルム状の外装体を用いることもできる。フィルムとしては、例えばポリエチレン、ポリプロピレン、ポリカーボネート、アイオノマー、ポリアミド等の材料からなる膜上に、アルミニウム、ステンレス、銅、ニッケル等の可撓性に優れた金属薄膜を設け、さらに該金属薄膜上に外装体の外面としてポリアミド系樹脂、ポリエステル系樹脂等の絶縁性合成樹脂膜を設けた三層構造のフィルムを用いることができる。
本実施の形態では、先の実施の形態で説明した正極活物質100を有する二次電池の形状の例について説明する。本実施の形態で説明する二次電池に用いる材料は、先の実施の形態の記載を参酌することができる。
まずコイン型の二次電池の一例について説明する。図5Aはコイン型(単層偏平型)の二次電池の外観図であり、図5Bは、その断面図である。
次に円筒型の二次電池の例について図6を参照して説明する。円筒型の二次電池600の外観図を図6Aに示す。図6Bは、円筒型の二次電池600の断面を模式的に示した図である。図6Bに示すように、円筒型の二次電池600は、上面に正極キャップ(電池蓋)601を有し、側面および底面に電池缶(外装缶)602を有している。これら正極キャップと電池缶(外装缶)602とは、ガスケット(絶縁パッキン)610によって絶縁されている。
二次電池の別の構造例について、図7乃至図11を用いて説明する。
次に、ラミネート型の二次電池の例について、図11乃至図17を参照して説明する。ラミネート型の二次電池は、可撓性を有する構成とすれば、可撓性を有する部位を少なくとも一部有する電子機器に実装すれば、電子機器の変形に合わせて二次電池も曲げることもできる。
ここで、図13に外観図を示すラミネート型二次電池の作製方法の一例について、図15B、図15Cを用いて説明する。
次に、曲げることのできる二次電池の例について図16および図17を参照して説明する。
本実施の形態では、本発明の一態様である二次電池を電子機器に実装する例について説明する。
本実施の形態では、車両に本発明の一態様である二次電池を搭載する例を示す。
本実施の形態では、本発明の一態様の正極活物質を有する二次電池を搭載することのできるウェアラブルデバイスの一例を示す。
作製した二次電池を用いて、45℃において、充電をCCCV(0.5C、4.6V、終止電流0.05C)、放電をCC(0.5C、2.5V)で繰り返し充放電を行い、サイクル特性を評価した。
正極活物質と導電助剤とバインダの混合比、電解質、電解液、セパレータ、正極缶および負極缶は実施例2と同様とした。
作製したコインセルを用いて、充電電圧を4.60V、4.62V、4.64Vおよび4.66Vとしてサイクル特性を評価した。具体的には25℃および45℃において、充電をCCCV(100mA/g、各種電圧、終止電流10mA/g)、放電をCC(100mA/g、終止電圧2.5V)で繰り返し充放電を行った。
次に、Sample 6乃至Sample 8の正極活物質を用いて作製したコインセルを用いて、25℃、45℃、50℃、55℃および60℃におけるサイクル特性を評価した。具体的には各温度において、充電をCCCV(100mA/g、4.6V、終止電流10mA/g)、放電をCC(100mA/g、終止電圧2.5V)で繰り返し充放電を行った。
次に、Sample 6乃至Sample 8の正極活物質を用いて作製したコインセルを用いて連続充電試験を行った。連続充電試験とは、二次電池を一定の電圧で長時間連続充電し、電池の安定性および安全性を評価する試験である。
Claims (12)
- 第1の材料、第2の材料および第3の材料が混合された第1の混合物を作製する第1のステップと、
前記第1の混合物を加熱し、第2の混合物を作製する第2のステップと、
前記第2の混合物、第4の材料および第5の材料が混合された第3の混合物を作製する第3のステップと、
前記第3の混合物を加熱し、第4の混合物を作製する第4のステップと、を有し、
前記第1の材料は、アルカリ金属を有するハロゲン化合物であり、
前記第2の材料は、マグネシウムを有し、
前記第3の材料は、前記アルカリ金属およびコバルトを有する金属酸化物であり、
前記第4の材料は、ニッケルを有し、
前記第5の材料は、アルミニウムを有し、
前記第4のステップにおいて、前記第3の混合物は、アニール装置の処理室において加熱され、
前記第4のステップにおいて、前記処理室で加熱される前記第3の混合物の総分量は15g以上であり、
前記第2のステップにおいて、前記加熱は酸素を有する雰囲気で行われ、
前記第2のステップにおいて、前記加熱は600℃以上950℃以下の温度範囲、かつ1時間以上100時間以下の範囲で行われ、
前記第4のステップにおいて、前記加熱は酸素を有する雰囲気で行われ、
前記第4のステップにおいて、前記加熱は600℃以上950℃以下の温度範囲、かつ1時間以上100時間以下の範囲で行われ、
前記第4のステップにおける前記加熱の温度は、前記第2のステップにおける前記加熱の温度よりも20℃以上低い、上極活物質の作製方法。 - 請求項1において、
前記アルカリ金属はリチウムであり、
前記第1の材料はフッ化リチウムであり、
前記第2の材料はフッ化マグネシウムである正極活物質の作製方法。 - 請求項1または請求項2において、
前記第3の材料は水酸化ニッケルであり、
前記第4の材料は水酸化アルミニウムである正極活物質の作製方法。 - 第1の材料、第2の材料、第3の材料および第4の材料が混合された第1の混合物を作製する第1のステップと、
前記第1の混合物を加熱し、第2の混合物を作製する第2のステップと、を有し、
前記第1の材料は、アルカリ金属を有するハロゲン化合物であり、
前記第2の材料は、マグネシウムを有し、
前記第3の材料は、ニッケル、アルミニウム、チタン、バナジウムおよびクロムから選ばれる一以上を有し、
前記第4の材料は、前記アルカリ金属およびコバルトを有する金属酸化物であり、
前記第2のステップにおいて、前記加熱は600℃以上950℃以下の温度範囲、かつ1時間以上100時間以下の範囲で行われ、
前記第1の材料、前記第2の材料および前記第3の材料は、前記第1の材料、前記第2の材料、および前記第3の材料を混合し、示差走査熱量測定において、620℃以上920℃以下の範囲に極小値を有する第1のピークを有し、
前記第1のピークは負のピークである正極活物質の作製方法。 - 請求項4において、
前記アルカリ金属はリチウムであり、
前記第1の材料はフッ化リチウムであり、
前記第2の材料はフッ化マグネシウムである正極活物質の作製方法。 - 請求項4または請求項5において、
前記第3の材料はニッケルを有し、
前記第1の混合物は、前記第1の材料、前記第2の材料、前記第3の材料および前記第4の材料に加えて第5の材料が混合された混合物であり、
前記第5の材料は、アルミニウムを有する正極活物質の作製方法。 - 請求項6において、
前記第3の材料は水酸化ニッケルである正極活物質の作製方法。 - 請求項4乃至請求項7のいずれか一において、
前記第1のピークの半値幅は100℃未満である正極活物質の作製方法。 - 請求項4乃至請求項8のいずれか一において、
示差走査熱量測定の測定温度範囲は少なくとも、200℃以上850℃以下の範囲を含む正極活物質の作製方法。 - 請求項4乃至請求項9のいずれか一において、
前記第2のステップにおける加熱の雰囲気は酸素を有する正極活物質の作製方法。 - 正極活物質を有する二次電池であって、
前記正極活物質は、リチウムと、コバルトと、マグネシウムと、フッ素と、を有し、
充電電圧4.60V、50℃で50サイクルの充放電を行い、50サイクル目の放電容量の1サイクル目からの減少分は、1サイクル目の放電容量を100%とした場合において、14%以下である二次電池。 - 請求項11において、前記正極活物質は、ニッケルと、アルミニウムと、を有する二次電池。
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