WO2014065067A1 - 電池 - Google Patents
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- WO2014065067A1 WO2014065067A1 PCT/JP2013/075864 JP2013075864W WO2014065067A1 WO 2014065067 A1 WO2014065067 A1 WO 2014065067A1 JP 2013075864 W JP2013075864 W JP 2013075864W WO 2014065067 A1 WO2014065067 A1 WO 2014065067A1
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- alkali metal
- battery
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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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/06—Oxides, Hydroxides
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/06—Oxides, Hydroxides
- C04B22/068—Peroxides, e.g. hydrogen peroxide
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- the present invention relates to a battery. More specifically, the present invention relates to a battery that can be suitably used for various applications in which a battery such as an electronic device or an automobile is used.
- Non-Patent Document 1 A method using an organic electrolyte has been reported for a lithium-air battery (see Non-Patent Document 1).
- a lithium-air battery has a large theoretical energy density, but an actual battery can realize a much lower energy density.
- the main factor is that the discharge product (Li 2 O 2 or Li 2 O) in the positive electrode closes the pores of the porous positive electrode (air electrode) and prevents the supply of oxygen.
- the clogging of the pores by the product also shows a hindering effect of preventing the release of oxygen generated during charging to the outside and making it difficult to fully charge.
- metal-air batteries such as lithium-air batteries have difficulties in reliability and handling. This is because an air electrode that exchanges oxygen with the outside world is used, so that it cannot be sealed in principle.
- This invention is made
- the inventors of the present invention have studied various types of batteries that have high theoretical voltage and theoretical capacity and can be repeatedly charged and discharged. When it is used as a substance, it is found that a battery using a reaction in which an alkali metal changes between A 2 O and A 2 O 2 (A is an alkali metal atom) in the positive electrode with charge / discharge can be constructed. It was. This battery has a significantly larger theoretical capacity than a lithium ion battery, and can be charged and discharged without oxygen molecules, so that the battery can be hermetically sealed. (Oxygen) supply obstruction does not occur. Furthermore, since it is possible to construct a battery without using a rare metal as a material constituting the battery, it is advantageous in terms of cost and environmental compatibility.
- the negative electrode active material includes at least one selected from the group consisting of alkali metal, tin, titanium, boron, nitrogen, silicon, and carbon, the same effect can be exhibited. .
- the present inventors have found that a new battery has such various characteristics, and have reached the present invention.
- the present invention is a battery including a positive electrode, a negative electrode, and an electrolyte
- the negative electrode contains a negative electrode active material comprising at least one selected from the group consisting of alkali metals, tin, titanium, boron, nitrogen, silicon, and carbon, and the battery comprises a positive electrode, a negative electrode And the electrolyte is hermetically sealed.
- the battery of the present invention by using a specific positive electrode containing a positive electrode active material containing a specific alkali metal compound, charging / discharging without oxygen molecules is possible, and therefore the battery cell is sealed. In addition, it is possible to obtain a battery that is low in cost, has high environmental compatibility, and can exhibit high battery performance.
- the positive electrode, the negative electrode, and the electrolyte are hermetically sealed, except for a part of the positive electrode and the negative electrode that are connected to the outside at the time of discharging or charging the battery. The remaining portion and the electrolyte are not in contact with the outside air.
- reaction at each electrode in the battery of the present invention and the overall reaction combining them include those expressed as follows (A represents an alkali metal atom).
- A represents an alkali metal atom
- the reaction from the left side to the right side is a discharge reaction
- the reverse reaction is a charge reaction.
- Reaction at the negative electrode A ⁇ A + + e ⁇
- Reaction at the positive electrode A 2 O 2 + 2A + + 2e ⁇ ⁇ 2A 2 O (II)
- a battery combining such reactions at the positive electrode and the negative electrode has not been known so far, and the battery of the present invention is a battery based on such a new principle.
- each of the above reactions can be expressed as follows. Reaction at the negative electrode: Li ⁇ Li + + e ⁇ Reaction at the positive electrode: Li 2 O 2 + 2Li + + 2e ⁇ ⁇ 2Li 2 O Overall reaction: Li + 1 / 2Li 2 O 2 ⁇ Li 2 O
- alkali metal atom of A in Formula (1) include Li, Na, K, Rb, Cs, and Fr. From the viewpoint of theoretical capacity, Li, Na and K are preferred, Li and Na are more preferred, and Li is more preferred.
- the alkali metal compounds can be used alone or in combination of two or more.
- the positive electrode active material used in the battery of the present invention contains the alkali metal compound, it may further contain a compound other than the alkali metal compound.
- the positive electrode includes a current collector and an active material layer, and the active material layer contains 0.1% of the alkali metal compound represented by the above formula (1) with respect to the mass of the active material layer. It is preferable to contain at least mass%. From the viewpoint of theoretical capacity, the content of the alkali metal compound represented by the above formula (1) is more preferably 1% by mass or more, further preferably 3% by mass or more, and particularly preferably 5% by mass or more. The upper limit is not particularly limited, but is preferably 99.99% by mass or less, more preferably 99.9% by mass or less from the viewpoint of electrical conductivity.
- the mass of the active material layer refers to the mass of the entire positive electrode (or negative electrode) excluding the current collector when the positive electrode (or negative electrode) is composed of a current collector and an active material layer. .
- the positive electrode active material has the following formula (2) with respect to the mass (100% by mass) of the active material layer of the positive electrode when fully charged: A 2 O 2 (2) It is preferable that 1% by mass or more of the alkali metal peroxide represented by (wherein A represents an alkali metal atom). By including in such a ratio, the reaction of the above reaction formula (II) becomes the main reaction of the positive electrode reaction of the battery of the present invention (50% or more of the total positive electrode reaction), and the battery of the present invention more fully provides the advantages described above. It will be possible to demonstrate.
- the ratio of the alkali metal peroxide represented by the above formula (2) to the mass of the active material layer of the positive electrode is more preferably 1 to 99.999% by mass, still more preferably 20 to 99.9% by mass. is there.
- Examples of the alkali metal atom of A in the above formula (2) include the same examples as those of the alkali metal atom of A in the above formula (1).
- the battery of the present invention has the following formula (2) included in the positive electrode when fully charged: A 2 O 2 (2) It is preferable that the molar ratio of the alkali metal contained in the negative electrode to the alkali metal peroxide represented by (wherein A represents an alkali metal atom) is 100 or less.
- the reaction from the right side to the left side of the above reaction formulas (I) and (II) occurs in the negative electrode and the positive electrode at the time of the charging reaction, respectively.
- the positive electrode active material becomes A 2 O 2 represented by the above formula (2).
- the reaction represented by the above reaction formula (II) is mainly performed with respect to the entire positive electrode reaction. It is preferable to be a reaction (50% or more of the total positive electrode reaction), and it is preferable that A 2 O 2 is contained in a predetermined ratio in the positive electrode during full charge. Therefore, the molar ratio of the alkali metal contained in the negative electrode to the alkali metal peroxide represented by the above formula (2) at the time of full charge, that is, (A / A 2 O 2 ) is preferably 100 or less. .
- the “alkali metal contained in the negative electrode” herein means an alkali metal involved in charge / discharge. That is, it means the one obtained by removing the alkali metal contained in the negative electrode during complete discharge from the alkali metal contained in the negative electrode during full charge.
- the contained negative electrode can be suitably used as a positive electrode and a negative electrode of a primary battery and a secondary battery.
- the alkali metal compound is used as the positive electrode active material and at least one selected from the group consisting of alkali metal, tin, titanium, boron, nitrogen, silicon, and carbon is used as the negative electrode active material
- the battery of the present invention The battery can be configured without using rare metals, can be manufactured at low cost, and is advantageous in terms of element strategy.
- the above-mentioned alkali metal compound is used as the positive electrode and the above-mentioned alkali metal is used as the negative electrode, a battery having excellent electromotive force can be obtained.
- the theoretical voltage is 2.87 V
- the theoretical value of the energy density is 2566 Wh / kg
- the battery has a high theoretical voltage and energy density.
- the energy density is much larger than that of the currently most popular lithium ion battery.
- the positive electrode material forming the active material layer of the positive electrode includes a positive electrode active material containing an alkali metal compound as an essential component, and includes an electrode catalyst, a conductive additive, and an organic compound.
- a positive electrode mixture is preferable, and other components may be included as necessary.
- the reaction from A 2 O to A 2 O 2 of the positive electrode reaction formula in the battery of the present invention described above (II) (reaction from right to left) is the reaction that is not known so far.
- this reaction has a lower overvoltage than the reaction from the right side to the left side of the reaction (O 2 + 4Li + + 4e ⁇ ⁇ 2Li 2 O) at the positive electrode of the lithium-air battery. It is preferable to proceed.
- reaction of the reaction (specifically from A 2 O in the positive electrode reaction formula (II) to the A 2 O 2 from Li 2 O to the Li 2 O 2 ) Can proceed at a lower overvoltage.
- a gas generation reaction (A 2 O ⁇ 2A + ) as a side reaction in the reaction from A 2 O to A 2 O 2 (reaction from the right side to the left side) in the positive electrode reaction formula (II) described above.
- + 2e ⁇ + 0.5O 2 the generated gas is easily reduced to A 2 O or A 2 O 2 inside the battery sealed at the time of discharge according to the discharge reaction formula at the positive electrode of the lithium air battery. Is possible.
- the electrode catalyst is not particularly limited, and examples thereof include a compound having an element belonging to Groups 1 to 17 in the periodic table or a simple substance.
- Elements belonging to Groups 1 to 17 in the periodic table include Li, Na, K, Rb, Cs, Ca, Sr, Ba, Y, La, Ce, Pr, Nd, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, Bi, Si, P, S, Ru, Rh, Pd, W, Examples include Re, Os, Ir, Pt, Au, O, S, F, Cl, and C.
- the elements belonging to Groups 5 to 11 in the periodic table are V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Ru, Rh, Pd, Ag, Ta, W, Re, Os, Ir, Pt, Au, and C. Even more preferred are Ag, Au, Cu, Fe, Mn, Co, Ni, C.
- the electrode catalyst is dissolved in the crystal structure of A 2 O or A 2 O 2 even in the form of contact with the A 2 O or A 2 O 2 particles of the positive electrode reaction formula (II). Even in such a form, the catalytic ability can be expressed.
- the electrode catalyst may be in the form of a single oxide which is an oxide of one kind of element represented by the following formula (3).
- M represents a metal atom other than an alkali metal atom.
- A represents a number of 1 to 3
- b represents a number of 1 to 4.
- metal atoms other than the alkali metal atoms include Ca, Sr, Ba, Y, La, Ce, Pr, Nd, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Zr, and Nb.
- Mo Ag, In, Sn, Sb, Hf, Ta, W, Pb, Bi, Si, P, and S are preferable.
- a 1, 2, or 3
- b 1, 2, 3, or 4
- the said electrode catalyst can be used by 1 type (s) or 2 or more types.
- the electrode catalyst may be in the form of a composite oxide containing two or more elements represented by the following formula (4).
- Q represents at least one element selected from the group consisting of elements belonging to Groups 1 to 3 in the periodic table.
- R represents an element belonging to Groups 4 to 15 in the periodic table.
- elements belonging to Groups 1 to 3 in the Q periodic table in the above formula (4) include Li, Na, K, Rb, Cs, Ca, Sr, Ba, Y, La, Ce, Pr, and Nd. It is done. Of these, elements belonging to Groups 1 and 2 are preferred.
- the element belonging to Groups 1 and 2 is more preferably Li or Sr.
- the elements belonging to Groups 4 to 16 in the R periodic table in the above formula (4) include Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, and Ag. , In, Sn, Sb, Hf, Ta, W, Pb, Bi, Si, P, and S. Particularly preferred is Fe or Co.
- n represents a number of 1 to 3, preferably a number of 2 to 3. More preferably, it is 2 or 2.5.
- the said electrode catalyst can be used by 1 type (s) or 2 or more types.
- the content of the electrode catalyst is preferably 0.1 to 99.9% by mass, more preferably 5 to 99.9% by mass with respect to the mass (100% by mass) of the active material layer of the positive electrode. %, And more preferably 10 to 99% by mass.
- the said electrode catalyst may have the said electrode catalyst on the conductive support agent mentioned later.
- the above-mentioned electrode catalyst is provided on the conductive auxiliary agent as long as the conductive auxiliary agent and the above-mentioned electrode catalyst are present in close proximity, contact or combination, and not only the surface of the conductive auxiliary agent but also the conductive auxiliary agent. You may have the said catalyst for electrodes in the agent.
- the proportion of the electrode catalyst with respect to 100% by mass of the conductive additive a compound or a simple substance having an element belonging to the above group 1 to group 17, a single oxide represented by the above formula (3), and the above
- the total ratio of the composite oxide represented by formula (4) is preferably 0.01 to 300% by mass. More preferably, the content is 0.1 to 150% by mass. More preferably, it is 10 mass% or more. Especially preferably, it is 40 mass% or more.
- the steps for constituting the method for producing a positive electrode using the positive electrode material are as follows. 1. Step of preparing alkali metal compound 2. Preparation step of positive electrode mixture; A step of forming a positive electrode can be given. A commercially available compound may be used in place of the alkali metal compound obtained in the above-mentioned “1. Preparation process of alkali metal compound”. The preparation step can be omitted.
- the alkali metal compound in the step of preparing the alkali metal compound, it is preferable to prepare the alkali metal compound by reacting the alkali metal with oxygen in the air or by heating and reacting the alkali metal in the air. According to this method, the alkali metal compound can be safely prepared under relatively mild conditions.
- the reaction temperature is preferably 0 to 180 ° C.
- the reaction time may be appropriately set according to the amount of alkali metal, reaction temperature, etc., but is preferably 0.5 to 20 hours.
- the alkali metal may be pulverized to an average particle size of 0.01 to 2 ⁇ m before the step of allowing air to act on the alkali metal.
- a mortar, bead mill, ball mill, cutter mill, disk mill, stamp mill, hammer mill, jet mill, or the like can be used.
- the step of pulverizing the alkali metal to an average particle size of 0.01 to 2 ⁇ m may be performed simultaneously with the step of causing air to act on the alkali metal. That is, air may be allowed to act on the alkali metal while pulverizing the alkali metal.
- the method for preparing the alkali metal compound may include a step of purifying the obtained alkali metal compound after performing the step of causing air to act on the alkali metal.
- the purification step includes washing with water, treatment with acid, washing with acetone, washing with methanol, and the like.
- the alkali metal compound is essential, and when it contains an electrode catalyst, a conductive additive, an organic compound, etc., it can be prepared by kneading the raw materials of these positive electrode mixtures.
- the positive electrode material (positive electrode mixture) in the present invention is in the form of particles, it is preferable to use particles having an average particle diameter of 1000 ⁇ m or less.
- the average particle diameter can be measured with a transmission electron microscope (TEM), a scanning electron microscope (SEM), a particle size distribution measuring device, or the like.
- TEM transmission electron microscope
- SEM scanning electron microscope
- the shape of the particles include fine powder, powder, granule, granule, scale, and polyhedron.
- the particles having an average particle size as described above may be, for example, a method in which the particles are pulverized by a ball mill or the like, the obtained coarse particles are dispersed in a dispersant to obtain a desired particle size, and then dried. In addition to the method of screening the particle diameter by sieving the particles, etc., it is possible to optimize the preparation conditions at the stage of producing the particles to obtain (nano) particles having a desired particle diameter.
- the particle diameter is defined as the average particle diameter.
- the particle length measured according to a general rule is used as it is.
- the major axis diameter and minor axis diameter of one particle are used. Measure two or more lengths, such as a constant direction diameter, and let the average value be the particle diameter. It is preferred to make measurements on at least 100 particles.
- the amount directly measured as the particle size is converted into a regular shape (eg, circle, sphere) by a geometric formula. And the particle diameter (equivalent diameter).
- the measured amount is calculated by using a physical law (eg Mie theory) derived when a specific particle shape and a specific physical condition are assumed. Calculated as (effective diameter).
- the particle diameter is calculated by measuring the speed (diffusion coefficient) at which particles in the liquid diffuse due to Brownian motion.
- the positive electrode forming step is preferably carried out as follows. First, if necessary, the positive electrode mixture is kneaded with water and / or an organic solvent, the above-mentioned electrode catalyst, the following conductive auxiliary agent, and an organic compound to form a paste. Next, the obtained paste mixture is applied on a metal foil such as an aluminum foil or a metal mesh such as an aluminum mesh / nickel mesh as a current collector so that the film thickness is as constant as possible. After coating, drying at 0 to 250 ° C. is preferable. The drying temperature is more preferably 15 to 200 ° C. Drying may be performed by vacuum drying. Further, after drying, pressing may be performed with a roll press or the like at a pressure of 0.0001 to 20 t.
- the pressure for pressing is more preferably 0.001 to 15 t. More preferably, it is 0.01 t or more, and particularly preferably 0.1 t or more.
- the film thickness of the positive electrode is preferably 1 nm to 2000 ⁇ m, for example. More preferably, it is 10 nm to 1500 ⁇ m, and still more preferably 100 nm to 1000 ⁇ m.
- a mixer, blender, kneader, bead mill, ball mill, mechanical milling, or the like can be used for mixing and kneading.
- water or an organic solvent such as methanol, ethanol, propanol, isopropanol, tetrahydrofuran, N-methylpyrrolidone may be added.
- operations such as sieving as described above may be performed before and after mixing and kneading operations in order to align the particles to a desired particle size.
- the negative electrode active material layer in the battery of the present invention contains a negative electrode active material containing at least one selected from the group consisting of alkali metals, tin, titanium, boron, nitrogen, silicon, and carbon.
- alkali metal include Li, Na, K, Rb, Cs, and Fr.
- Li and Na are preferable, and Li is more preferable.
- the carbon include graphite, amorphous carbon, carbon nanofoam, activated carbon, graphene, nanographene, graphene nanoribbon, fullerene, carbon black, fibrous carbon, carbon nanotube, carbon nanohorn, ketjen black, acetylene black, carbon fiber, Examples include vapor grown carbon fiber.
- graphite, graphene, fibrous carbon, carbon nanotube, and acetylene black are preferable. More preferred are graphite, graphene, fibrous carbon, carbon nanotube, acetylene black, carbon fiber, and vapor grown carbon fiber.
- the negative electrode active material used in the battery of the present invention contains other compounds as long as it contains at least one selected from the group consisting of alkali metals, tin, titanium, boron, nitrogen, silicon, and carbon. You may go out.
- the total content of the negative electrode active material comprising at least one selected from the group consisting of the alkali metal, tin, titanium, boron, nitrogen, silicon, and carbon is the mass of the active material layer contained in the negative electrode (100 mass). %) Is preferably 1.0% by mass or more from the viewpoint of theoretical capacity. More preferably, the content is 2.0 to 100% by mass, and still more preferably 30 to 100% by mass. Especially preferably, it is 90 mass% or more.
- the active material layer of the negative electrode may be formed of a negative electrode mixture that may include the negative electrode active material, a conductive additive, and an organic compound. It may be.
- the negative electrode is composed of an active material layer of the negative electrode and a current collector made of a metal foil such as an aluminum foil or a metal mesh such as an aluminum mesh or a nickel mesh, which is bound to the active material layer.
- the conductive assistant and the organic compound will be described later.
- the electrolyte contained in the battery of the present invention is not particularly limited, but preferably contains an alkali metal ion dissolved in a medium. That is, the battery of the present invention preferably includes an electrolytic solution in which alkali metal ions are dissolved in a medium.
- the electrolyte include LiPF 6 , LiBF 4 , LiClO 4 , LiN (SO 2 F) 2 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , Li (BC 4 O 8 ).
- LiF, LiB (CN) 4 LiPF 6 , NaBF 4 , NaClO 4 , NaN (SO 2 F) 2 , NaN (SO 2 CF 3 ) 2 , NaN (SO 2 C 2 F 5 ) 2 , Na (BC 4 O 8 ), NaF, NaB (CN) 4 , potassium hydroxide, sodium hydroxide, lithium carbonate, lithium hydroxide, potassium fluoride, potassium borate and the like.
- LiPF 6 LiBF 4 , LiClO 4 , LiN (SO 2 F) 2 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , Li (BC 4 O 8 ), LiF, LiB (CN) 4 .
- organic solvent electrolytes include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ⁇ -butyrolactone, diethyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, dimethoxymethane.
- aqueous electrolyte examples include alkaline aqueous solutions such as potassium hydroxide aqueous solution, sodium hydroxide aqueous solution and lithium hydroxide aqueous solution; acidic aqueous solutions such as sulfuric acid aqueous solution.
- alkaline aqueous solutions such as potassium hydroxide aqueous solution, sodium hydroxide aqueous solution and lithium hydroxide aqueous solution
- acidic aqueous solutions such as sulfuric acid aqueous solution.
- the electrolytic solution one or more of the above can be used. When using 2 or more types, they may be in a mixed state or in a state of being separated by a partition.
- the electrolyte concentration is preferably 0.01 to 15 mol / L. By using the electrolytic solution having such a concentration, good battery performance can be exhibited. More preferably, it is 0.1 to 12 mol / L.
- the electrolytic solution may contain an additive. Examples of the additive include a material that forms a protective film for a positive electrode and a negative electrode, and a material that suppresses the insertion of propylene carbonate into graphite when propylene carbonate is used as an electrolyte, such as vinylene carbonate and fluoroethylene.
- Examples include carbonate, chloroethylene carbonate, ethylene bromide carbonate, ethylene sulfite, propylene sulfite, crown ethers, boron-containing anion receptors, and aluminum-containing anion receptors.
- One or more additives may be used as described above.
- the conductive aid is preferably a conductive substance that can be used as an electronic material.
- the conductive assistant is preferably made of a metal, conductive ceramic, or carbon material. Examples of the metal include nickel powder, aluminum powder, zinc powder, gold powder, and mesoporous gold.
- Carbon materials include graphite, amorphous carbon, carbon nanofoam, activated carbon, graphene, nanographene, graphene nanoribbon, fullerene, carbon black, fibrous carbon, carbon nanotube, carbon nanohorn, ketjen black, acetylene black, Examples thereof include carbon fiber and vapor grown carbon fiber.
- graphene, fibrous carbon, carbon nanotube, acetylene black, carbon fiber, and vapor grown carbon fiber are preferable.
- the conductive assistant is graphene, fibrous carbon, carbon nanotube, acetylene black, metallic zinc, gold powder, or mesoporous gold.
- the said conductive support agent has the effect
- the blending amount of the conductive assistant is preferably 0.001 to 90% by mass with respect to the mass (100% by mass) of the active material layer of the positive electrode (or negative electrode).
- the positive electrode (or the negative electrode) will exhibit better battery performance.
- the content is 0.01 to 70% by mass, still more preferably 0.05 to 55% by mass, and particularly preferably 0.05 to 50% by mass.
- organic compound salt can be illustrated other than an organic compound, 1 type (s) or 2 or more types can be used.
- organic compound or organic compound salt when the organic compound or organic compound salt is a polymer, radical polymerization, radical (alternate) copolymerization, anionic polymerization, anion (alternate) copolymerization, cation (alternate) are selected from monomers corresponding to the constituent units of the polymer. It can be obtained by polymerization, cationic (alternate) copolymerization, electrolytic polymerization or the like.
- the organic compound and the organic compound salt can also act as a binder that binds particles or particles and a current collector, or a dispersant that effectively disperses them.
- the organic compound and organic compound salt are preferably poly (meth) acrylate-containing polymer, polyvinyl alcohol-containing polymer, polyethylene oxide-containing polymer, polypropylene oxide-containing polymer, polybutene oxide-containing polymer, cellulose, cellulose acetate, hydroxyalkyl.
- Cellulose carboxymethyl cellulose, polytetrafluoroethylene-containing polymer, polyvinylidene fluoride-containing polymer, polypentafluoroethylene-containing polymer, polymaleate-containing polymer, polyitaconate-containing polymer, ion-exchange membrane polymer, sulfonate-containing polymer, Examples include quaternary ammonium salt-containing polymers, quaternary phosphonium salt polymers, and the like.
- the blending amount of the organic compound and organic compound salt is 0.01 to 50% by mass with respect to the mass (100% by mass) of the active material layer of the positive electrode (or negative electrode). It is preferable. When the blending amount of these organic compounds, organic compound salts, and more preferably the polymer is within such a range, the positive electrode (or the negative electrode) will exhibit better battery performance. More preferably, the content is 0.01 to 45% by mass, and still more preferably 0.1 to 40% by mass.
- the blending amount is the mass (100 mass) of the active material layer of the positive electrode (or the negative electrode). %) To 0.01 to 10% by mass. More preferably, it is 0.05 to 7% by mass, and still more preferably 0.1 to 5% by mass.
- the said separator is a member which isolate
- the separator is not particularly limited, but polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, cellulose, cellulose acetate, hydroxyalkyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, cellophane, polystyrene, polyacrylonitrile, polyacrylamide, polychlorinated.
- High molecular weight polymer having micropores such as vinyl, polyamide, vinylon, poly (meth) acrylic acid, gel compound, ion-exchange membrane polymer, cyclized polymer, polymer containing poly (meth) acrylic acid (salt), sulfone Examples include acid (salt) -containing polymers, quaternary ammonium salt-containing polymers, quaternary phosphonium salt-containing polymers, solid electrolytes such as ion conductive polymers and ion conductive glasses.
- the battery of the present invention includes the positive electrode, the negative electrode, and the electrolyte, and these are sealed in the battery.
- the form of the battery of the present invention is not particularly limited, and includes a primary battery, a chargeable / dischargeable secondary battery (storage battery), use of mechanical charge, use of a third electrode other than the positive electrode and the negative electrode, and the like. Any form may be adopted. Also, it can be assembled in a charged state or in a discharged state.
- the battery of the present invention has the above-described configuration and uses a new principle different from that of the conventional batteries, has a high theoretical voltage and a theoretical capacity, and can be repeatedly charged and discharged.
- the battery is advantageous in that it has battery performance, is low in cost, and has high environmental compatibility.
- FIG. It is a figure which shows the result of having measured cyclic voltammetry using the positive electrode prepared in the preparation example 1.
- FIG. It is a figure which shows the result of having measured cyclic voltammetry using the positive electrode prepared in the preparation example 2.
- FIG. It is a figure which shows the XRD measurement result of the solid powder prepared in Preparation Example 7. It is a figure which shows the XRD measurement result of the solid powder prepared in Preparation Example 8. It is a figure which shows the XRD measurement result of the solid powder prepared in Preparation Example 9. It is a figure which shows the XRD measurement result of the solid powder prepared in Preparation Example 10. It is a figure which shows the XRD measurement result of the solid powder prepared in the preparation example 11.
- Example 24 It is the figure which showed the charging / discharging test result in Example 24. It is the figure which showed the charging / discharging test result in Example 25. It is the figure which showed the charging / discharging test result in Example 26. It is the figure which showed the charging / discharging test result in Example 27. It is a figure which shows the XRD measurement result of the solid powder prepared in Preparation Example 18. It is a figure which shows the XRD measurement result of the solid powder prepared in Preparation Example 19. It is the figure which showed the charging / discharging test result in Example 28. It is the figure which showed the charging / discharging test result in Example 29. It is the figure which showed the charging / discharging test result in Example 30.
- Example 31 It is the figure which showed the charging / discharging test result in Example 31. It is the figure which showed the XRD measurement result before and behind charging / discharging in Example 32. It is a figure which shows the XRD measurement result of the solid powder prepared in Preparation Example 20. It is a figure which shows the XRD measurement result of the solid powder prepared in the preparation example 21. It is a figure which shows the XRD measurement result of the solid powder prepared in Preparation Example 22. It is a figure which shows the XRD measurement result of the solid powder prepared in the preparation example 23. It is the figure which showed the charging / discharging test result in Example 34. It is the figure which showed the charging / discharging test result in Example 35. It is the figure which showed the charging / discharging test result in Example 36. It is the figure which showed the charging / discharging test result in Example 37.
- Preparation Example 1 As a positive electrode active material, lithium oxide (Li 2 O, manufactured by Strem Chemical) 28 mg, electrode catalyst (60% Ag / C, manufactured by Alfa Aesar) 80 mg, polytetrafluoroethylene (PTFE) 15 mg are kneaded, and positive electrode mixture Got. 14 mg of this positive electrode mixture was pressure-bonded to an 80 mg nickel mesh to obtain a positive electrode.
- lithium oxide Li 2 O, manufactured by Strem Chemical
- electrode catalyst 60% Ag / C, manufactured by Alfa Aesar
- PTFE polytetrafluoroethylene
- Preparation Example 2 85 mg of an electrode catalyst (60% Ag / C, manufactured by Alfa Aesar) and 15 mg of PTFE were kneaded to obtain a positive electrode mixture. 14 mg of this positive electrode mixture was pressure-bonded to an 80 mg nickel mesh to obtain a positive electrode.
- an electrode catalyst (60% Ag / C, manufactured by Alfa Aesar) and 15 mg of PTFE were kneaded to obtain a positive electrode mixture. 14 mg of this positive electrode mixture was pressure-bonded to an 80 mg nickel mesh to obtain a positive electrode.
- Example 1 Using a positive electrode prepared in Preparation Example 1 as a working electrode, using a lithium metal as a counter electrode and a reference electrode, and using a tripolar cell using 1M LiClO 4 / propylene carbonate (PC) electrolyte as an electrolyte, Cyclic voltammetry (CV) was measured in the box. At this time, the electrode potential was swept as 3.38 V open circuit voltage (OCV) ⁇ 4 V ⁇ 1.2 V ⁇ OCV 3.38 V, and the sweep speed was set to 0.2 mV / sec. The result is shown in FIG. In FIG. 1, the horizontal axis represents potential, and the vertical axis represents current. From the results of FIG.
- Preparation Example 3 As the positive electrode active material, 44 mg of lithium oxide (Li 2 O, manufactured by Strem Chemicals), 84 mg of artificial graphite KS6L (manufactured by TIMCAL), and 7 mg of polytetrafluoroethylene (PTFE) were kneaded to obtain a positive electrode mixture. 6 mg of this positive electrode mixture was pressure-bonded to an 80 mg nickel mesh to obtain a positive electrode.
- lithium oxide Li 2 O, manufactured by Strem Chemicals
- KS6L artificial graphite KS6L (manufactured by TIMCAL)
- PTFE polytetrafluoroethylene
- Preparation Example 4 A positive electrode mixture was obtained in the same manner as in Preparation Example 3, except that lithium peroxide (Li 2 O 2 , manufactured by Alfa Aesar) was used instead of lithium oxide as the positive electrode active material. 6 mg of this positive electrode mixture was pressure-bonded to an 80 mg nickel mesh to obtain a positive electrode.
- lithium peroxide Li 2 O 2 , manufactured by Alfa Aesar
- Preparation Example 5 A positive electrode mixture was obtained in the same manner as in Preparation Example 3, except that sodium oxide (Na 2 O, manufactured by Alfa Aesar) was used as the positive electrode active material instead of lithium oxide. 6 mg of this positive electrode mixture was pressure-bonded to an 80 mg nickel mesh to obtain a positive electrode.
- sodium oxide Na 2 O, manufactured by Alfa Aesar
- Preparation Example 6 A positive electrode mixture was obtained in the same manner as in Preparation Example 3, except that sodium peroxide (Na 2 O 2 , manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of lithium oxide as the positive electrode active material. 6 mg of this positive electrode mixture was pressure-bonded to an 80 mg nickel mesh to obtain a positive electrode.
- sodium peroxide Na 2 O 2 , manufactured by Wako Pure Chemical Industries, Ltd.
- Example 2 Using a positive electrode produced in Preparation Examples 3 to 6 as a working electrode, using lithium metal as a counter electrode and a reference electrode, and using a tripolar cell using propylene carbonate (PC) electrolyte as an electrolyte, in a glove box A charge / discharge test was conducted. The charge and discharge were performed with a cut-off potential of 1.4 to 4.2 V and a load of 0.134 ampere per mole of active material. When the positive electrodes prepared in Preparation Examples 3 and 5 were used, the cycle was performed from charging, and when the positive electrodes prepared in Preparation Examples 4 and 6 were used, the cycle was performed from discharge. The results are shown in Table 1.
- Preparation Example 7 (Li 2 O / Fe 2 O 3 positive electrode preparation step) 1.99 g of lithium oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd.) as a positive electrode active material and 2.09 g of ⁇ -iron oxide (manufactured by Wako Pure Chemical Industries, Ltd.) as an electrode catalyst are placed in a pot for a planetary ball mill. Planetary ball mill mixing (mixing conditions: treatment using 60 10 mm ⁇ zirconia balls at a rotation speed of 600 rpm for 60 hours) was performed. All operations were performed in a glove box with a water concentration of 1 ppm or less, which was purged with argon. The XRD measurement result of the obtained solid powder is shown in FIG.
- the obtained solid powder was a mixture of Li 2 O and LiFeO 2 . 172 mg of the obtained solid powder, 200 mg of acetylene black as a conductive assistant, and 28 mg of polytetrafluoroethylene powder as a binder were mixed in an agate mortar and processed into a clay to obtain a positive electrode mixture. The obtained positive electrode mixture was pressure-bonded to a 60 mg aluminum mesh to obtain a positive electrode.
- Preparation Example 8 Li 2 O / Co 3 O 4 positive electrode preparation step
- Li 2 O / Co 3 O 4 positive electrode preparation step 1.43 g of lithium oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd.) as the positive electrode active material and 1.54 g of cobalt oxide (Co 3 O 4 , manufactured by Wako Pure Chemical Industries, Ltd.) as the electrode catalyst are used in a planetary ball mill pot. Then, planetary ball mill mixing (mixing conditions; treatment using 25 10 mm ⁇ zirconia balls at a rotation speed of 600 rpm for 60 hours) was performed. All operations were performed in a glove box with a water concentration of 1 ppm or less, which was purged with argon. The XRD measurement result of the obtained solid powder is shown in FIG.
- the obtained solid powder was a mixture of Li 2 O and Co 3 O 4 .
- 126 mg of the obtained solid powder, 142 mg of acetylene black as a conductive assistant, and 20 mg of polytetrafluoroethylene powder as a binder were mixed in an agate mortar and processed into a clay to obtain a positive electrode mixture.
- the obtained positive electrode mixture was pressure-bonded to a 60 mg aluminum mesh to obtain a positive electrode.
- Preparation Example 9 Li 2 O / NiO positive electrode preparation step
- 2.75 g of lithium oxide manufactured by High Purity Chemical Research Co., Ltd.
- 2.74 g of nickel oxide NiO, manufactured by Kanto Chemical Co., Ltd.
- All operations were performed in a glove box with a water concentration of 1 ppm or less, which was purged with argon.
- the XRD measurement result of the obtained solid powder is shown in FIG.
- the obtained solid powder was a mixture of Li 2 O and NiO.
- Preparation Example 10 Li 2 O / LiCoO 2 positive electrode preparation step
- 2.32 g of lithium oxide manufactured by Kojundo Chemical Laboratory Co., Ltd.
- 3.05 g of lithium cobaltate manufactured by Wako Pure Chemical Industries, Ltd.
- All operations were performed in a glove box with a water concentration of 1 ppm or less, which was purged with argon.
- the XRD measurement result of the obtained solid powder is shown in FIG.
- the obtained solid powder was a mixture of Li 2 O and LiCoO 2 .
- 61 mg of the obtained solid powder, 77 mg of acetylene black as a conductive additive and 10 mg of polytetrafluoroethylene powder as a binder were mixed in an agate mortar and processed into a clay shape to obtain a positive electrode mixture.
- the obtained positive electrode mixture was pressure-bonded to a 60 mg aluminum mesh to obtain a positive electrode.
- Preparation Example 11 Li 2 O / MnO 2 positive electrode preparation step
- 1.90 g of lithium oxide manufactured by Kojundo Chemical Laboratory Co., Ltd.
- 2.22 g of manganese dioxide manufactured by Wako Pure Chemical Industries, Ltd.
- All operations were performed in a glove box with a water concentration of 1 ppm or less, which was purged with argon.
- the XRD measurement result of the obtained solid powder is shown in FIG.
- the obtained solid powder was a mixture of Li 2 O and MnO 2 .
- 113 mg of the obtained solid powder, 134 mg of acetylene black as a conductive assistant, and 21 mg of polytetrafluoroethylene powder as a binder were mixed in an agate mortar and processed into a clay to obtain a positive electrode mixture.
- the obtained positive electrode mixture was pressure-bonded to a 60 mg aluminum mesh to obtain a positive electrode.
- Preparation Example 12 Li 2 O / SrCoO 2.5 positive electrode preparation step
- Strontium carbonate made by Wako Pure Chemical Industries
- cobalt oxide Co 3 O 4 , Wako Pure Chemical Industries
- SrCoO 2.5 which is an oxygen deficient perovskite compound was obtained.
- 35 mg of the obtained solid powder, 46 mg of acetylene black as a conductive additive, and 7 mg of polytetrafluoroethylene powder as a binder were mixed in an agate mortar and processed into a clay shape to obtain a positive electrode mixture.
- the obtained positive electrode mixture was pressure-bonded to a 60 mg aluminum mesh to obtain a positive electrode.
- Example 3 charge / discharge test
- Li 2 O / Fe 2 O 3 positive electrode mixture electrode prepared in Preparation Example 7, counter electrode and reference electrode were used for the working electrode, and lithium metal was used for the electrolyte, and 1M LiTFSI DME electrolyte (LiTFSI: lithium bistrifluoro) was used for the electrolyte.
- LiTFSI lithium bistrifluoro
- DME 1,2-dimethoxyethane
- the positive electrode active material was charged at a current density of 4.5 mA / g and then discharged at the same current density.
- the results of the charge / discharge test are shown in FIG. As shown in FIG. 9, it was shown that charging / discharging can be repeated using lithium oxide as a positive electrode active material.
- Example 4 charge / discharge test
- Li 2 O / Co 3 O 4 positive electrode mixture electrode prepared in Preparation Example 8 as a working electrode.
- the measurement results are shown in FIG. As shown in FIG. 10, it was shown that charging / discharging was possible using lithium oxide as a positive electrode active material.
- Example 5 charge / discharge test
- Li 2 O / NiO positive electrode mixture electrode prepared in Preparation Example 9 as a working electrode.
- the measurement results are shown in FIG. As shown in FIG. 11, it was shown that charging / discharging was possible using lithium oxide as a positive electrode active material.
- Example 6 Charge / discharge test
- Li 2 O / LiCoO 2 positive electrode mixture electrode prepared in Preparation Example 10 as a working electrode
- a charge / discharge test was performed under the same conditions as in Example 3.
- the measurement results are shown in FIG. As shown in FIG. 12, it was shown that charging / discharging was possible using lithium oxide as a positive electrode active material.
- Example 7 Charge / discharge test
- Li 2 O / MnO 2 positive electrode mixture electrode prepared in Preparation Example 11 as a working electrode
- a charge / discharge test was performed under the same conditions as in Example 3.
- the measurement results are shown in FIG. As shown in FIG. 13, it was shown that charging / discharging was possible using lithium oxide as a positive electrode active material.
- Example 8 Charge / discharge test
- Li 2 O / SrCoO 2.5 positive electrode mixture electrode prepared in Preparation Example 12 as a working electrode, a charge / discharge test was performed under the same conditions as in Example 3. The measurement results are shown in FIG. As shown in FIG. 14, it was shown that charging / discharging was possible using lithium oxide as a positive electrode active material.
- Example 9 Analysis of evolved gas during charging
- a charge test was performed under the same conditions as in Example 3, and the gas phase components contained in the cell were identified and quantified using a quadrupole mass spectrometer. The measurement results are shown in FIG. Significant gas evolution until 600 mAh / g as the oxidizing capacity as shown in FIG. 15 is not observed, it was shown that Li 2 O is converted to Li 2 O 2 without oxygen generation.
- an arrow indicates whether the graph indicates the scale on the right vertical axis or the scale on the left vertical axis.
- Example 10 (XRD analysis of positive electrode after charging) A charge test was performed under the same conditions as in Example 5. The cut-off voltage was 3.3 V, and the charged positive electrode was washed with a DME (1,2-dimethoxyethane) solvent and then dried. The obtained positive electrode after charging was placed in an airtight sample table filled with argon, and XRD measurement was performed. The results are shown in FIG. The Li 2 O signal near 33.5 ° was attenuated depending on the oxidation capacity, and the Li 2 O 2 signal was confirmed at 34.5 ° and 39.8 °. Li 2 O in the charging process from these it was shown to be converted to Li 2 O 2.
- Example 11 Quantification of Li 2 O 2 contained in positive electrode after charging
- a charge test was performed under the same conditions as in Example 4. 8.24 mg of the positive electrode mixture was pressure-bonded to a 60 mg aluminum mesh to obtain a positive electrode. The cut-off voltage was 3.3 V, and the charged positive electrode was washed with a DME (1,2-dimethoxyethane) solvent and then dried. The oxidized positive electrode and 1 mg of manganese dioxide obtained in a glove box in an argon atmosphere were dispersed in 1 ml of deoxygenated water.
- Example 12 (Charge / Discharge Test with Bipolar Cell) The charge / discharge test was conducted using a commercially available bipolar cell (HS cell, manufactured by Hosen Co., Ltd.). Li 2 O / Fe 2 O 3 positive electrode mixture electrode prepared in Preparation Example 7 was used as the working electrode, lithium metal was used as the counter electrode, and 4.2 M LiTFSI acetonitrile electrolyte (LiTFSI: lithium bistrifluoromethane) was used as the electrolyte. Sulfonylimide [LiN (SO 2 CF 3 ) 2 ]) was used. The positive electrode active material was charged at a current density of 4.5 mA / g and then discharged at the same current density. The results of the charge / discharge test are shown in FIG. As shown in FIG. 17, it was shown that charging / discharging was possible using lithium oxide as a positive electrode active material.
- LiCoO 2 used in Preparation Example 10 and Example 6 is a compound generally known as a positive electrode active material, but the charge / discharge potential of LiCoO 2 is around 3.8 V (vs. Li metal).
- the charge potential is around 3.2 V (vs. Li metal)
- LiCoO 2 is considered to be an electrode catalyst.
- LiFeO 2 in Preparation Example 7 and Example 3 and SrCoO 2.5 in Preparation Example 12 and Example 8 are also considered to be electrode catalysts in Example 8.
- the single oxide (Co 3 O 4 , NiO, MnO 2 ) was not mixed with Li 2 O alone, the flat portion of charge / discharge observed in this example was not observed. It is considered to be an electrode catalyst.
- Preparation Example 13 (Preparation process of Li 2 O / Fe 2 O 3 / Co 3 O 4 positive electrode) 2.62 g of lithium oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd.) as the positive electrode active material, 1.38 g of ⁇ -iron oxide (manufactured by Wako Pure Chemical Industries, Ltd.) as the electrode catalyst, cobalt oxide (Co 3 O 4 , sum) 1.36 g (manufactured by Kojunkaku Kogyo Co., Ltd.) was put in a pot for a planetary ball mill and mixed with a planetary ball mill (mixing conditions; treated with 25 10-mm ⁇ zirconia balls for 60 hours at a rotational speed of 600 rpm).
- Example 13 (Charge / Discharge Test Using a Bipolar Cell) The charge / discharge test was conducted using a commercially available bipolar cell (HS cell, manufactured by Hosen Co., Ltd.). Li 2 O / Fe 2 O 3 / Co 3 O 4 positive electrode mixture electrode prepared in Preparation Example 13 was used for the working electrode, lithium metal was used for the counter electrode, and 4.2 M LiTFSI acetonitrile electrolyte (LiTFSI) was used for the electrolyte. : Lithium bistrifluoromethanesulfonylimide [LiN (SO 2 CF 3 ) 2 ]) was used.
- the positive electrode active material was charged at a current density of 4.5 mA / g and then discharged at the same current density.
- the results of the charge / discharge test are shown in FIG. As shown in FIG. 19, it was shown that charging / discharging was possible using lithium oxide as a positive electrode active material.
- Example 14 (XRD analysis of positive electrode after charging) A charge test was performed under the same conditions as in Example 13. The cutoff voltage was 3.3 V, and the positive electrode after charging was washed with an acetonitrile solvent and then dried. The obtained positive electrode after charging was placed in an airtight sample table filled with argon, and XRD measurement was performed. The results are shown in FIG. Attenuation of the Li 2 O signal around 33.5 ° was observed depending on the oxidation capacity. Li 2 O in the charging process from these it was shown to be converted to Li 2 O 2.
- Example 15 Quantification of Li 2 O 2 contained in positive electrode after charge / discharge
- a charge / discharge test was performed under the same conditions as in Example 13.
- the quantification of lithium peroxide contained in the positive electrode was performed in the same manner as in Example 11 at each charge / discharge depth.
- FIG. 21 shows the result of plotting the detected amount of Li 2 O 2 against the charge capacity at the time of initial charge.
- the theoretical amount of Li 2 O 2 assumed for the charge capacity according to the reaction formula (II) is shown by a solid line.
- FIG. 21 it was confirmed that Li 2 O 2 was generated by the charging reaction according to the reaction formula (II) with a theoretical efficiency of about 80% with respect to the charging capacity.
- FIG. 21 shows the result of plotting the detected amount of Li 2 O 2 against the charge capacity at the time of initial charge.
- the theoretical amount of Li 2 O 2 assumed for the charge capacity according to the reaction formula (II) is shown by a solid line.
- FIG. 21 it was confirmed that Li 2 O 2 was generated by the
- Preparation Example 14 (Preparation Step of Li 2 O / Fe 2 O 3 / Co 3 O 4 Positive Electrode) 2.46 g of lithium oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd.) as the positive electrode active material, 0.65 g of ⁇ -iron oxide (manufactured by Wako Pure Chemical Industries, Ltd.) as the electrode catalyst, cobalt oxide (Co 3 O 4 , 0.67 g (manufactured by Kojun Pharmaceutical Co., Ltd.) was put in a pot for a planetary ball mill and mixed with a planetary ball mill (mixing conditions; treated with 25 zirconia balls of 10 mm ⁇ for 120 hours at a rotation speed of 600 rpm).
- Preparation Example 15 (Preparation Step of Li 2 O / Fe 2 O 3 / Co 3 O 4 Positive Electrode) 2.47 g of lithium oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd.) as the positive electrode active material, 0.33 g of ⁇ -iron oxide (manufactured by Wako Pure Chemical Industries, Ltd.) as the electrode catalyst, cobalt oxide (Co 3 O 4 , 0.33 g (manufactured by Kojun Pharmaceutical Co., Ltd.) was put in a pot for a planetary ball mill, and mixed with a planetary ball mill (mixing conditions: treated with 25 zirconia balls of 10 mm ⁇ for 120 hours at a rotation speed of 600 rpm).
- Example 16 (Charge / Discharge Test with Bipolar Cell) Using the Li 2 O / Fe 2 O 3 / Co 3 O 4 positive electrode mixture electrode prepared in Preparation Example 14 as a working electrode, a charge / discharge test was performed under the same conditions as in Example 13. The results of the charge / discharge test are shown in FIG. As shown in FIG. 25, it was shown that charging / discharging was possible using lithium oxide as a positive electrode active material.
- Example 17 (Charge / Discharge Test with Bipolar Cell) A charge / discharge test was conducted under the same conditions as in Example 13 using the Li 2 O / Fe 2 O 3 / Co 3 O 4 positive electrode mixture electrode prepared in Preparation Example 15 as a working electrode. The results of the charge / discharge test are shown in FIG. As shown in FIG. 26, it was shown that charging / discharging was possible using lithium oxide as a positive electrode active material.
- Example 18 (Charge / Discharge Test with Bipolar Cell) Instead of 4.2M LiTFSI acetonitrile electrolyte (LiTFSI: lithium bistrifluoromethanesulfonylimide [LiN (SO 2 CF 3 ) 2 ]) in the electrolyte, 4.2M LiFSI acetonitrile electrolyte (LiFSI: lithium bisfluorosulfonylimide [LiN The charge / discharge test was conducted under the same conditions as in Example 13 except that (SO 2 F) 2 ]) was used. The results of the charge / discharge test are shown in FIG. As shown in FIG. 27, it was shown that charging / discharging was possible using lithium oxide as the positive electrode active material even under these conditions.
- Example 19 (Charge / Discharge Test with Bipolar Cell) Instead of 4.2M LiTFSI acetonitrile electrolyte (LiTFSI: lithium bistrifluoromethanesulfonylimide [LiN (SO 2 CF 3 ) 2 ]) in the electrolyte, 4.2M LiFSI acetonitrile electrolyte (LiFSI: lithium bisfluorosulfonylimide [LiN A charge / discharge test was performed under the same conditions as in Example 16 except that (SO 2 F) 2 ]) was used. The results of the charge / discharge test are shown in FIG. As shown in FIG. 28, it was shown that charging / discharging was possible using lithium oxide as the positive electrode active material even under these conditions.
- LiTFSI lithium bistrifluoromethanesulfonylimide [LiN (SO 2 CF 3 ) 2 ]
- LiFSI lithium bisfluorosulfonylimide [LiN
- Example 20 (Charge / Discharge Test Using a Bipolar Cell) Instead of 4.2M LiTFSI acetonitrile electrolyte (LiTFSI: lithium bistrifluoromethanesulfonylimide [LiN (SO 2 CF 3 ) 2 ]) in the electrolyte, 4.2M LiFSI acetonitrile electrolyte (LiFSI: lithium bisfluorosulfonylimide [LiN A charge / discharge test was performed under the same conditions as in Example 17 except that (SO 2 F) 2 ]) was used. The results of the charge / discharge test are shown in FIG. As shown in FIG. 29, it was shown that charging / discharging was possible using lithium oxide as the positive electrode active material even under these conditions.
- LiTFSI lithium bistrifluoromethanesulfonylimide [LiN (SO 2 CF 3 ) 2 ]
- LiFSI lithium bisfluorosulfonylimide [LiN
- Example 21 (charging test with a bipolar cell) The charge test was performed using a commercially available bipolar cell (HS cell, manufactured by Hosen Co., Ltd.). Li 2 O / Fe 2 O 3 / Co 3 O 4 positive electrode mixture electrode prepared in Preparation Example 13 was used for the working electrode, lithium metal was used for the counter electrode, and 4.2 M LiTFSI acetonitrile electrolyte (LiTFSI) was used for the electrolyte. : Lithium bistrifluoromethanesulfonylimide [LiN (SO 2 CF 3 ) 2 ]) was used. The positive electrode active material was charged at a current density of 4.5 mA / g. The result of the charge test is shown in FIG.
- Example 22 (charging test with a bipolar cell) The charge test was performed using a commercially available bipolar cell (HS cell, manufactured by Hosen Co., Ltd.). Li 2 O / Fe 2 O 3 / Co 3 O 4 positive electrode mixture electrode prepared in Preparation Example 14 was used as the working electrode, lithium metal was used as the counter electrode, and 4.2 M LiTFSI acetonitrile electrolyte (LiTFSI) was used as the electrolyte. : Lithium bistrifluoromethanesulfonylimide [LiN (SO 2 CF 3 ) 2 ]) was used. The positive electrode active material was charged at a current density of 4.5 mA / g. The result of the charge test is shown in FIG.
- Example 23 (charging test with a bipolar cell) The charge test was performed using a commercially available bipolar cell (HS cell, manufactured by Hosen Co., Ltd.). Li 2 O / Fe 2 O 3 / Co 3 O 4 positive electrode mixture electrode prepared in Preparation Example 15 was used as the working electrode, lithium metal was used as the counter electrode, and 4.2 M LiTFSI acetonitrile electrolyte (LiTFSI) was used as the electrolyte. : Lithium bistrifluoromethanesulfonylimide [LiN (SO 2 CF 3 ) 2 ]) was used. The positive electrode active material was charged at a current density of 4.5 mA / g. The result of the charge test is shown in FIG.
- Preparation Example 16 (Preparation process of Li 2 O / Co 3 O 4 positive electrode) 2.09 g of lithium oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd.) as the positive electrode active material and 2.23 g of cobalt oxide (Co 3 O 4 , manufactured by Wako Pure Chemical Industries, Ltd.) as the electrode catalyst are used in a pot for a planetary ball mill. Then, planetary ball mill mixing (mixing conditions: treatment using 180 10 mm ⁇ zirconia balls for 180 hours at a rotation speed of 600 rpm) was performed. All operations were performed in a glove box with a water concentration of 1 ppm or less, which was purged with argon. The XRD measurement result of the obtained solid powder is shown in FIG.
- the presence of Li 2 O and LiCoO 2 was confirmed.
- 57 mg of the obtained solid powder, 69 mg of acetylene black as a conductive assistant, and 6 mg of polytetrafluoroethylene powder as a binder were mixed in an agate mortar and processed into a clay to obtain a positive electrode mixture.
- the obtained positive electrode mixture was pressure-bonded to a 60 mg aluminum mesh to obtain a positive electrode.
- Preparation Example 17 Li 2 O / Co 3 O 4 positive electrode preparation step
- 2.19 g of lithium oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd.) as the positive electrode active material and 1.16 g of cobalt oxide (Co 3 O 4 , manufactured by Wako Pure Chemical Industries, Ltd.) as the electrode catalyst are used in a planetary ball mill pot.
- planetary ball mill mixing mixing conditions: treatment using 180 10 mm ⁇ zirconia balls for 180 hours at a rotation speed of 600 rpm
- All operations were performed in a glove box with a water concentration of 1 ppm or less, which was purged with argon.
- the XRD measurement result of the obtained solid powder is shown in FIG.
- the presence of Li 2 O and LiCoO 2 was confirmed.
- 67 mg of the obtained solid powder, 70 mg of acetylene black as a conductive additive, and 6 mg of polytetrafluoroethylene powder as a binder were mixed in an agate mortar and processed into a clay to obtain a positive electrode mixture.
- the obtained positive electrode mixture was pressure-bonded to a 60 mg aluminum mesh to obtain a positive electrode.
- Example 24 (Charge / Discharge Test Using a Bipolar Cell) Using the Li 2 O / Co 3 O 4 positive electrode mixture electrode prepared in Preparation Example 16 as a working electrode, a charge / discharge test was performed under the same conditions as in Example 13. The results of the charge / discharge test are shown in FIG. As shown in FIG. 35, it was shown that charging / discharging was possible using lithium oxide as a positive electrode active material.
- Example 25 (Charge / Discharge Test Using a Bipolar Cell) A charge / discharge test was performed under the same conditions as in Example 13 using the Li 2 O / Co 3 O 4 positive electrode mixture electrode prepared in Preparation Example 17 as a working electrode. The result of the charge / discharge test is shown in FIG. As shown in FIG. 36, it was shown that charging / discharging was possible using lithium oxide as a positive electrode active material.
- Example 26 (Charge / Discharge Test Using a Bipolar Cell) Instead of 4.2M LiTFSI acetonitrile electrolyte (LiTFSI: lithium bistrifluoromethanesulfonylimide [LiN (SO 2 CF 3 ) 2 ]) in the electrolyte, 4.2M LiFSI acetonitrile electrolyte (LiFSI: lithium bisfluorosulfonylimide [LiN The charge / discharge test was conducted under the same conditions as in Example 24 except that (SO 2 F) 2 ]) was used. The result of the charge / discharge test is shown in FIG. As shown in FIG. 37, it was shown that charging / discharging was possible using lithium oxide as the positive electrode active material even under these conditions.
- LiTFSI lithium bistrifluoromethanesulfonylimide [LiN (SO 2 CF 3 ) 2 ]
- LiFSI lithium bisfluorosulfonylimide [LiN
- Example 27 (Charge / Discharge Test Using a Bipolar Cell) Instead of 4.2M LiTFSI acetonitrile electrolyte (LiTFSI: lithium bistrifluoromethanesulfonylimide [LiN (SO 2 CF 3 ) 2 ]) in the electrolyte, 4.2M LiFSI acetonitrile electrolyte (LiFSI: lithium bisfluorosulfonylimide [LiN The charge / discharge test was conducted under the same conditions as in Example 25 except that (SO 2 F) 2 ]) was used. The results of the charge / discharge test are shown in FIG. As shown in FIG. 38, it was shown that charging / discharging was possible using lithium oxide as the positive electrode active material even under these conditions.
- LiTFSI lithium bistrifluoromethanesulfonylimide [LiN (SO 2 CF 3 ) 2 ]
- LiFSI lithium bisfluorosulfonylimide [LiN
- Preparation Example 18 (Preparation process of Li 2 O / Co 3 O 4 positive electrode) 2.43 g of lithium oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd.) as the positive electrode active material and 0.66 g of cobalt oxide (Co 3 O 4 , manufactured by Wako Pure Chemical Industries, Ltd.) as the electrode catalyst are used in a pot for a planetary ball mill. Then, planetary ball mill mixing (mixing conditions: treatment using 180 10 mm ⁇ zirconia balls for 180 hours at a rotation speed of 600 rpm) was performed. All operations were performed in a glove box with a water concentration of 1 ppm or less, which was purged with argon. The XRD measurement result of the obtained solid powder is shown in FIG.
- the presence of Li 2 O was confirmed in the obtained solid powder.
- 51 mg of the obtained solid powder, 63 mg of acetylene black as a conductive additive, and 4 mg of polytetrafluoroethylene powder as a binder were mixed in an agate mortar and processed into a clay to obtain a positive electrode mixture.
- the obtained positive electrode mixture was pressure-bonded to a 60 mg aluminum mesh to obtain a positive electrode.
- Preparation Example 19 Li 2 O / Co 3 O 4 positive electrode preparation step
- 2.63 g of lithium oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd.) as the positive electrode active material and 0.36 g of cobalt oxide (Co 3 O 4 , manufactured by Wako Pure Chemical Industries, Ltd.) as the electrode catalyst are used in a pot for a planetary ball mill.
- planetary ball mill mixing mixing conditions: treatment using 180 10 mm ⁇ zirconia balls for 180 hours at a rotation speed of 600 rpm
- All operations were performed in a glove box with a water concentration of 1 ppm or less, which was purged with argon.
- the XRD measurement result of the obtained solid powder is shown in FIG.
- the presence of Li 2 O was confirmed in the obtained solid powder.
- 57 mg of the obtained solid powder, 61 mg of acetylene black as a conductive assistant, and 5 mg of polytetrafluoroethylene powder as a binder were mixed in an agate mortar and processed into a clay to obtain a positive electrode mixture.
- the obtained positive electrode mixture was pressure-bonded to a 60 mg aluminum mesh to obtain a positive electrode.
- Example 28 (Charge / Discharge Test Using a Bipolar Cell) A charge / discharge test was conducted under the same conditions as in Example 13 using the Li 2 O / Co 3 O 4 positive electrode mixture electrode prepared in Preparation Example 18 as a working electrode. The results of the charge / discharge test are shown in FIG. As shown in FIG. 41, it was shown that charging / discharging was possible using lithium oxide as a positive electrode active material.
- Example 29 (Charge / Discharge Test Using a Bipolar Cell) Using the Li 2 O / Co 3 O 4 positive electrode mixture electrode prepared in Preparation Example 19 as a working electrode, a charge / discharge test was performed under the same conditions as in Example 13. The results of the charge / discharge test are shown in FIG. As shown in FIG. 42, it was shown that charging / discharging was possible using lithium oxide as a positive electrode active material.
- Example 30 (Charge / Discharge Test Using a Bipolar Cell) Instead of 4.2M LiTFSI acetonitrile electrolyte (LiTFSI: lithium bistrifluoromethanesulfonylimide [LiN (SO 2 CF 3 ) 2 ]) in the electrolyte, 4.2M LiFSI acetonitrile electrolyte (LiFSI: lithium bisfluorosulfonylimide [LiN A charge / discharge test was performed under the same conditions as in Example 28 except that (SO 2 F) 2 ]) was used. The results of the charge / discharge test are shown in FIG. As shown in FIG. 43, it was shown that charging / discharging was possible using lithium oxide as the positive electrode active material even under these conditions.
- LiTFSI lithium bistrifluoromethanesulfonylimide [LiN (SO 2 CF 3 ) 2 ]
- LiFSI lithium bisfluorosulfonylimide [LiN
- Example 31 (Charge / Discharge Test Using a Bipolar Cell) Instead of 4.2M LiTFSI acetonitrile electrolyte (LiTFSI: lithium bistrifluoromethanesulfonylimide [LiN (SO 2 CF 3 ) 2 ]) in the electrolyte, 4.2M LiFSI acetonitrile electrolyte (LiFSI: lithium bisfluorosulfonylimide [LiN The charge / discharge test was conducted under the same conditions as in Example 29 except that (SO 2 F) 2 ]) was used. The results of the charge / discharge test are shown in FIG. As shown in FIG. 44, it was shown that charging / discharging was possible using lithium oxide as the positive electrode active material even under these conditions.
- LiTFSI lithium bistrifluoromethanesulfonylimide [LiN (SO 2 CF 3 ) 2 ]
- LiFSI lithium bisfluorosulfonylimide [LiN
- Example 32 (XRD analysis of positive electrode after charging) A charge test was performed under the same conditions as in Example 27. After charging with 400 mAh / g, the positive electrode was washed with an acetonitrile solvent and then dried. The obtained positive electrode after charging was placed in an airtight sample table filled with argon, and XRD measurement was performed. The results are shown in FIG. Attenuation of the Li 2 O signal around 33.5 ° was observed depending on the oxidation capacity. Li 2 O in the charging process from these it was shown to be converted to Li 2 O 2.
- Example 33 Quantification of Li 2 O 2 contained in positive electrode after charge / discharge
- a charge / discharge test was conducted under the same conditions as in Example 27.
- the quantification of lithium peroxide contained in the positive electrode was performed in the same manner as in Example 11 for each charge / discharge.
- the amount of lithium peroxide contained in the mixture after the first charge was 4.17 mmol / g per weight of lithium oxide contained in the mixture initially.
- the amount of lithium peroxide contained in the mixture after the first discharge after the first charge is 0.17 mmol / g per weight of lithium oxide contained in the mixture initially, It was confirmed that lithium peroxide was consumed. Further, the amount of lithium peroxide contained after the second charge was 3.89 mmol / g, indicating that it was reversibly oxidized to lithium peroxide again by charging.
- Preparation Example 20 Li 2 O / CoO positive electrode preparation step
- 2.30 g of lithium oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd.) as the positive electrode active material and 2.31 g of cobalt oxide (CoO, manufactured by Wako Pure Chemical Industries, Ltd.) as the electrode catalyst are placed in a planetary ball mill pot.
- Ball mill mixing mixing conditions: treatment using 180 10 mm ⁇ zirconia balls at 180 rpm for 180 hours
- All operations were performed in a glove box with a water concentration of 1 ppm or less, which was purged with argon.
- the XRD measurement result of the obtained solid powder is shown in FIG. The presence of Li 2 O was confirmed in the obtained solid powder.
- Preparation Example 21 Li 2 O / CoO positive electrode preparation step
- 2.30 g of lithium oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd.) as the positive electrode active material and 1.15 g of cobalt oxide (CoO, manufactured by Wako Pure Chemical Industries, Ltd.) as the electrode catalyst are placed in a planetary ball mill pot.
- Ball mill mixing mixing conditions: treatment using 180 10 mm ⁇ zirconia balls at 180 rpm for 180 hours
- All operations were performed in a glove box with a water concentration of 1 ppm or less, which was purged with argon.
- the XRD measurement result of the obtained solid powder is shown in FIG. The presence of Li 2 O was confirmed in the obtained solid powder.
- Preparation Example 22 Li 2 O / CoO positive electrode preparation step
- 2.95 g of lithium oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd.) as a positive electrode active material and 0.75 g of cobalt oxide (CoO, manufactured by Wako Pure Chemical Industries, Ltd.) as an electrode catalyst are placed in a pot for a planetary ball mill.
- Ball mill mixing mixing conditions: treatment using 180 10 mm ⁇ zirconia balls at 180 rpm for 180 hours
- All operations were performed in a glove box with a water concentration of 1 ppm or less, which was purged with argon.
- the XRD measurement result of the obtained solid powder is shown in FIG. The presence of Li 2 O was confirmed in the obtained solid powder.
- Preparation Example 23 Li 2 O / CoO positive electrode preparation step
- a planetary ball mill pot 3.09 g of lithium oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd.) as the positive electrode active material and 0.39 g of cobalt oxide (CoO, manufactured by Wako Pure Chemical Industries, Ltd.) as the electrode catalyst were placed in the planetary ball mill.
- Ball mill mixing (mixing conditions: treatment using 180 10 mm ⁇ zirconia balls at 180 rpm for 180 hours) was performed. All operations were performed in a glove box with a water concentration of 1 ppm or less, which was purged with argon.
- the XRD measurement result of the obtained solid powder is shown in FIG.
- the presence of Li 2 O was confirmed in the obtained solid powder.
- 87 mg of the obtained solid powder, 94 mg of acetylene black as a conductive assistant, and 7 mg of polytetrafluoroethylene powder as a binder were mixed in an agate mortar and processed into a clay to obtain a positive electrode mixture.
- the obtained positive electrode mixture was pressure-bonded to a 60 mg aluminum mesh to obtain a positive electrode.
- Example 34 (Charge / Discharge Test Using a Bipolar Cell) Instead of 4.2M LiTFSI acetonitrile electrolyte (LiTFSI: lithium bistrifluoromethanesulfonylimide [LiN (SO 2 CF 3 ) 2 ]) in the electrolyte, 4.2M LiFSI acetonitrile electrolyte (LiFSI: lithium bisfluorosulfonylimide [LiN A charge / discharge test was performed under the same conditions as in Example 28 except that (SO 2 F) 2 ]) was used. The results of the charge / discharge test are shown in FIG. As shown in FIG. 50, it was shown that charging / discharging was possible using lithium oxide as the positive electrode active material even under these conditions.
- Example 35 (Charge / Discharge Test Using a Bipolar Cell) Instead of 4.2M LiTFSI acetonitrile electrolyte (LiTFSI: lithium bistrifluoromethanesulfonylimide [LiN (SO 2 CF 3 ) 2 ]) in the electrolyte, 4.2M LiFSI acetonitrile electrolyte (LiFSI: lithium bisfluorosulfonylimide [LiN The charge / discharge test was conducted under the same conditions as in Example 29 except that (SO 2 F) 2 ]) was used. The results of the charge / discharge test are shown in FIG. As shown in FIG. 51, it was shown that charging / discharging was possible using lithium oxide as the positive electrode active material even under these conditions.
- LiTFSI lithium bistrifluoromethanesulfonylimide [LiN (SO 2 CF 3 ) 2 ]
- LiFSI lithium bisfluorosulfonylimide [LiN
- Example 36 (Charge / Discharge Test Using a Bipolar Cell) Instead of 4.2M LiTFSI acetonitrile electrolyte (LiTFSI: lithium bistrifluoromethanesulfonylimide [LiN (SO 2 CF 3 ) 2 ]) in the electrolyte, 4.2M LiFSI acetonitrile electrolyte (LiFSI: lithium bisfluorosulfonylimide [LiN (SO 2 F) 2 ]) was used, and a charge / discharge test was performed under the same conditions as in Example 28 except that the active material was charged / discharged at a current density of 22.5 mA / g. The results of the charge / discharge test are shown in FIG. As shown in FIG. 52, it was shown that charging / discharging was possible using lithium oxide as the positive electrode active material even under these conditions.
- LiTFSI lithium bistrifluoromethanesulfonylimide [LiN (SO 2 CF 3
- Example 37 (Charge / Discharge Test Using a Bipolar Cell) Instead of 4.2M LiTFSI acetonitrile electrolyte (LiTFSI: lithium bistrifluoromethanesulfonylimide [LiN (SO 2 CF 3 ) 2 ]) in the electrolyte, 4.2M LiFSI acetonitrile electrolyte (LiFSI: lithium bisfluorosulfonylimide [LiN (SO 2 F) 2 ]) was used, and a charge / discharge test was performed under the same conditions as in Example 29 except that the active material was charged / discharged at a current density of 22.5 mA / g. The results of the charge / discharge test are shown in FIG. As shown in FIG. 53, it was shown that charging / discharging was possible using lithium oxide as the positive electrode active material even under these conditions.
- LiTFSI lithium bistrifluoromethanesulfonylimide [LiN (SO 2 CF 3
- the battery including the positive electrode in the present invention has a high theoretical voltage and theoretical capacity, and can be repeatedly charged and discharged. Moreover, in the said Example, it is the same as all the mechanism of action which has the effect that it has a high theoretical voltage and theoretical capacity
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Abstract
Description
AxOy (1)
(式中、Aは、アルカリ金属原子を表す。x=0.5~2.5、y=0.5~2.5を表す。)で表されるアルカリ金属化合物を含んでなる正極活物質を含有し、該負極は、アルカリ金属、錫、チタン、ホウ素、窒素、ケイ素、及び、炭素からなる群より選ばれる少なくとも一種を含んでなる負極活物質を含有し、該電池は、正極、負極、及び、電解質が密閉されていることを特徴とする電池である。
なお、以下において記載する本発明の個々の好ましい形態を2つ以上組み合わせたものもまた、本発明の好ましい形態である。
AxOy (1)
(式中、Aは、アルカリ金属原子を表す。x=0.5~2.5、y=0.5~2.5を表す。)で表されるアルカリ金属化合物を含んでなる正極活物質を含有し、該負極は、アルカリ金属、錫、チタン、ホウ素、窒素、ケイ素、及び、炭素からなる群より選ばれる少なくとも一種を含んでなる負極活物質を含有し、該電池は、正極、負極、及び、電解質が密閉されていることを特徴とするものである。
なお、本発明において、正極、負極、及び、電解質が密閉されているとは、電池の外部への放電や電池への充電の際に外部と接続する正極、負極の一部分を除き、正極、負極の残りの部分、及び、電解質が外気と接触しない状態にあることをいう。
負極での反応:A⇔A++e- (I)
正極での反応:A2O2+2A++2e-⇔2A2O (II)
全体の反応:A+1/2A2O2⇔A2O (III)
このような正極、負極での反応を組み合わせた電池はこれまで知られておらず、本発明の電池は、このような新たな原理による電池である。
負極での反応:Li⇔Li++e-
正極での反応:Li2O2+2Li++2e-⇔2Li2O
全体の反応:Li+1/2Li2O2⇔Li2O
AxOy (1)
(式中、Aは、アルカリ金属原子を表す。x=0.5~2.5、y=0.5~2.5を表す。)で表されるアルカリ金属化合物を含んでなる正極活物質を含有するものである。
式(1)におけるAのアルカリ金属原子としては、Li、Na、K、Rb、Cs、Frが挙げられる。理論容量の点から、好ましくはLi、Na、Kであり、より好ましくはLi、Naであり、更に好ましくはLiである。
式(1)において、x=1又は2であることが好ましく、また、y=1又は2であることが好ましい。
上記アルカリ金属化合物としては、アルカリ金属酸化物(A2O;つまりx=2、y=1)、アルカリ金属過酸化物(A2O2;つまりx=2、y=2)、アルカリ金属超酸化物(AO2;つまりx=1、y=2)がより好ましく、アルカリ金属酸化物、アルカリ金属過酸化物が更に好ましい。
上記アルカリ金属化合物は、1種でも2種以上でも用いることができる。
上記式(1)で表されるアルカリ金属化合物の含有量は、理論容量の点から、1質量%以上がより好ましく、3質量%以上が更に好ましく、5質量%以上が特に好ましい。また、その上限としては、特に限定されないが、電気伝導性の点から、99.99質量%以下が好ましく、99.9質量%以下がより好ましい。
なお、本明細書中、活物質層の質量は、正極(又は負極)が集電体と活物質層とから構成される場合、集電体を除いた正極(又は負極)全体の質量を言う。
A2O2 (2)
(式中、Aは、アルカリ金属原子を表す。)で表されるアルカリ金属過酸化物を1質量%以上含むことが好ましい。このような割合で含むことにより、上記反応式(II)の反応が本発明の電池の正極反応の主反応(正極反応全体の50%以上)となり、本発明の電池が上述した利点をより充分に発揮することができるものとなる。
正極の活物質層の質量に対する上記式(2)で表されるアルカリ金属過酸化物の割合は、より好ましくは1~99.999質量%であり、更に好ましくは20~99.9質量%である。
上記式(2)中のAのアルカリ金属原子としては、上述の式(1)中のAのアルカリ金属原子の例示と同じものが挙げられる。
A2O2 (2)
(式中、Aは、アルカリ金属原子を表す。)で表されるアルカリ金属過酸化物に対する、負極に含まれるアルカリ金属のモル比が、100以下であることが好ましい。
本発明の電池では、充電反応時には、負極、正極ではそれぞれ上記反応式(I)、(II)の右側から左側への反応がおこり、完全充電時には、負極活物質は全てアルカリ金属イオンからアルカリ金属となり、正極活物質は上記式(2)で表されるA2O2となる。上述したように、本発明の電池は、正極活物質としてアルカリ金属化合物以外の他の化合物も用いることができるが、正極反応全体に対して、上記反応式(II)で表される反応が主反応(正極反応全体の50%以上)となることが好ましく、完全充電時の正極中にA2O2が所定の割合で含まれていることが好ましい。したがって、完全充電時の上記式(2)で表されるアルカリ金属過酸化物に対する負極に含まれるアルカリ金属のモル比、すなわち、(A/A2O2)は、100以下であることが好ましい。(A/A2O2)がこのような値であることにより、本発明の電池は、上述した種々の特性により優れたものとなる。なお、ここでいう「負極に含まれるアルカリ金属」とは、充放電に関与するアルカリ金属を意味する。すなわち、完全充電時における負極に含まれるアルカリ金属から完全放電時における負極に含まれるアルカリ金属を除いたものを意味する。
また、正極活物質としてアルカリ金属化合物を、負極活物質としてアルカリ金属、錫、チタン、ホウ素、窒素、ケイ素、及び、炭素からなる群より選ばれる少なくとも一種を用いているため、本発明の電池は、レアメタルを使用することなく構成することが可能であり、低コストで製造することができ、元素戦略的にも有利な電池である。
上述した本発明の電池における正極反応式(II)のA2OからA2O2への反応(右側から左側への反応)は、これまでに知られていない反応である。本発明の電池で充放電を円滑に進めるため、この反応が、リチウム空気電池の正極での反応(O2+4Li++4e-⇔2Li2O)の右側から左側への反応よりも、低い過電圧で進行するようにすることが好ましい。正極の活物質層において電極用触媒を用いることで、上記正極反応式(II)のA2OからA2O2への反応(具体的にはLi2OからLi2O2への反応等)を、より低い過電圧で進行させることが可能となる。
上記周期律表における第1~17族に属する元素としては、Li、Na、K、Rb、Cs、Ca、Sr、Ba、Y、La、Ce、Pr、Nd、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Zr、Nb、Mo、Ag、In、Sn、Sb、Hf、Ta、W、Pb、Bi、Si、P、S、Ru、Rh、Pd、W、Re、Os、Ir、Pt、Au、O、S、F、Cl、Cが挙げられる。より好ましくは、周期律表における第5~11族に属する元素である。該周期律表における第5~11族に属する元素としては、更に好ましくは、V、Cr、Mn、Fe、Co、Ni、Cu、Nb、Mo、Ru、Rh、Pd、Ag、Ta、W、Re、Os、Ir、Pt、Au、Cである。更により好ましくは、Ag、Au、Cu、Fe、Mn、Co、Ni、Cである。
MaOb (3)
(式中、Mは、アルカリ金属原子以外の金属原子を表す。aは、1~3の数を表し、bは、1~4の数を表す。)
上記アルカリ金属原子以外の金属原子としては、Ca、Sr、Ba、Y、La、Ce、Pr、Nd、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Zr、Nb、Mo、Ag、In、Sn、Sb、Hf、Ta、W、Pb、Bi、Si、P、Sが好ましいものとして挙げられる。より好ましくは、V、Cr、Mn、Fe、Co、Ni、Cu、Nb、Mo、Ag、Ta、Wである。更に好ましくは、Mn、Co、又は、Niである。
式(3)において、aは、1、2、又は、3であることが好ましく、また、bは、1、2、3、又は、4であることが好ましい。
上記単一酸化物としては、MO(つまりa=1、b=1)、MO2(つまりa=1、b=2)、M2O3(つまりa=2、b=3)、又は、M3O4(つまりa=3、b=4)がより好ましい。
上記電極用触媒は、1種でも2種以上でも用いることができる。
QROn (4)
(式中、Qは、周期律表における第1~3族に属する元素からなる群より選択される少なくとも1種の元素を表す。Rは、周期律表における第4~15族に属する元素からなる群より選択される少なくとも1種の元素を表す。nは、1~3の数を表す。)
上記式(4)におけるQの周期律表における第1~3族に属する元素としては、Li、Na、K、Rb、Cs、Ca、Sr、Ba、Y、La、Ce、Pr、Ndが挙げられる。中でも、第1~2族に属する元素が好ましい。該第1~2族に属する元素は、より好ましくは、Li又はSrである。
上記式(4)におけるRの周期律表における第4~16族に属する元素としては、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Zr、Nb、Mo、Ag、In、Sn、Sb、Hf、Ta、W、Pb、Bi、Si、P、Sが挙げられる。特に好ましくは、Fe又はCoである。
nは、1~3の数を表し、好ましくは2~3の数である。より好ましくは、2又は2.5である。
上記電極用触媒は、1種でも2種以上でも用いることができる。
上記「1.アルカリ金属化合物の調製工程」で得られるアルカリ金属化合物の代わりに市販の化合物を用いてもよく、その場合は1.の調製工程を省略することができる。
微粉化する方法は特に制限されず、乳鉢、ビーズミル、ボールミル、カッターミル、ディスクミル、スタンプミル、ハンマーミル、ジェットミル等を使用することができる。
アルカリ金属を平均粒子径が0.01~2μmに微粉化する工程は、アルカリ金属に空気を作用させる工程と同時に行ってもよい。すなわち、アルカリ金属を微粉化しながら、アルカリ金属に空気を作用させてもよい。
本発明における正極材料(正極合剤)を粒子状の形態とする場合、平均粒子径が1000μm以下である粒子とすることが好ましい。
先ず、正極合剤を必要により水及び/又は有機溶媒と、上記電極用触媒や、下記導電助剤や有機化合物と共に混練し、ペースト状とする。次に、得られたペースト混合物を、集電体である、アルミ箔等の金属箔やアルミニウムメッシュ・ニッケルメッシュ等の金属メッシュ上に、できる限り膜厚が一定になるように塗工する。塗工後、0~250℃で乾燥することが好ましい。乾燥温度として、より好ましくは15~200℃である。乾燥は、真空乾燥を行ってもよい。また、乾燥後に0.0001~20tの圧力で、ロールプレス機等によりプレスを行ってもよい。プレスする圧力として、より好ましくは0.001~15tである。更に好ましくは、0.01t以上であり、特に好ましくは、0.1t以上である。
正極の膜厚は、例えば、1nm~2000μmであることが好ましい。より好ましくは10nm~1500μmであり、更に好ましくは100nm~1000μmである。
上記アルカリ金属としては、Li、Na、K、Rb、Cs、Frが挙げられる。理論容量と元素戦略の点から、好ましくはLi、Naであり、より好ましくはLiである。
上記炭素としては、例えば、黒鉛、アモルファス炭素、カーボンナノフォーム、活性炭、グラフェン、ナノグラフェン、グラフェンナノリボン、フラーレン、カーボンブラック、ファイバー状カーボン、カーボンナノチューブ、カーボンナノホーン、ケッチェンブラック、アセチレンブラック、炭素繊維、気相成長炭素繊維等が挙げられる。これらの中でも、黒鉛、グラフェン、ファイバー状カーボン、カーボンナノチューブ、アセチレンブラック、が好ましい。より好ましくは、黒鉛、グラフェン、ファイバー状カーボン、カーボンナノチューブ、アセチレンブラック、炭素繊維、気相成長炭素繊維である。
上記アルカリ金属、錫、チタン、ホウ素、窒素、ケイ素、及び、炭素からなる群より選ばれる少なくとも一種を含んでなる負極活物質の合計含有量は、負極に含まれる活物質層の質量(100質量%)に対して、1.0質量%以上であることが、理論容量の点から好ましい。より好ましくは2.0~100質量%であり、更に好ましくは30~100質量%である。特に好ましくは、90質量%以上である。
導電助剤、有機化合物については後述する。
電解質としては、例えば、LiPF6、LiBF4、LiClO4、LiN(SO2F)2、LiN(SO2CF3)2、LiN(SO2C2F5)2、Li(BC4O8)、LiF、LiB(CN)4、NaPF6、NaBF4、NaClO4、NaN(SO2F)2、NaN(SO2CF3)2、NaN(SO2C2F5)2、Na(BC4O8)、NaF、NaB(CN)4、水酸化カリウム、水酸化ナトリウム、炭酸リチウム、水酸化リチウム、フッ化カリウム、ホウ酸カリウム等が挙げられる。好ましくはLiPF6、LiBF4、LiClO4、LiN(SO2F)2、LiN(SO2CF3)2、LiN(SO2C2F5)2、Li(BC4O8)、LiF、LiB(CN)4である。
また、電解液は添加剤を含んでいてもよい。添加剤としては、例えば正極や負極の保護皮膜を形成する材料や、プロピレンカーボネートを電解液に使用した場合に、プロピレンカーボネートの黒鉛への挿入を抑制する材料等が挙げられ、ビニレンカーボネート、フルオロエチレンカーボネート、クロロエチレンカーボネート、臭化エチレンカーボネート、エチレンサルファイト、プロピレンサルファイト、クラウンエーテル類、ホウ素含有アニオンレセプター類、アルミニウム含有アニオンレセプター等が挙げられる。添加剤は、上記1種又は2種以上使用してもよい。
上記導電助剤としては、電子材料となり得る導電性を有する物質であることが好ましく、具体的には、金属、導電性セラミックス、炭素材料からなることが好ましい。金属としては、ニッケル粉、アルミニウム粉、亜鉛粉、金粉、メソポーラス金等が挙げられる。炭素材料(導電性カーボン)としては、黒鉛、アモルファス炭素、カーボンナノフォーム、活性炭、グラフェン、ナノグラフェン、グラフェンナノリボン、フラーレン、カーボンブラック、ファイバー状カーボン、カーボンナノチューブ、カーボンナノホーン、ケッチェンブラック、アセチレンブラック、炭素繊維、気相成長炭素繊維等が挙げられる。これらの中でも、グラフェン、ファイバー状カーボン、カーボンナノチューブ、アセチレンブラック、炭素繊維、気相成長炭素繊維が好ましい。上記導電助剤は、より好ましくは、グラフェン、ファイバー状カーボン、カーボンナノチューブ、アセチレンブラック、金属亜鉛、金粉、メソポーラス金である。
上記導電助剤は、電極における導電性を向上させる作用を有するものであり、1種又は2種以上を用いることが出来る。上記アルカリ金属化合物をカーボンコートすることにより、導電性を向上させてもよい。また、正極での反応式(II)の反応の過電圧低減のための触媒能を有していてもよい。
上記有機化合物、有機化合物塩は、粒子同士や粒子と集電体とを結着させる結着剤やそれらを効果的に分散させる分散剤として働くこともできる。
上記有機化合物、有機化合物塩としては、好ましくは、ポリ(メタ)アクリル酸塩含有ポリマー、ポリビニルアルコール含有ポリマー、ポリエチレンオキシド含有ポリマー、ポリプロピレンオキシド含有ポリマー、ポリブテンオキシド含有ポリマー、セルロース、酢酸セルロース、ヒドロキシアルキルセルロース、カルボキシメチルセルロース、ポリテトラフルオロエチレン含有ポリマー、ポリフッ化ビニリデン含有ポリマー、ポリペンタフルオロエチレン含有ポリマー、ポリマレイン酸塩含有ポリマー、ポリイタコン酸塩含有ポリマー、イオン交換膜性重合体、スルホン酸塩含有ポリマー、第四級アンモニウム塩含有ポリマー、第四級ホスホニウム塩ポリマー、等が挙げられる。
正極活物質として酸化リチウム(Li2O、Strem Chemical社製)28mg、電極用触媒(60%Ag/C、Alfa Aesar社製)80mg、ポリテトラフルオロエチレン(PTFE)15mgを混練し、正極合剤を得た。この正極合剤14mgを80mgのニッケルメッシュに圧着し、正極を得た。
電極用触媒(60%Ag/C、Alfa Aesar社製)85mg、PTFE15mgを混練し、正極合剤を得た。この正極合剤14mgを80mgのニッケルメッシュに圧着し、正極を得た。
ワーキング電極として調製例1で作製した正極を用い、カウンター電極及びリファレンス電極としてリチウム金属を用い、電解液として1M LiClO4/プロピレンカーボネート(PC)電解液を用いた三極式セルを使用し、グローブボックス中で、サイクリックボルタンメトリー(CV)を測定した。この際、電極電位を、3.38Vの開回路電圧(OCV)→4V→1.2V→OCV3.38Vのように掃引し、掃引速度を0.2mV/秒とした。
この結果を図1に示す。図1において、横軸は電位、縦軸は電流を示す。
図1の結果から、調製例1で作製した正極を用いると、約3.05V、約3.7Vに酸化波のピークが生じ、約2.25Vに還元波のピークが生じた。2Li2O→Li2O2+2Li++2e-における理論電位は2.87Vであることから、今回観測された酸化波・還元波はそれぞれ上記反応の順反応・逆反応に対応する酸化還元波であった。
ワーキング電極として調製例2で作製した正極を用いた以外は、実施例1と同様にしてサイクリックボルタンメトリー(CV)を測定した。
この結果を図2に示す。図2の結果から、調製例2で作製したLi2Oの存在しない正極を用いると、酸化波や還元波は生じなかったことがわかった。
正極活物質として酸化リチウム(Li2O、Strem Chemicals社製)44mg、人造黒鉛KS6L(TIMCAL社製)84mg、ポリテトラフルオロエチレン(PTFE)7mgを混練し、正極合剤を得た。この正極合剤6mgを80mgのニッケルメッシュに圧着し、正極を得た。
正極活物質として酸化リチウムの代わりに過酸化リチウム(Li2O2、Alfa Aesar社製)を用いた以外は調製例3と同様の方法にて、正極合剤を得た。この正極合剤6mgを80mgのニッケルメッシュに圧着し、正極を得た。
正極活物質として酸化リチウムの代わりに酸化ナトリウム(Na2O、Alfa Aesar社製)を用いた以外は調製例3と同様の方法にて、正極合剤を得た。この正極合剤6mgを80mgのニッケルメッシュに圧着し、正極を得た。
正極活物質として酸化リチウムの代わりに過酸化ナトリウム(Na2O2、和光純薬工業社製)を用いた以外は調製例3と同様の方法にて、正極合剤を得た。この正極合剤6mgを80mgのニッケルメッシュに圧着し、正極を得た。
ワーキング電極として調製例3~6で作製した正極を用い、カウンター電極及びリファレンス電極としてリチウム金属を用い、電解液としてプロピレンカーボネート(PC)電解液を用いた三極式セルを使用し、グローブボックス中で充放電試験を実施した。カットオフ電位は1.4~4.2V、活物質1モルあたり0.134アンペア電流負荷にて充放電を行った。調製例3、5で作成した正極を用いた際は充電からサイクルを実施し、調製例4、6で作成した正極を用いた際は放電からサイクルを実施した。結果を表1に示す。
正極活物質として酸化リチウム(株式会社高純度化学研究所製)1.99gと、電極用触媒となるα-酸化鉄(和光純薬工業社製)2.09gを遊星ボールミル用のポットに入れ、遊星ボールミル混合(混合条件;10mmφのジルコニアボール25個を用いて回転数600rpmにて60時間処理)を行った。作業は全てアルゴン置換された水分濃度1ppm以下のグローブボックス中で行った。得られた固体粉末のXRD測定結果を図3に示す。得られた固体粉末はLi2OとLiFeO2の混合物であった。得られた固体粉末172mg、導電助剤としてのアセチレンブラック200mg、結着剤としてのポリテトラフルオロエチレン粉末28mgをメノウ乳鉢で混合し、粘土状に加工して正極合剤を得た。得られた正極合剤を60mgのアルミニウムメッシュに圧着して正極とした。
正極活物質として酸化リチウム(株式会社高純度化学研究所製)1.43gと、電極用触媒として酸化コバルト(Co3O4、和光純薬工業社製)1.54gを遊星ボールミル用のポットに入れ、遊星ボールミル混合(混合条件;10mmφのジルコニアボール25個を用いて回転数600rpmにて60時間処理)を行った。作業は全てアルゴン置換された水分濃度1ppm以下のグローブボックス中で行った。得られた固体粉末のXRD測定結果を図4に示す。得られた固体粉末はLi2OとCo3O4の混合物であった。得られた固体粉末126mg、導電助剤としてのアセチレンブラック142mg、結着剤としてのポリテトラフルオロエチレン粉末20mgをメノウ乳鉢で混合し、粘土状に加工して正極合剤を得た。得られた正極合剤を60mgのアルミニウムメッシュに圧着して正極とした。
正極活物質として酸化リチウム(株式会社高純度化学研究所製)2.75gと、電極用触媒として酸化ニッケル(NiO、関東化学社製)2.74gを遊星ボールミル用のポットに入れ、遊星ボールミル混合(混合条件;10mmφのジルコニアボール25個を用いて回転数600rpmにて60時間処理)を行った。作業は全てアルゴン置換された水分濃度1ppm以下のグローブボックス中で行った。得られた固体粉末のXRD測定結果を図5に示す。得られた固体粉末はLi2OとNiOの混合物であった。得られた固体粉末73mg、導電助剤としてのアセチレンブラック89mg、結着剤としてのポリテトラフルオロエチレン粉末14mgをメノウ乳鉢で混合し、粘土状に加工して正極合剤を得た。得られた正極合剤を60mgのアルミニウムメッシュに圧着して正極とした。
正極活物質として酸化リチウム(株式会社高純度化学研究所製)2.32gと、電極用触媒としてコバルト酸リチウム(和光純薬工業社製)3.05gを遊星ボールミル用のポットに入れ、遊星ボールミル混合(混合条件;10mmφのジルコニアボール25個を用いて回転数600rpmにて60時間処理)を行った。作業は全てアルゴン置換された水分濃度1ppm以下のグローブボックス中で行った。得られた固体粉末のXRD測定結果を図6に示す。得られた固体粉末はLi2OとLiCoO2の混合物であった。得られた固体粉末61mg、導電助剤としてのアセチレンブラック77mg、結着剤としてのポリテトラフルオロエチレン粉末10mgをメノウ乳鉢で混合し、粘土状に加工して正極合剤を得た。得られた正極合剤を60mgのアルミニウムメッシュに圧着して正極とした。
正極活物質として酸化リチウム(株式会社高純度化学研究所製)1.90gと、電極用触媒として二酸化マンガン(和光純薬工業社製)2.22gを遊星ボールミル用のポットに入れ、遊星ボールミル混合(混合条件;10mmφのジルコニアボール25個を用いて回転数600rpmにて60時間処理)を行った。作業は全てアルゴン置換された水分濃度1ppm以下のグローブボックス中で行った。得られた固体粉末のXRD測定結果を図7に示す。得られた固体粉末はLi2OとMnO2の混合物であった。得られた固体粉末113mg、導電助剤としてのアセチレンブラック134mg、結着剤としてのポリテトラフルオロエチレン粉末21mgをメノウ乳鉢で混合し、粘土状に加工して正極合剤を得た。得られた正極合剤を60mgのアルミニウムメッシュに圧着して正極とした。
炭酸ストロンチウム(和光純薬工業社製)4.43gと酸化コバルト(Co3O4、和光純薬工業社製)2.41gをメノウ乳鉢で混合し空気雰囲気にて900℃12時間焼成を行うことで酸素欠損型ペロブスカイト化合物であるSrCoO2.5を得た。
正極活物質として酸化リチウム(株式会社高純度化学研究所製)0.98gと、電極用触媒として上記で得られたSrCoO2.50.48gを遊星ボールミル用のポットに入れ、遊星ボールミル混合(混合条件;10mmφのジルコニアボール25個を用いて回転数600rpmにて60時間処理)を行った。作業は全てアルゴン置換された水分濃度1ppm以下のグローブボックス中で行った。得られた固体粉末のXRD測定結果を図8に示す。得られた固体粉末はLi2OとアモルファスとなったSrCoO2.5の混合物であった。得られた固体粉末35mg、導電助剤としてのアセチレンブラック46mg、結着剤としてのポリテトラフルオロエチレン粉末7mgをメノウ乳鉢で混合し、粘土状に加工して正極合剤を得た。得られた正極合剤を60mgのアルミニウムメッシュに圧着して正極とした。
充放電試験は従来の三極式セルを用いて行った。ワーキング電極に調製例7において作成したLi2O/Fe2O3正極合剤電極、カウンター電極、リファレンス電極にはリチウム金属を使用し、電解液には1M LiTFSI DME電解液(LiTFSI:リチウムビストリフルオロメタンスルホニルイミド〔LiN(SO2CF3)2〕、DME:1,2-ジメトキシエタン)を使用した。正極活物質に対して4.5mA/gの電流密度で充電を行った後に同様の電流密度にて放電を行った。充放電試験の結果を図9に示す。図9に示すように酸化リチウムを正極活物質として繰り返し充放電が可能であることが示された。
調製例8において作成したLi2O/Co3O4正極合剤電極をワーキング電極として、実施例3と同様の条件により充放電試験を行った。その測定結果を図10に示す。図10に示すように酸化リチウムを正極活物質として充放電が可能であることが示された。
調製例9において作成したLi2O/NiO正極合剤電極をワーキング電極として、実施例3と同様の条件により充放電試験を行った。その測定結果を図11に示す。図11に示すように酸化リチウムを正極活物質として充放電が可能であることが示された。
調製例10において作成したLi2O/LiCoO2正極合剤電極をワーキング電極として、実施例3と同様の条件により充放電試験を行った。その測定結果を図12に示す。図12に示すように酸化リチウムを正極活物質として充放電が可能であることが示された。
調製例11において作成したLi2O/MnO2正極合剤電極をワーキング電極として、実施例3と同様の条件により充放電試験を行った。その測定結果を図13に示す。図13に示すように酸化リチウムを正極活物質として充放電が可能であることが示された。
調製例12において作成したLi2O/SrCoO2.5正極合剤電極をワーキング電極として、実施例3と同様の条件により充放電試験を行った。その測定結果を図14に示す。図14に示すように酸化リチウムを正極活物質として充放電が可能であることが示された。
実施例3と同様の条件により充電試験を行い、セル中に含まれる気相成分を四重極質量分析計により同定・定量を行った。その測定結果を図15に示す。図15に示すように酸化容量として600mAh/gまで有意なガス発生は見られず、Li2Oが酸素発生せずにLi2O2に転化していることが示された。なお、図15中、矢印は、グラフが右側の縦軸の目盛りと左側の縦軸の目盛りのいずれを示すのかを指し示している。
実施例5と同様の条件にて充電試験を行った。カットオフ電圧は3.3Vとし充電後の正極をDME(1,2-ジメトキシエタン)溶媒にて洗浄した後に乾燥した。得られた充電後の正極をアルゴン封入した気密試料台に入れXRD測定を行った。結果を図16に示す。酸化容量に応じて33.5°付近のLi2Oのシグナルが減衰し、34.5°、39.8°にLi2O2のシグナルを確認した。これらのことから充電過程でLi2OがLi2O2に転化したことが示された。
実施例4と同様の条件にて充電試験を行った。8.24mgの正極合剤を60mgのアルミニウムメッシュに圧着し正極とした。カットオフ電圧は3.3Vとし充電後の正極をDME(1,2-ジメトキシエタン)溶媒にて洗浄した後に乾燥した。アルゴン雰囲気のグローブボックス中にて得られた酸化後の正極と二酸化マンガン1mgを脱酸素した水1mlに分散させた。Li2Oから充電によって得られたLi2O2が水に溶解しH2O2となった後に二酸化マンガンを触媒として(H2O2→H2O+0.5O2)の反応を介して発生した酸素ガスを四重極質量分析計により同定・定量を行った。その結果2.3μモルの酸素発生が見られたことから、Li2Oの充電反応によりLi2O2が生成したことを確認した。
充放電試験は市販の2極式セル(HSセル、宝泉社製)を用いて行った。ワーキング電極に調製例7において作成したLi2O/Fe2O3正極合剤電極、カウンター電極にはリチウム金属を使用し、電解液には4.2M LiTFSI アセトニトリル電解液(LiTFSI:リチウムビストリフルオロメタンスルホニルイミド〔LiN(SO2CF3)2〕)を使用した。正極活物質に対して4.5mA/gの電流密度で充電を行った後に同様の電流密度にて放電を行った。充放電試験の結果を図17に示す。図17に示すように酸化リチウムを正極活物質として充放電が可能であることが示された。
正極活物質として酸化リチウム(株式会社高純度化学研究所製)2.62gと、電極用触媒としてα-酸化鉄(和光純薬工業社製)1.38g、酸化コバルト(Co3O4、和光純薬工業社製)1.36gを遊星ボールミル用のポットに入れ、遊星ボールミル混合(混合条件;10mmφのジルコニアボール25個を用いて回転数600rpmにて60時間処理)を行った。作業は全てアルゴン置換された水分濃度1ppm以下のグローブボックス中で行った。得られた固体粉末のXRD測定結果を図18に示す。得られた固体粉末中、Li2OとLiFeO2の存在を確認した。得られた固体粉末81mg、導電助剤としてのアセチレンブラック100mg、結着剤としてのポリテトラフルオロエチレン粉末15mgをメノウ乳鉢で混合し、粘土状に加工して正極合剤を得た。得られた正極合剤を60mgのアルミニウムメッシュに圧着して正極とした。
充放電試験は市販の2極式セル(HSセル、宝泉社製)を用いて行った。ワーキング電極に調製例13において作成したLi2O/Fe2O3/Co3O4正極合剤電極、カウンター電極にはリチウム金属を使用し、電解液には4.2M LiTFSI アセトニトリル電解液(LiTFSI:リチウムビストリフルオロメタンスルホニルイミド〔LiN(SO2CF3)2〕)を使用した。正極活物質に対して4.5mA/gの電流密度で充電を行った後に同様の電流密度にて放電を行った。充放電試験の結果を図19に示す。図19に示すように酸化リチウムを正極活物質として充放電が可能であることが示された。
実施例13と同様の条件にて充電試験を行った。カットオフ電圧は3.3Vとし充電後の正極をアセトニトリル溶媒にて洗浄した後に乾燥した。得られた充電後の正極をアルゴン封入した気密試料台に入れXRD測定を行った。結果を図20に示す。酸化容量に応じて33.5°付近のLi2Oのシグナルの減衰が見られた。これらのことから充電過程でLi2OがLi2O2に転化したことが示された。
実施例13と同様の条件にて充放電試験を行った。正極中に含まれる過酸化リチウムの定量は各充放電深度毎に実施例11と同様の手法で行った。図21に初回充電時における充電容量に対して検出されたLi2O2の量をプロットした結果を示す。併せて反応式(II)に従って充電容量に対して想定されるLi2O2の理論量を実線で図示する。図21に示すように充電容量に対して80%程度の理論効率で反応式(II)に従ってLi2O2が充電反応により生成していることが確認出来た。図22に初回充電後の初回放電時における放電容量に対して検出されたLi2O2の量をプロットした結果を示す。併せて反応式(II)に従って放電容量に対して想定されるLi2O2の理論量を実線で図示する。図22に示すように放電容量に対してほぼ100%の理論効率で反応式(II)に従ってLi2O2が消費されていることが確認出来た。
正極活物質として酸化リチウム(株式会社高純度化学研究所製)2.46gと、電極用触媒としてα-酸化鉄(和光純薬工業社製)0.65g、酸化コバルト(Co3O4、和光純薬工業社製)0.67gを遊星ボールミル用のポットに入れ、遊星ボールミル混合(混合条件;10mmφのジルコニアボール25個を用いて回転数600rpmにて120時間処理)を行った。作業は全てアルゴン置換された水分濃度1ppm以下のグローブボックス中で行った。得られた固体粉末のXRD測定結果を図23に示す。得られた固体粉末中、Li2Oの存在を確認した。得られた固体粉末79mg、導電助剤としてのアセチレンブラック83mg、結着剤としてのポリテトラフルオロエチレン粉末12mgをメノウ乳鉢で混合し、粘土状に加工して正極合剤を得た。得られた正極合剤を60mgのアルミニウムメッシュに圧着して正極とした。
正極活物質として酸化リチウム(株式会社高純度化学研究所製)2.47gと、電極用触媒としてα-酸化鉄(和光純薬工業社製)0.33g、酸化コバルト(Co3O4、和光純薬工業社製)0.33gを遊星ボールミル用のポットに入れ、遊星ボールミル混合(混合条件;10mmφのジルコニアボール25個を用いて回転数600rpmにて120時間処理)を行った。作業は全てアルゴン置換された水分濃度1ppm以下のグローブボックス中で行った。得られた固体粉末のXRD測定結果を図24に示す。得られた固体粉末中、Li2Oの存在を確認した。得られた固体粉末66mg、導電助剤としてのアセチレンブラック70mg、結着剤としてのポリテトラフルオロエチレン粉末6mgをメノウ乳鉢で混合し、粘土状に加工して正極合剤を得た。得られた正極合剤を60mgのアルミニウムメッシュに圧着して正極とした。
調製例14において作成したLi2O/Fe2O3/Co3O4正極合剤電極をワーキング電極として、実施例13と同様の条件により充放電試験を行った。充放電試験の結果を図25に示す。図25に示すように酸化リチウムを正極活物質として充放電が可能であることが示された。
調製例15において作成したLi2O/Fe2O3/Co3O4正極合剤電極をワーキング電極として、実施例13と同様の条件により充放電試験を行った。充放電試験の結果を図26に示す。図26に示すように酸化リチウムを正極活物質として充放電が可能であることが示された。
電解液に4.2M LiTFSI アセトニトリル電解液(LiTFSI:リチウムビストリフルオロメタンスルホニルイミド〔LiN(SO2CF3)2〕)の代わりに4.2M LiFSI アセトニトリル電解液(LiFSI:リチウムビスフルオロスルホニルイミド〔LiN(SO2F)2〕)を使用した以外は実施例13と同様の条件にて充放電試験を行った。充放電試験の結果を図27に示す。図27に示すように本条件に於いても酸化リチウムを正極活物質として充放電が可能であることが示された。
電解液に4.2M LiTFSI アセトニトリル電解液(LiTFSI:リチウムビストリフルオロメタンスルホニルイミド〔LiN(SO2CF3)2〕)の代わりに4.2M LiFSI アセトニトリル電解液(LiFSI:リチウムビスフルオロスルホニルイミド〔LiN(SO2F)2〕)を使用した以外は実施例16と同様の条件にて充放電試験を行った。充放電試験の結果を図28に示す。図28に示すように本条件に於いても酸化リチウムを正極活物質として充放電が可能であることが示された。
電解液に4.2M LiTFSI アセトニトリル電解液(LiTFSI:リチウムビストリフルオロメタンスルホニルイミド〔LiN(SO2CF3)2〕)の代わりに4.2M LiFSI アセトニトリル電解液(LiFSI:リチウムビスフルオロスルホニルイミド〔LiN(SO2F)2〕)を使用した以外は実施例17と同様の条件にて充放電試験を行った。充放電試験の結果を図29に示す。図29に示すように本条件に於いても酸化リチウムを正極活物質として充放電が可能であることが示された。
充電試験は市販の2極式セル(HSセル、宝泉社製)を用いて行った。ワーキング電極に調製例13において作成したLi2O/Fe2O3/Co3O4正極合剤電極、カウンター電極にはリチウム金属を使用し、電解液には4.2M LiTFSI アセトニトリル電解液(LiTFSI:リチウムビストリフルオロメタンスルホニルイミド〔LiN(SO2CF3)2〕)を使用した。正極活物質に対して4.5mA/gの電流密度で充電を行った。充電試験の結果を図30に示す。図30に示すように正極での充電反応(2Li2O→Li2O2+2Li++2e-)の理論充電容量(894mAh/g)近傍で急激な電位の立ち上がりが見られ、正極での充電反応が非常に効率良く進行していることが示された。
充電試験は市販の2極式セル(HSセル、宝泉社製)を用いて行った。ワーキング電極に調製例14において作成したLi2O/Fe2O3/Co3O4正極合剤電極、カウンター電極にはリチウム金属を使用し、電解液には4.2M LiTFSI アセトニトリル電解液(LiTFSI:リチウムビストリフルオロメタンスルホニルイミド〔LiN(SO2CF3)2〕)を使用した。正極活物質に対して4.5mA/gの電流密度で充電を行った。充電試験の結果を図31に示す。図31に示すように正極での充電反応(2Li2O→Li2O2+2Li++2e-)の理論充電容量(894mAh/g)近傍で急激な電位の立ち上がりが見られ、正極での充電反応が非常に効率良く進行していることが示された。
充電試験は市販の2極式セル(HSセル、宝泉社製)を用いて行った。ワーキング電極に調製例15において作成したLi2O/Fe2O3/Co3O4正極合剤電極、カウンター電極にはリチウム金属を使用し、電解液には4.2M LiTFSI アセトニトリル電解液(LiTFSI:リチウムビストリフルオロメタンスルホニルイミド〔LiN(SO2CF3)2〕)を使用した。正極活物質に対して4.5mA/gの電流密度で充電を行った。充電試験の結果を図32に示す。図32に示すように正極での充電反応(2Li2O→Li2O2+2Li++2e-)の理論充電容量(894mAh/g)近傍で急激な電位の立ち上がりが見られ、正極での充電反応が非常に効率良く進行していることが示された。
正極活物質として酸化リチウム(株式会社高純度化学研究所製)2.09gと、電極用触媒として酸化コバルト(Co3O4、和光純薬工業社製)2.23gを遊星ボールミル用のポットに入れ、遊星ボールミル混合(混合条件;10mmφのジルコニアボール25個を用いて回転数600rpmにて180時間処理)を行った。作業は全てアルゴン置換された水分濃度1ppm以下のグローブボックス中で行った。得られた固体粉末のXRD測定結果を図33に示す。得られた固体粉末中、Li2OとLiCoO2の存在を確認した。得られた固体粉末57mg、導電助剤としてのアセチレンブラック69mg、結着剤としてのポリテトラフルオロエチレン粉末6mgをメノウ乳鉢で混合し、粘土状に加工して正極合剤を得た。得られた正極合剤を60mgのアルミニウムメッシュに圧着して正極とした。
正極活物質として酸化リチウム(株式会社高純度化学研究所製)2.19gと、電極用触媒として酸化コバルト(Co3O4、和光純薬工業社製)1.16gを遊星ボールミル用のポットに入れ、遊星ボールミル混合(混合条件;10mmφのジルコニアボール25個を用いて回転数600rpmにて180時間処理)を行った。作業は全てアルゴン置換された水分濃度1ppm以下のグローブボックス中で行った。得られた固体粉末のXRD測定結果を図34に示す。得られた固体粉末中、Li2OとLiCoO2の存在を確認した。得られた固体粉末67mg、導電助剤としてのアセチレンブラック70mg、結着剤としてのポリテトラフルオロエチレン粉末6mgをメノウ乳鉢で混合し、粘土状に加工して正極合剤を得た。得られた正極合剤を60mgのアルミニウムメッシュに圧着して正極とした。
調製例16において作成したLi2O/Co3O4正極合剤電極をワーキング電極として、実施例13と同様の条件により充放電試験を行った。充放電試験の結果を図35に示す。図35に示すように酸化リチウムを正極活物質として充放電が可能であることが示された。
調製例17において作成したLi2O/Co3O4正極合剤電極をワーキング電極として、実施例13と同様の条件により充放電試験を行った。充放電試験の結果を図36に示す。図36に示すように酸化リチウムを正極活物質として充放電が可能であることが示された。
電解液に4.2M LiTFSI アセトニトリル電解液(LiTFSI:リチウムビストリフルオロメタンスルホニルイミド〔LiN(SO2CF3)2〕)の代わりに4.2M LiFSI アセトニトリル電解液(LiFSI:リチウムビスフルオロスルホニルイミド〔LiN(SO2F)2〕)を使用した以外は実施例24と同様の条件にて充放電試験を行った。充放電試験の結果を図37に示す。図37に示すように本条件に於いても酸化リチウムを正極活物質として充放電が可能であることが示された。
電解液に4.2M LiTFSI アセトニトリル電解液(LiTFSI:リチウムビストリフルオロメタンスルホニルイミド〔LiN(SO2CF3)2〕)の代わりに4.2M LiFSI アセトニトリル電解液(LiFSI:リチウムビスフルオロスルホニルイミド〔LiN(SO2F)2〕)を使用した以外は実施例25と同様の条件にて充放電試験を行った。充放電試験の結果を図38に示す。図38に示すように本条件に於いても酸化リチウムを正極活物質として充放電が可能であることが示された。
正極活物質として酸化リチウム(株式会社高純度化学研究所製)2.43gと、電極用触媒として酸化コバルト(Co3O4、和光純薬工業社製)0.66gを遊星ボールミル用のポットに入れ、遊星ボールミル混合(混合条件;10mmφのジルコニアボール25個を用いて回転数600rpmにて180時間処理)を行った。作業は全てアルゴン置換された水分濃度1ppm以下のグローブボックス中で行った。得られた固体粉末のXRD測定結果を図39に示す。得られた固体粉末中、Li2Oの存在を確認した。得られた固体粉末51mg、導電助剤としてのアセチレンブラック63mg、結着剤としてのポリテトラフルオロエチレン粉末4mgをメノウ乳鉢で混合し、粘土状に加工して正極合剤を得た。得られた正極合剤を60mgのアルミニウムメッシュに圧着して正極とした。
正極活物質として酸化リチウム(株式会社高純度化学研究所製)2.63gと、電極用触媒として酸化コバルト(Co3O4、和光純薬工業社製)0.36gを遊星ボールミル用のポットに入れ、遊星ボールミル混合(混合条件;10mmφのジルコニアボール25個を用いて回転数600rpmにて180時間処理)を行った。作業は全てアルゴン置換された水分濃度1ppm以下のグローブボックス中で行った。得られた固体粉末のXRD測定結果を図40に示す。得られた固体粉末中、Li2Oの存在を確認した。得られた固体粉末57mg、導電助剤としてのアセチレンブラック61mg、結着剤としてのポリテトラフルオロエチレン粉末5mgをメノウ乳鉢で混合し、粘土状に加工して正極合剤を得た。得られた正極合剤を60mgのアルミニウムメッシュに圧着して正極とした。
調製例18において作成したLi2O/Co3O4正極合剤電極をワーキング電極として、実施例13と同様の条件により充放電試験を行った。充放電試験の結果を図41に示す。図41に示すように酸化リチウムを正極活物質として充放電が可能であることが示された。
調製例19において作成したLi2O/Co3O4正極合剤電極をワーキング電極として、実施例13と同様の条件により充放電試験を行った。充放電試験の結果を図42に示す。図42に示すように酸化リチウムを正極活物質として充放電が可能であることが示された。
電解液に4.2M LiTFSI アセトニトリル電解液(LiTFSI:リチウムビストリフルオロメタンスルホニルイミド〔LiN(SO2CF3)2〕)の代わりに4.2M LiFSI アセトニトリル電解液(LiFSI:リチウムビスフルオロスルホニルイミド〔LiN(SO2F)2〕)を使用した以外は実施例28と同様の条件にて充放電試験を行った。充放電試験の結果を図43に示す。図43に示すように本条件に於いても酸化リチウムを正極活物質として充放電が可能であることが示された。
電解液に4.2M LiTFSI アセトニトリル電解液(LiTFSI:リチウムビストリフルオロメタンスルホニルイミド〔LiN(SO2CF3)2〕)の代わりに4.2M LiFSI アセトニトリル電解液(LiFSI:リチウムビスフルオロスルホニルイミド〔LiN(SO2F)2〕)を使用した以外は実施例29と同様の条件にて充放電試験を行った。充放電試験の結果を図44に示す。図44に示すように本条件に於いても酸化リチウムを正極活物質として充放電が可能であることが示された。
実施例27と同様の条件にて充電試験を行った。400mAh/g充電した後に正極をアセトニトリル溶媒にて洗浄した後に乾燥した。得られた充電後の正極をアルゴン封入した気密試料台に入れXRD測定を行った。結果を図45に示す。酸化容量に応じて33.5°付近のLi2Oのシグナルの減衰が見られた。これらのことから充電過程でLi2OがLi2O2に転化したことが示された。
実施例27と同様の条件にて充放電試験を行った。正極中に含まれる過酸化リチウムの定量は各充放電毎に実施例11と同様の手法で行った。一回目の充電をした後に合剤の中に含まれる過酸化リチウムの量は初期に合剤中に含まれる酸化リチウムの重量当たり4.17mmol/gであった。また、一回目の充電後に一回目の放電をした後に合剤の中に含まれる過酸化リチウムの量は初期に合剤中に含まれる酸化リチウム重量当たり0.17mmol/gであり、放電後にほぼ過酸化リチウムが消費されていることを確認した。また二回目の充電後に含まれる過酸化リチウムの量は3.89mmol/gであり、再度充電することで再度過酸化リチウムへ可逆的に酸化されたことが示された。
正極活物質として酸化リチウム(株式会社高純度化学研究所製)2.30gと、電極用触媒として酸化コバルト(CoO、和光純薬工業社製)2.31gを遊星ボールミル用のポットに入れ、遊星ボールミル混合(混合条件;10mmφのジルコニアボール25個を用いて回転数600rpmにて180時間処理)を行った。作業は全てアルゴン置換された水分濃度1ppm以下のグローブボックス中で行った。得られた固体粉末のXRD測定結果を図46に示す。得られた固体粉末中、Li2Oの存在を確認した。得られた固体粉末75mg、導電助剤としてのアセチレンブラック85mg、結着剤としてのポリテトラフルオロエチレン粉末6mgをメノウ乳鉢で混合し、粘土状に加工して正極合剤を得た。得られた正極合剤を60mgのアルミニウムメッシュに圧着して正極とした。
正極活物質として酸化リチウム(株式会社高純度化学研究所製)2.30gと、電極用触媒として酸化コバルト(CoO、和光純薬工業社製)1.15gを遊星ボールミル用のポットに入れ、遊星ボールミル混合(混合条件;10mmφのジルコニアボール25個を用いて回転数600rpmにて180時間処理)を行った。作業は全てアルゴン置換された水分濃度1ppm以下のグローブボックス中で行った。得られた固体粉末のXRD測定結果を図47に示す。得られた固体粉末中、Li2Oの存在を確認した。得られた固体粉末59mg、導電助剤としてのアセチレンブラック66mg、結着剤としてのポリテトラフルオロエチレン粉末4mgをメノウ乳鉢で混合し、粘土状に加工して正極合剤を得た。得られた正極合剤を60mgのアルミニウムメッシュに圧着して正極とした。
正極活物質として酸化リチウム(株式会社高純度化学研究所製)2.95gと、電極用触媒として酸化コバルト(CoO、和光純薬工業社製)0.75gを遊星ボールミル用のポットに入れ、遊星ボールミル混合(混合条件;10mmφのジルコニアボール25個を用いて回転数600rpmにて180時間処理)を行った。作業は全てアルゴン置換された水分濃度1ppm以下のグローブボックス中で行った。得られた固体粉末のXRD測定結果を図48に示す。得られた固体粉末中、Li2Oの存在を確認した。得られた固体粉末89mg、導電助剤としてのアセチレンブラック107mg、結着剤としてのポリテトラフルオロエチレン粉末8mgをメノウ乳鉢で混合し、粘土状に加工して正極合剤を得た。得られた正極合剤を60mgのアルミニウムメッシュに圧着して正極とした。
正極活物質として酸化リチウム(株式会社高純度化学研究所製)3.09gと、電極用触媒として酸化コバルト(CoO、和光純薬工業社製)0.39gを遊星ボールミル用のポットに入れ、遊星ボールミル混合(混合条件;10mmφのジルコニアボール25個を用いて回転数600rpmにて180時間処理)を行った。作業は全てアルゴン置換された水分濃度1ppm以下のグローブボックス中で行った。得られた固体粉末のXRD測定結果を図49に示す。得られた固体粉末中、Li2Oの存在を確認した。得られた固体粉末87mg、導電助剤としてのアセチレンブラック94mg、結着剤としてのポリテトラフルオロエチレン粉末7mgをメノウ乳鉢で混合し、粘土状に加工して正極合剤を得た。得られた正極合剤を60mgのアルミニウムメッシュに圧着して正極とした。
電解液に4.2M LiTFSI アセトニトリル電解液(LiTFSI:リチウムビストリフルオロメタンスルホニルイミド〔LiN(SO2CF3)2〕)の代わりに4.2M LiFSI アセトニトリル電解液(LiFSI:リチウムビスフルオロスルホニルイミド〔LiN(SO2F)2〕)を使用した以外は実施例28と同様の条件にて充放電試験を行った。充放電試験の結果を図50に示す。図50に示すように本条件に於いても酸化リチウムを正極活物質として充放電が可能であることが示された。
電解液に4.2M LiTFSI アセトニトリル電解液(LiTFSI:リチウムビストリフルオロメタンスルホニルイミド〔LiN(SO2CF3)2〕)の代わりに4.2M LiFSI アセトニトリル電解液(LiFSI:リチウムビスフルオロスルホニルイミド〔LiN(SO2F)2〕)を使用した以外は実施例29と同様の条件にて充放電試験を行った。充放電試験の結果を図51に示す。図51に示すように本条件に於いても酸化リチウムを正極活物質として充放電が可能であることが示された。
電解液に4.2M LiTFSI アセトニトリル電解液(LiTFSI:リチウムビストリフルオロメタンスルホニルイミド〔LiN(SO2CF3)2〕)の代わりに4.2M LiFSI アセトニトリル電解液(LiFSI:リチウムビスフルオロスルホニルイミド〔LiN(SO2F)2〕)を使用し、活物質に対して22.5mA/gの電流密度で充放電を実施した以外は実施例28と同様の条件にて充放電試験を行った。充放電試験の結果を図52に示す。図52に示すように本条件に於いても酸化リチウムを正極活物質として充放電が可能であることが示された。
電解液に4.2M LiTFSI アセトニトリル電解液(LiTFSI:リチウムビストリフルオロメタンスルホニルイミド〔LiN(SO2CF3)2〕)の代わりに4.2M LiFSI アセトニトリル電解液(LiFSI:リチウムビスフルオロスルホニルイミド〔LiN(SO2F)2〕)を使用し、活物質に対して22.5mA/gの電流密度で充放電を実施した以外は実施例29と同様の条件にて充放電試験を行った。充放電試験の結果を図53に示す。図53に示すように本条件に於いても酸化リチウムを正極活物質として充放電が可能であることが示された。
したがって、上記実施例の結果から、本発明の技術的範囲全般において、また、本明細書において開示した種々の形態において本発明が適用でき、有利な作用効果を発揮することができるといえる。
Claims (3)
- 正極、負極、及び、電解質を含んで構成される電池であって、
該正極は、下記式(1);
AxOy (1)
(式中、Aは、アルカリ金属原子を表す。x=0.5~2.5、y=0.5~2.5を表す。)で表されるアルカリ金属化合物を含んでなる正極活物質を含有し、
該負極は、アルカリ金属、錫、チタン、ホウ素、窒素、ケイ素、及び、炭素からなる群より選ばれる少なくとも一種を含んでなる負極活物質を含有し、
該電池は、正極、負極、及び、電解質が密閉されていることを特徴とする電池。 - 前記正極は、集電体と活物質層とを含んで構成され、
該活物質層は、活物質層の質量に対して、前記式(1)で表されるアルカリ金属化合物を、3質量%以上含むことを特徴とする請求項1に記載の電池。 - 前記電池は、完全充電時における、正極に含まれる下記式(2);
A2O2 (2)
(式中、Aは、アルカリ金属原子を表す。)で表されるアルカリ金属過酸化物に対する、負極に含まれるアルカリ金属のモル比が、100以下であることを特徴とする請求項1又は2に記載の電池。
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US10651469B2 (en) | 2016-07-21 | 2020-05-12 | Lg Chem, Ltd. | Lithium secondary battery comprising positive electrode active material for synthesis of lithium cobalt oxide and preparation method thereof |
JP2018523890A (ja) * | 2016-07-21 | 2018-08-23 | エルジー・ケム・リミテッド | コバルト酸リチウムを合成するための正極活物質を含むリチウム二次電池、この製造方法 |
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EP2911230A1 (en) | 2015-08-26 |
KR102120508B1 (ko) | 2020-06-08 |
JP2015053244A (ja) | 2015-03-19 |
JP6230149B2 (ja) | 2017-11-15 |
EP2911230B1 (en) | 2017-06-28 |
US10566618B2 (en) | 2020-02-18 |
EP2911230A4 (en) | 2016-07-13 |
US20150280230A1 (en) | 2015-10-01 |
KR20150074021A (ko) | 2015-07-01 |
CN104737352A (zh) | 2015-06-24 |
CN104737352B (zh) | 2017-05-24 |
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