WO2010004718A1 - リチウム一次電池用電解二酸化マンガンとその製造方法およびそれを用いたリチウム一次電池 - Google Patents
リチウム一次電池用電解二酸化マンガンとその製造方法およびそれを用いたリチウム一次電池 Download PDFInfo
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- WO2010004718A1 WO2010004718A1 PCT/JP2009/003122 JP2009003122W WO2010004718A1 WO 2010004718 A1 WO2010004718 A1 WO 2010004718A1 JP 2009003122 W JP2009003122 W JP 2009003122W WO 2010004718 A1 WO2010004718 A1 WO 2010004718A1
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- manganese dioxide
- electrolytic manganese
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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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; 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
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
Definitions
- the present invention relates to electrolytic manganese dioxide for a lithium primary battery, a method for producing the same, and a lithium primary battery using the same as a positive electrode active material.
- a light metal such as lithium is used as a negative electrode active material, and manganese dioxide, graphite fluoride, or the like is used as a positive electrode active material.
- Such a lithium primary battery has features not found in other primary batteries, such as high voltage and high energy density, low self-discharge, and extremely long shelf life. Therefore, lithium primary batteries are used in many electronic devices.
- manganese dioxide is often used as a positive electrode active material because it is inexpensive and abundant.
- manganese dioxide is used as the positive electrode active material of a lithium primary battery, it is common to use electrolytic manganese dioxide that has good discharge performance and long-term storage performance.
- This electrolytic manganese dioxide is usually synthesized by electrolytic treatment in a sulfuric acid solution containing manganese ions. Therefore, in order to use the obtained electrolytic manganese dioxide as a positive electrode active material of a lithium primary battery, it is necessary to neutralize with an alkali. As alkali used for this neutralization, ammonia and sodium hydroxide are often used.
- Electrolytic manganese dioxide prepared through neutralization with ammonia has been widely used as electrolytic manganese dioxide for lithium primary batteries.
- ammonia neutralized product there are only a limited number of manufacturers that produce ammonia-neutralized products, compared with electrolytic manganese dioxide (hereinafter referred to as sodium-neutralized products) produced through neutralization with sodium hydroxide. It is low in availability and expensive.
- the electrolytic manganese dioxide is heat-treated for the purpose of removing moisture for use as a positive electrode active material for a lithium primary battery. At that time, in the case of an ammonia neutralized product, ammonia volatilizes and emits an irritating odor. Therefore, a dedicated exhaust system is required to preserve the work environment.
- sodium neutralized products are mainly used as positive electrode active materials for dry batteries.
- a sodium-neutralized product contains about 0.3% by mass to 0.5% by mass of sodium. Therefore, when sodium neutralized products are used as electrolytic manganese dioxide for lithium primary batteries, the discharge performance may be reduced. This is because sodium present in the sodium-neutralized product is deposited on lithium as the negative electrode active material to form a resistance film. This precipitation becomes more prominent as the storage conditions of the battery increase at a high temperature for a long period of time. For this reason, sodium neutralized products are highly available, but are not often used as positive electrode active materials for lithium primary batteries.
- sodium neutralized products are inexpensive and are manufactured in large quantities, it is industrially valuable to use these sodium neutralized products as electrolytic manganese dioxide for lithium primary batteries.
- the sodium content of the electrolytic manganese dioxide after neutralization should be as small as possible within a certain range, specifically 0.05 to 0.2% by mass. It has been proposed (for example, Patent Document 1).
- a sodium-neutralized product having a low pH is baked and used as a positive electrode active material for a lithium primary battery, even if the initial discharge performance is obtained, a weak discharge over a long period of more than a year If done, the internal resistance of the battery increases.
- the present invention relates to electrolytic manganese dioxide for lithium primary batteries using a sodium-neutralized product as electrolytic manganese dioxide.
- the electrolytic manganese dioxide for lithium primary batteries of the present invention contains 0.05% by mass or more and 0.2% by mass or less of sodium, and has a pH of 5 or more and 7 or less as measured by the JIS-K-1467 method. It is characterized by.
- the lithium primary battery using the electrolytic manganese dioxide for a lithium primary battery of the present invention as a positive electrode active material suppresses an increase in the internal resistance of the battery even when a weak discharge is performed over a long period of one year or more. it can.
- the method for producing electrolytic manganese dioxide for lithium primary batteries comprises a step of neutralizing electrolytic manganese dioxide electrolytically synthesized in an acidic electrolytic cell with sodium hydroxide to prepare neutralized electrolytic manganese dioxide;
- the neutralized electrolytic manganese dioxide is adjusted so that the sodium content is 0.05% by mass or more and 0.2% by mass or less and the pH is 5 or more and 7 or less as measured by the JIS-K-1467 method. Washing with water.
- the lithium primary battery of the present invention has a sodium content of 0.05 mass% or more and 0.2 mass% or less, and a pH of 5 or more and 7 or less as measured by the JIS-K-1467 method.
- An electrolytic manganese dioxide for a lithium primary battery is used as a positive electrode active material. As a result, it is possible to suppress the formation of a resistance film containing sodium or manganese on the negative electrode, so that the initial discharge performance and the long-term discharge performance are excellent.
- FIG. 1 is a schematic cross-sectional view of a lithium primary battery according to an embodiment of the present invention.
- the sodium content in electrolytic manganese dioxide for lithium primary batteries is measured by ICP analysis.
- the sodium content in the electrolytic manganese dioxide for the lithium primary battery is 0.2.
- sodium elutes from the electrolytic manganese dioxide for lithium primary batteries is deposited on lithium as the negative electrode active material to form a resistance film, so that the discharge performance of the lithium primary battery is lowered.
- the pH of the electrolytic manganese dioxide for lithium primary batteries measured by the JIS-K-1467 method is lower than 5, due to the action of the acid generated from the reaction with a very small amount of moisture in the battery, the primary lithium ions are discharged during long-term discharge.
- Manganese ions are eluted from electrolytic manganese dioxide for batteries. Since the eluted manganese ions are deposited on lithium as the negative electrode active material to form a resistance film, the internal resistance of the battery is increased.
- Electrolytic manganese dioxide having a pH greater than 7 and a sodium content of 0.05% by mass or more and 0.2% by mass or less is produced by a production method in which it is electrolyzed in an acidic electrolytic cell and neutralized with sodium. It is not possible.
- the sodium content in the sodium-neutralized product is less than 0.05% by mass, it is difficult to adjust the pH to 5 or more by the water washing treatment described later.
- the sodium content is determined by ICP analysis. First, 1 g of manganese dioxide as a sample is weighed into a 200 ml beaker. Thereto, 20 ml of hydrochloric acid (50% by volume aqueous solution) is added and heated to dissolve manganese dioxide. When manganese dioxide is dissolved, let cool. Thereafter, filtration is performed, and pure water is added to the solution after filtration to make 100 ml. Using the solution, sodium is quantified by the standard addition method using an atomic absorption spectrometer.
- electrolytic manganese dioxide obtained by electrolytic synthesis in an acidic electrolytic bath containing a sulfuric acid solution.
- this electrolytic manganese dioxide is neutralized using sodium hydroxide aqueous solution, and neutralized electrolytic manganese dioxide is prepared.
- neutralization treatment is performed using an aqueous sodium hydroxide solution such that sodium hydroxide is 2.0 g or more and 10.0 g or less per kg of electrolytic manganese dioxide.
- sodium content of neutralized electrolytic manganese dioxide can be 0.05 mass% or more and 0.5 mass% or less.
- the pH of the neutralized electrolytic manganese dioxide thus obtained is measured by the JIS-K-1467 method, it is generally 2 or more and 4 or less.
- the neutralized electrolytic manganese dioxide is washed with water by adding water and stirring. Then, when water is removed by centrifugation and dried, electrolyzed manganese dioxide that has been washed with water can be obtained.
- the water-washed electrolytic manganese dioxide is washed with water so that the sodium content is 0.05% by mass or more and 0.2% by mass or less.
- the water-washed electrolytic manganese dioxide by JIS-K-1467 is washed with water so that the pH measurement result is 5 or more and 7 or less.
- the sodium content in the neutralized electrolytic manganese dioxide is preferably 0.1% by mass or more and 0.4% by mass or less.
- FIG. 1 is a schematic cross-sectional view of a lithium primary battery according to an embodiment of the present invention.
- the lithium primary battery has a positive electrode 1 using electrolytic manganese dioxide for a lithium primary battery as an active material and a negative electrode 2 using lithium as an active material.
- An electrode group is configured by winding the positive electrode 1, the negative electrode 2, and the separator 3 interposed therebetween in a spiral shape. This electrode group is housed in the case 9 together with a non-aqueous electrolyte (not shown).
- a sealing plate 8 is attached to the opening of the case 9.
- a lead 4 connected to the core material of the positive electrode 1 is connected to the sealing plate 8.
- the lead 5 connected to the negative electrode 2 is coupled to the case 9.
- an upper insulating plate 6 and a lower insulating plate 7 are respectively provided at the upper and lower portions of the electrode group to prevent internal short circuits.
- the positive electrode 1 is manufactured as follows. After mixing the electrolytic manganese dioxide for a lithium primary battery obtained by neutralization and washing with water as described above and a conductive agent, a positive electrode mixture is prepared by adding a binder and water and kneading.
- the conductive agent include graphite powder such as artificial graphite and natural graphite, or a mixture of graphite powder and carbon black such as acetylene black.
- the blending amount thereof may be an amount with which the filling amount of electrolytic manganese dioxide for a lithium primary battery is high and the electric resistance in the positive electrode 1 is reduced by forming a conductive path.
- this positive electrode material mixture is filled in a core material having a mesh shape or pores such as expanded metal, net, punching metal, and rolled. Then, it cuts into fixed size, peels a part of positive electrode mixture, welds the lead
- the strip-like negative electrode 2 is made of metallic lithium or a lithium alloy such as Li—Al, Li—Sn, Li—NiSi, Li—Pb.
- the solvent used for the non-aqueous electrolyte is not particularly limited as long as it is an organic solvent that is usually used for the non-aqueous electrolyte of a lithium battery.
- ⁇ -Butyllactone, propylene carbonate, ethylene carbonate, 1,2-dimethoxyethane and the like can be used alone or in combination.
- the supporting electrolyte constituting the non-aqueous electrolyte includes lithium borofluoride, lithium phosphorus hexafluoride, lithium trifluoromethanesulfonate, and LiN (CF 3 SO 2 ) 2 , LiN (C 2 having an imide bond in the molecular structure. F 5 SO 2) 2, LiN (CF 3 SO 2) (C 4 F 9 SO 2) , or the like can be used.
- the separator 3 is made of polyolefin nonwoven fabric, woven fabric, or microporous membrane.
- a sodium hydroxide aqueous solution concentration is adjusted so that sodium hydroxide is 3.0 g per 1 kg of electrolytic manganese dioxide obtained by electrolysis in a sulfuric acid tank, and neutralized to prepare neutralized electrolytic manganese dioxide.
- the sodium content of the obtained neutralized electrolytic manganese dioxide is 0.10% by mass.
- the neutralized electrolytic manganese dioxide is filtered and dried, and then heat treated at 400 ° C. for 4 hours.
- To 1 kg of the heat-treated electrolytic manganese dioxide obtained 10 kg of water is added and stirred and washed with water. After washing with water, the water is removed by centrifugation and dried.
- water-washed electrolytic manganese dioxide having a sodium content of 0.05% by mass and a pH measured by the JIS-K-1467 method of 5.0 is prepared.
- the obtained washed electrolytic manganese dioxide as a positive electrode active material
- 5% by mass of graphite as a conductive agent and 2% by mass of polytetrafluoroethylene as a binder are mixed with the washed electrolytic manganese dioxide.
- 35% by mass of pure water is added to the mixture and kneaded to prepare a positive electrode mixture in a wet state.
- the wet positive electrode mixture is passed through two rotating rolls rotating at a constant speed together with a 0.1 mm thick stainless steel expanded metal, and the positive electrode mixture is filled into the expanded metal to prepare a mixture sheet.
- the mixture sheet is rolled by a rolling roller press. This is cut into predetermined dimensions (thickness 0.40 mm, width 26 mm, length 235 mm), and the positive electrode 1 is manufactured.
- a lithium metal plate is used, and the metal plate is cut into predetermined dimensions (thickness 0.18 mm, width 24 mm, length 260 mm).
- a polyethylene microporous membrane separator is interposed between the positive electrode 1 and the negative electrode 2 thus prepared, and the electrode group is produced by winding it in a spiral shape. This electrode group is inserted into the case 9. Thereafter, the stainless steel lead 4 connected to the core of the positive electrode 1 is connected to the positive terminal of the sealing plate 8, and the nickel lead 5 connected to the negative electrode 2 is connected to the case 9.
- a non-aqueous electrolyte (not shown) is poured into the case 9, the opening of the case 9 is sealed, and 10 cylindrical lithium manganese dioxide primary batteries having a diameter of 17 mm and a height of 33.5 mm shown in FIG. Make it.
- the non-aqueous electrolyte is a mixed solvent prepared by mixing propylene carbonate and dimethoxyethane as a non-aqueous solvent at a volume ratio of 1: 1, and lithium trifluoromethanesulfonate as a supporting electrolyte at a concentration of 0.5 mol / liter. Prepare by dissolving.
- the lithium manganese dioxide primary battery thus produced is referred to as battery A.
- a sodium hydroxide aqueous solution concentration is adjusted so that sodium hydroxide is 7.0 g per 1 kg of electrolytic manganese dioxide obtained by electrolysis in a sulfuric acid tank, and neutralized to prepare neutralized electrolytic manganese dioxide.
- the sodium content of the obtained neutralized electrolytic manganese dioxide is 0.30% by mass.
- the neutralized electrolytic manganese dioxide is filtered and dried, and then heat treated at 400 ° C. for 4 hours. To 1 kg of the heat-treated electrolytic manganese dioxide obtained, 10 kg of water is added and stirred and washed with water. After washing with water, the water was removed by centrifugation and dried.
- washed electrolytic manganese dioxide having a sodium content of 0.20% by mass and a pH measured by the JIS-K-1467 method of 5.0 was obtained.
- a battery is produced in the same manner as the battery A except that the washed electrolytic manganese dioxide thus obtained is used.
- a sodium hydroxide aqueous solution concentration is adjusted so that sodium hydroxide is 9.0 g per 1 kg of electrolytic manganese dioxide obtained by electrolysis in a sulfuric acid tank, and neutralized to prepare neutralized electrolytic manganese dioxide.
- the sodium content of the obtained neutralized electrolytic manganese dioxide is 0.40% by mass.
- the neutralized electrolytic manganese dioxide is filtered and dried, and then heat treated at 400 ° C. for 4 hours. To 1 kg of the heat-treated electrolytic manganese dioxide obtained, 20 kg of water is added and stirred and washed with water. After washing with water, the water was removed by centrifugation and dried.
- the washed electrolytic manganese dioxide having a sodium content of 0.20% by mass and a pH measured by the JIS-K-1467 method of 7.0 was obtained.
- a battery is produced in the same manner as the battery A except that the water-washed electrolytic manganese dioxide thus obtained is used, and this is referred to as a battery C.
- a sodium hydroxide aqueous solution concentration is adjusted so that sodium hydroxide is 4.0 g per 1 kg of electrolytic manganese dioxide obtained by electrolysis in a sulfuric acid tank, and neutralized to prepare neutralized electrolytic manganese dioxide.
- the sodium content of the obtained neutralized electrolytic manganese dioxide is 0.15% by mass.
- the neutralized electrolytic manganese dioxide is filtered and dried, and then heat treated at 400 ° C. for 4 hours. To 1 kg of the heat-treated electrolytic manganese dioxide obtained, 20 kg of water is added and stirred and washed with water. After washing with water, the water was removed by centrifugation and dried.
- washed electrolytic manganese dioxide having a sodium content of 0.05% by mass and a pH measured by the JIS-K-1467 method of 7.0 was obtained.
- a battery is produced in the same manner as the battery A except that the water-washed electrolytic manganese dioxide thus obtained is used.
- a sodium hydroxide aqueous solution concentration is adjusted so that sodium hydroxide is 5.0 g per 1 kg of electrolytic manganese dioxide obtained by electrolysis in a sulfuric acid tank, and neutralized to prepare neutralized electrolytic manganese dioxide.
- the sodium content of the obtained neutralized electrolytic manganese dioxide is 0.20% by mass.
- the neutralized electrolytic manganese dioxide is filtered and dried, and then heat treated at 400 ° C. for 4 hours. To 1 kg of the heat-treated electrolytic manganese dioxide obtained, 10 kg of water is added and stirred and washed with water. After washing with water, the water is removed by centrifugation and dried.
- the washed electrolytic manganese dioxide having a sodium content of 0.10% by mass and a pH measured by the JIS-K-1467 method of 6.0 is obtained.
- a battery is produced in the same manner as the battery A except that the water-washed electrolytic manganese dioxide thus obtained is used.
- a sodium hydroxide aqueous solution concentration is adjusted so that sodium hydroxide is 9.0 g per 1 kg of electrolytic manganese dioxide obtained by electrolysis in a sulfuric acid tank, and neutralized to prepare neutralized electrolytic manganese dioxide.
- the sodium content of the obtained neutralized electrolytic manganese dioxide is 0.40% by mass.
- the neutralized electrolytic manganese dioxide is filtered and dried, and then heat treated at 400 ° C. for 4 hours. To 1 kg of the heat-treated electrolytic manganese dioxide obtained, 10 kg of water is added and stirred and washed with water. After washing with water, the water was removed by centrifugation and dried.
- washed electrolytic manganese dioxide having a sodium content of 0.25% by mass and a pH measured by the JIS-K-1467 method of 6.0 was obtained.
- a battery is produced in the same manner as the battery A except that the water-washed electrolytic manganese dioxide thus obtained is used, and this is designated as a battery F.
- a sodium hydroxide aqueous solution concentration is adjusted so that sodium hydroxide is 5.0 g per 1 kg of electrolytic manganese dioxide obtained by electrolysis in a sulfuric acid tank, and neutralized to prepare neutralized electrolytic manganese dioxide.
- the sodium content of the obtained neutralized electrolytic manganese dioxide is 0.15% by mass.
- the neutralized electrolytic manganese dioxide is filtered and dried, and then heat treated at 400 ° C. for 4 hours. To 1 kg of the heat-treated electrolytic manganese dioxide obtained, 5 kg of water is added and stirred and washed with water. After washing with water, the water was removed by centrifugation and dried.
- washed electrolytic manganese dioxide having a sodium content of 0.10% by mass and a pH measured by the JIS-K-1467 method of 4.5 was obtained.
- a battery is produced in the same manner as the battery A except that the water-washed electrolytic manganese dioxide thus obtained is used.
- a sodium hydroxide aqueous solution concentration is adjusted so that sodium hydroxide is 5.0 g per 1 kg of electrolytic manganese dioxide obtained by electrolysis in a sulfuric acid tank, and neutralized to prepare neutralized electrolytic manganese dioxide.
- the sodium content of the obtained neutralized electrolytic manganese dioxide is 0.20% by mass.
- the neutralized electrolytic manganese dioxide is filtered and dried, and then heat treated at 400 ° C. for 4 hours.
- the pH of the obtained heat-treated electrolytic manganese dioxide measured by JIS-K-1467 method is 4.5.
- a battery is produced in the same manner as Battery A except that the heat-treated electrolytic manganese dioxide is used without being washed with water, and this is referred to as Battery H.
- a sodium hydroxide aqueous solution concentration is adjusted so that sodium hydroxide is 1.5 g per 1 kg of electrolytic manganese dioxide obtained by electrolysis in a sulfuric acid tank, and neutralized to prepare neutralized electrolytic manganese dioxide.
- the sodium content of the obtained neutralized electrolytic manganese dioxide is 0.05% by mass.
- the neutralized electrolytic manganese dioxide is filtered and dried, and then heat treated at 400 ° C. for 4 hours. To 1 kg of the heat-treated electrolytic manganese dioxide obtained, 20 kg of water is added and stirred and washed with water. After washing with water, the water was removed by centrifugation and dried.
- the sodium content of electrolytic manganese dioxide that has not been neutralized with an aqueous sodium hydroxide solution is 0.01% by mass.
- This electrolytic manganese dioxide is heat-treated at 400 ° C. for 4 hours. To 1 kg of the heat-treated electrolytic manganese dioxide obtained, 10 kg of water is added and stirred and washed with water. After washing with water, the water is removed by centrifugation and drying is performed to prepare water-washed electrolytic manganese dioxide. The sodium content of this washed electrolytic manganese dioxide is 0.01% by mass and does not change from that before washing.
- the pH of this washed electrolytic manganese dioxide measured by JIS-K-1467 is 2.0.
- a battery is produced in the same manner as Battery A except that the above washed manganese dioxide is used, and this is referred to as Battery J.
- a sodium hydroxide aqueous solution concentration is adjusted so that sodium hydroxide is 10.0 g per 1 kg of electrolytic manganese dioxide obtained by electrolysis in the sulfuric acid layer, and neutralized to prepare neutralized electrolytic manganese dioxide.
- the sodium content of the obtained neutralized electrolytic manganese dioxide is 0.50% by mass.
- the neutralized electrolytic manganese dioxide is filtered and dried, and then heat treated at 400 ° C. for 4 hours. To 1 kg of the heat-treated electrolytic manganese dioxide obtained, 40 kg of water is added and stirred and washed with water. After washing with water, the water is removed by centrifugation and drying is performed to prepare water-washed electrolytic manganese dioxide.
- This water-washed electrolytic manganese dioxide has a sodium content of 0.20% by mass, and the pH measured by the JIS-K-1467 method is 7.0.
- a battery is produced in the same manner as Battery A except that the above electrolytic manganese dioxide is used, and this is referred to as Battery K.
- Battery F has low initial discharge performance. This is presumably because the sodium content of the electrolytic manganese dioxide, which is the positive electrode active material, is large, so that sodium in the positive electrode 1 is deposited on the negative electrode 2 to form a resistance film and inhibit the discharge reaction.
- the batteries G, H, I, and J have good initial discharge characteristics, but the internal resistance after one year of 300 k ⁇ discharge is increased and the long-term discharge performance is inferior.
- the pH of electrolytic manganese dioxide which is the positive electrode active material, is lower than 5, so that manganese ions are eluted from the positive electrode 1 by the action of the acid generated from the reaction with a small amount of moisture in the battery, and on the negative electrode 2. This is thought to be due to the deposition of a resistance film.
- the batteries A to E and the battery K have excellent long-term discharge performance since the internal resistance after one year of discharge is 300 k ⁇ . Also, the initial discharge performance is excellent.
- battery K is washed with 40 kg of water for 1 kg of heat-treated electrolytic manganese dioxide, and the amount of water used is larger than those of other batteries A to E. From the above, in order to save water used during washing, the sodium content in the neutralized manganese dioxide is preferably 0.1% by mass or more and 0.4% by mass or less.
- a cylindrical battery using a wound electrode group has been described as an example, but the present invention is not limited to such an electrode group configuration or battery shape.
- An electrode configuration in which electrodes are stacked may be used, and the present invention may be applied to a prismatic or coin battery.
- the sodium-neutralized electrolytic manganese dioxide according to the present invention is not only excellent in initial discharge characteristics, but can be a positive electrode active material for a lithium primary battery excellent in long-term discharge characteristics, and thus requires a long life. Useful for electrical equipment.
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- Inorganic Chemistry (AREA)
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Abstract
Description
2 負極
3 セパレータ
4,5 リード
6 上部絶縁板
7 下部絶縁板
8 封口板
9 ケース
Claims (4)
- ナトリウムを0.05質量%以上、0.2質量%以下含み、JIS-K-1467法によって測定した際のpHが5以上、7以下であるリチウム一次電池用電解二酸化マンガン。
- 酸性の電解槽で電解合成された電解二酸化マンガンを水酸化ナトリウムによって中和処理して中和済電解二酸化マンガンを調製するステップと、
前記中和済電解二酸化マンガンをナトリウムの含有量が0.05質量%以上、0.2質量%以下かつJIS-K-1467法によって測定した際のpHが5以上、7以下になるように水洗するステップと、を備えたリチウム一次電池用電解二酸化マンガンの製造方法。 - 前記中和済電解二酸化マンガン中のナトリウム含有量は0.1質量%以上、0.4質量%以下である、
請求項2記載のリチウム一次電池用電解二酸化マンガンの製造方法。 - 請求項1に記載のリチウム一次電池用電解二酸化マンガンを用いた正極と、リチウム金属あるいはリチウム合金からなる負極と、前記正極と前記負極との間に介在するセパレータと非水電解液と、を備えた、リチウム一次電池。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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US12/681,500 US9023119B2 (en) | 2008-07-09 | 2009-07-06 | Electrolytic manganese dioxide for lithium primary battery, manufacturing method therefor, and lithium primary battery using same |
JP2009548531A JP5278332B2 (ja) | 2008-07-09 | 2009-07-06 | リチウム一次電池用電解二酸化マンガンとその製造方法およびそれを用いたリチウム一次電池 |
CN2009801028868A CN101999186A (zh) | 2008-07-09 | 2009-07-06 | 锂一次电池用电解二氧化锰及其制造方法、以及采用该电解二氧化锰的锂一次电池 |
US14/680,758 US20150214546A1 (en) | 2008-07-09 | 2015-04-07 | Electrolytic manganese dioxide for lithium primary battery, and lithium primary battery using the same |
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JP2008-178819 | 2008-07-09 | ||
JP2008178819 | 2008-07-09 |
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US12/681,500 A-371-Of-International US9023119B2 (en) | 2008-07-09 | 2009-07-06 | Electrolytic manganese dioxide for lithium primary battery, manufacturing method therefor, and lithium primary battery using same |
US14/680,758 Division US20150214546A1 (en) | 2008-07-09 | 2015-04-07 | Electrolytic manganese dioxide for lithium primary battery, and lithium primary battery using the same |
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WO2010004718A1 true WO2010004718A1 (ja) | 2010-01-14 |
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US (2) | US9023119B2 (ja) |
JP (1) | JP5278332B2 (ja) |
CN (1) | CN101999186A (ja) |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011251862A (ja) * | 2010-06-01 | 2011-12-15 | Tosoh Corp | マンガン酸化物及びその製造方法 |
CN102347479A (zh) * | 2010-08-06 | 2012-02-08 | 无锡晶石新型能源有限公司 | 一种加工锂离子电池用电解二氧化锰的方法及装置 |
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JP2001026425A (ja) * | 1999-07-16 | 2001-01-30 | Mitsui Mining & Smelting Co Ltd | 二酸化マンガン及びその製造方法 |
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JP2004273169A (ja) * | 2003-03-05 | 2004-09-30 | Mitsui Mining & Smelting Co Ltd | 電解二酸化マンガン |
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JP3456181B2 (ja) * | 1999-11-30 | 2003-10-14 | 日本電気株式会社 | リチウムマンガン複合酸化物およびそれを用いた非水電解液二次電池 |
JP4199811B2 (ja) * | 2007-01-15 | 2008-12-24 | パナソニック株式会社 | アルカリ乾電池 |
-
2009
- 2009-07-06 US US12/681,500 patent/US9023119B2/en active Active
- 2009-07-06 JP JP2009548531A patent/JP5278332B2/ja active Active
- 2009-07-06 CN CN2009801028868A patent/CN101999186A/zh active Pending
- 2009-07-06 WO PCT/JP2009/003122 patent/WO2010004718A1/ja active Application Filing
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2015
- 2015-04-07 US US14/680,758 patent/US20150214546A1/en not_active Abandoned
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JPH11506721A (ja) * | 1995-06-07 | 1999-06-15 | デュラセル、インコーポレーテッド | リチウム電池用の改良された二酸化マンガン |
JP2001026425A (ja) * | 1999-07-16 | 2001-01-30 | Mitsui Mining & Smelting Co Ltd | 二酸化マンガン及びその製造方法 |
JP2001236957A (ja) * | 2000-02-25 | 2001-08-31 | Mitsui Mining & Smelting Co Ltd | リチウム一次電池用二酸化マンガン及びその製造方法 |
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JP2004273169A (ja) * | 2003-03-05 | 2004-09-30 | Mitsui Mining & Smelting Co Ltd | 電解二酸化マンガン |
JP2007012599A (ja) * | 2005-05-30 | 2007-01-18 | Matsushita Electric Ind Co Ltd | 熱電池 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2011251862A (ja) * | 2010-06-01 | 2011-12-15 | Tosoh Corp | マンガン酸化物及びその製造方法 |
CN102347479A (zh) * | 2010-08-06 | 2012-02-08 | 无锡晶石新型能源有限公司 | 一种加工锂离子电池用电解二氧化锰的方法及装置 |
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JP5278332B2 (ja) | 2013-09-04 |
JPWO2010004718A1 (ja) | 2011-12-22 |
CN101999186A (zh) | 2011-03-30 |
US20100239911A1 (en) | 2010-09-23 |
US20150214546A1 (en) | 2015-07-30 |
US9023119B2 (en) | 2015-05-05 |
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