WO2010044176A1 - アルカリ電池 - Google Patents
アルカリ電池 Download PDFInfo
- Publication number
- WO2010044176A1 WO2010044176A1 PCT/JP2009/002026 JP2009002026W WO2010044176A1 WO 2010044176 A1 WO2010044176 A1 WO 2010044176A1 JP 2009002026 W JP2009002026 W JP 2009002026W WO 2010044176 A1 WO2010044176 A1 WO 2010044176A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- positive electrode
- manganese dioxide
- battery
- gasket
- negative electrode
- Prior art date
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- 239000003513 alkali Substances 0.000 title 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 156
- 238000007789 sealing Methods 0.000 claims abstract description 14
- 230000035699 permeability Effects 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910000474 mercury oxide Inorganic materials 0.000 claims description 3
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011149 active material Substances 0.000 abstract description 3
- 238000003860 storage Methods 0.000 description 57
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 41
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 14
- 238000006722 reduction reaction Methods 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 11
- 239000007774 positive electrode material Substances 0.000 description 10
- 230000002829 reductive effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000006479 redox reaction Methods 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 239000010426 asphalt Substances 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 229920001971 elastomer Polymers 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000002594 fluoroscopy Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
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- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
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- 239000004753 textile Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Images
Classifications
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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
- H01M10/24—Alkaline accumulators
- H01M10/28—Construction or manufacture
- H01M10/283—Cells or batteries with two cup-shaped or cylindrical collectors
-
- 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
- H01M10/24—Alkaline accumulators
- H01M10/28—Construction or manufacture
-
- 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
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/244—Zinc electrodes
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/147—Lids or covers
- H01M50/148—Lids or covers characterised by their shape
- H01M50/154—Lid or cover comprising an axial bore for receiving a central current collector
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/172—Arrangements of electric connectors penetrating the casing
- H01M50/174—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells
- H01M50/182—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells for cells with a collector centrally disposed in the active mass, e.g. Leclanché cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/463—Separators, membranes or diaphragms characterised by their shape
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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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
- H01M2004/023—Gel electrode
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative 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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M2010/4292—Aspects relating to capacity ratio of electrodes/electrolyte or anode/cathode
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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
Definitions
- the present invention relates to an alkaline battery using electrolytic manganese dioxide as a positive electrode active material.
- Electrolytic manganese dioxide is known as a typical material for the positive electrode active material of alkaline batteries.
- electrolytic manganese dioxide contains moisture, ash, and other inevitable components, and the net purity (functioning as an active material) of manganese dioxide (MnO 2 ) in electrolytic manganese dioxide is 90 several percent.
- the technique which raises the electric potential of manganese dioxide typically 270 mV or more is known (refer patent document 1).
- Table 1 shows the results of measurement of initial discharge performance, discharge performance after storage, and storage characteristics (residual rate) by the inventors of the present invention using a high potential electrolytic manganese dioxide to produce AA alkaline batteries. Is shown.
- the initial discharge performance is as follows: high load pulse discharge (process of discharging at 1.55 W for 2 seconds and then discharging at 0.65 W for 28 seconds within one month after producing the battery. Cycle), and the discharge duration (cycle) until the closed circuit voltage reaches 1.05V is evaluated, and the discharge performance after storage is equivalent to one week at a temperature of 60 ° C. ) After storage, the discharge duration (cycle) until the closed circuit voltage reached 1.05 V was evaluated under the same high-load pulse discharge conditions as the initial discharge performance. The storage characteristics were evaluated by the ratio (residual ratio) of the discharge performance after storage to the initial discharge performance.
- the initial discharge performance is improved as the electrolytic manganese dioxide potential increases, the storage characteristics (residual rate) are greatly deteriorated, and in the batteries 2 to 5 having the EMD potential of 275 mV to 320 mV.
- the discharge performance after storage has a reversal phenomenon that is lower than the discharge performance after storage in the battery 1 having an EMD potential of 265 mV.
- Patent Document 2 Such deterioration in storage characteristics is considered to be caused by distortion of manganese dioxide crystals when an alkaline battery using electrolytic manganese dioxide having a high potential of 270 mV or higher is stored for a long time.
- Patent Document 2 electrolytic manganese dioxide having a stable crystal structure and a potential of less than 270 mV is used as a positive electrode active material, and graphite having a predetermined ratio (5 to 7 wt%) with respect to the positive electrode active material is used.
- a technique for improving the initial discharge performance and suppressing the deterioration of the discharge performance after storage is disclosed.
- the advantage of the initial discharge performance is ensured as long as electrolytic manganese dioxide having a potential of less than 270 mV is used as the positive electrode active material. It ’s difficult.
- the present invention has been made in view of such a point, and the main object of the present invention is to prevent deterioration in discharge performance after storage even when high potential electrolytic manganese dioxide is used as a positive electrode active material. It is to provide an alkaline battery with performance.
- an alkaline battery according to the present invention is an alkaline battery using electrolytic manganese dioxide having a high potential (275 to 320 mV) as a positive electrode active material, a positive electrode and a negative electrode housed in a battery case, a gasket, A configuration is adopted in which the volume of the closed space formed between is in a range of 2.0 to 6.0% with respect to the internal volume of the battery formed by the battery case and the sealing plate.
- the alkaline battery according to the present invention is an alkaline battery in which a positive electrode and a negative electrode are accommodated in a battery case via a separator, and the opening of the battery case is sealed by a sealing plate via a gasket,
- the positive electrode contains electrolytic manganese dioxide, and the potential of the electrolytic manganese dioxide is in the range of 275 to 320 mV with respect to a mercury oxide (Hg / HgO) reference electrode
- the negative electrode contains zinc
- the positive and negative electrodes in the battery case The volume of the closed space formed between the battery and the gasket is in the range of 2.0 to 6.0% with respect to the internal volume of the battery formed by the battery case and the sealing plate.
- the height of the negative electrode housed in the battery case is higher than the height of the positive electrode.
- the density of manganese dioxide (MnO 2 ) in the positive electrode is in the range of 2.55 to 2.70 g / cm 3 . is there.
- the separator has an air permeability in the range of 4.0 to 10.0 cc / cm 2 / sec.
- a protective film is formed on the gasket side surface of the positive electrode.
- the length with which the end of the separator contacts the gasket is in the range of 1.0 to 2.5 mm.
- the volume of the closed space formed between the positive electrode and the negative electrode in the battery case and the gasket is reduced. It is possible to suppress the reduction reaction of manganese by hydrogen gas, thereby improving the initial discharge performance and obtaining a high-performance alkaline battery that suppresses the decrease in discharge performance after storage.
- FIG. 1 is a half cross-sectional view showing a configuration of an alkaline battery in an embodiment of the present invention. It is the fragmentary sectional view of the alkaline battery which showed the reaction path
- the inventor of the present application examined factors other than distortion of manganese dioxide crystals as a cause of a significant decrease in the remaining rate after storage when using electrolytic manganese dioxide at a high potential. Obtained knowledge.
- the present inventor has come up with the idea that by suppressing the reduction reaction of manganese dioxide with hydrogen gas, even when high-potential electrolytic manganese dioxide is used, a significant decrease in storage characteristics can be suppressed. .
- the volume of the closed space formed between the positive electrode and the negative electrode in the battery case and the gasket is reduced to reduce the hydrogen gas retention space, which reduces the reduction reaction of manganese dioxide with hydrogen gas. It is effective to suppress.
- FIG. 1 is a half sectional view showing a configuration of an alkaline battery in an embodiment of the present invention.
- a positive electrode 2 containing electrolytic manganese dioxide and a gelled negative electrode 3 containing zinc are accommodated in a battery case 1 having a bottomed cylindrical shape via a separator 4.
- the gasket 5, the negative electrode current collector 6, and the negative electrode terminal plate (sealing plate) 7 are sealed together.
- Table 2 shows the positive electrode 2 and the negative electrode in the battery case 1 by changing the heights of the positive electrode 2 and the negative electrode 3 with respect to alkaline batteries in which the potential of electrolytic manganese dioxide (EMD) was set to 275 mV, 305 mV, and 320 mV, respectively.
- EMD electrolytic manganese dioxide
- the volume of the closed space 10 formed between the gasket 3 and the gasket 5 was changed to a range of 10.8 to 2.0% with respect to the battery internal volume formed by the battery case 1 and the sealing plate 7.
- AA alkaline batteries 6 to 20 were prepared, and the results of measuring the initial discharge performance, the discharge performance after storage, and the ratio of the discharge performance after storage to the initial discharge performance (residual ratio) were shown for each battery. Is.
- the potential of electrolytic manganese dioxide is adjusted by changing the molar ratio of manganese and sulfuric acid in an electrolysis process using a manganese sulfate solution as an electrolytic solution, and the obtained electrolytic manganese dioxide is immersed in a 40% aqueous KOH solution.
- the potential of electrolytic manganese dioxide was determined by measuring the potential difference of mercury oxide (Hg / HgO) from the reference electrode.
- the filling height of the positive electrode 2 and the negative electrode 3 can be obtained by, for example, photographing the battery with an X-ray fluoroscopic camera and measuring the distance from the bottom surface to the top surface of the positive electrode 2 or the negative electrode 3.
- the top surface of the negative electrode 3 may not be horizontal with the bottom surface, in that case, the measurement was performed with the middle between the top surface and the bottom surface as the top surface.
- the residual rate after storage is improved by reducing the volume of the closed space 10. I understand. That is, by reducing the residence space of hydrogen gas generated during storage, it is possible to suppress the reduction reaction of manganese dioxide by hydrogen gas, thereby suppressing the deterioration of storage characteristics.
- the remaining rate after storage can be reduced.
- the level can be recovered to a level close to that of the low potential EMD battery 1 shown in Table 1.
- the filling height of the positive electrode 2 and the negative electrode 3 housed in the battery case 1 may be increased.
- the effect of improving the discharge performance is also obtained.
- the closed space 10 formed between the positive electrode 2 and the negative electrode 3 and the gasket 5 is a hydrogen gas generated by some trouble in the battery manufacturing process (for example, iron or nickel in the negative electrode 3).
- impurities such as these are mixed, it is preferable to secure a volume necessary for suppressing a pressure increase of zinc to form a local battery and generate hydrogen gas.
- high-potential electrolytic manganese dioxide since high-potential electrolytic manganese dioxide is used, hydrogen gas generated by some trouble (aside from hydrogen gas staying in the closed space 10 during storage) is efficiently absorbed. Therefore, even if the volume of the closed space 10 is reduced, it is possible to suppress an increase in pressure when a manufacturing trouble occurs.
- the “closed space 10” in the present invention refers to a space formed between the positive electrode 2 and the negative electrode 3 and the gasket 5 in the battery case 1, and protrudes upward from the surfaces of the positive electrode 2 and the negative electrode 3 to form the gasket 5.
- the volume occupied by the separator 4 in contact with the lower surface of the electrode and the negative electrode current collector 6 protruding upward from the negative electrode 3 and passing through the gasket 5 is excluded. Further, the space formed between the gasket 5 and the sealing plate 7 is not included.
- the volume of the closed space 10 can be measured using, for example, an underwater substitution method. That is, the volume of the closed space 10 can be measured by disassembling the battery to be measured in water and collecting the air in the closed space 10. A battery within 6 months, preferably within 3 months after the battery configuration is measured.
- electrolytic manganese dioxide refers to manganese dioxide produced by electrolysis in an aqueous manganese sulfate solution, ⁇ -type, ⁇ -type, ⁇ -type, ⁇ -type, ⁇ -type, ⁇ -type, ⁇ -type, ⁇ -type, ⁇ -type, ⁇ -type, ⁇ -type, ⁇ -type, ⁇ -type, It may have any crystal structure of ramsdellite type. Among these, the ⁇ type is preferred because it is widely distributed industrially, is easily available, and is inexpensive.
- spinel-type electrolytic manganese dioxide obtained by adding lithium compound to electrolytic manganese dioxide and firing it to synthesize lithium manganese spinel and then removing lithium by oxalic acid treatment may be used. Further, it may take the form of a composite oxide in which a part of the manganese atom is substituted with an atom such as nickel, cobalt, copper, tin, or titanium.
- the type of the alkaline electrolyte is not particularly limited, but preferably an aqueous solution containing 32-38 wt% potassium hydroxide and 1-4 wt% zinc oxide can be used.
- the battery voltage becomes high.
- the battery voltage becomes high.
- the potential of the negative electrode can be increased by increasing the amount of zinc oxide contained in the alkaline electrolyte, thereby reducing the battery voltage. Can be expected to lower.
- the battery voltage is suppressed to a predetermined voltage (for example, 1.65 V) or less by increasing the amount of zinc oxide contained in the alkaline electrolyte according to the potential level of electrolytic manganese dioxide.
- a predetermined voltage for example, 1.65 V
- the content of zinc oxide in the alkaline electrolyte is preferably 1.5% by weight or more.
- the potential of electrolytic manganese dioxide is 300 mV or more
- the content of zinc oxide is 1.9% by weight or more
- the potential of electrolytic manganese dioxide is 310 mV or more
- the content of zinc oxide is It is preferable to make it 2.4% by weight or more.
- the material of the gasket is not particularly limited, but polyamide resins such as 6,6-nylon, 6,10-nylon, and 6,12-nylon can be preferably used. Since these materials have high permeability, hydrogen gas staying in the closed space 10 can be effectively released to the outside.
- the present invention reduces the volume of the closed space 10, thereby suppressing the reduction reaction of manganese dioxide by the hydrogen gas staying in the closed space 10 during storage, thereby improving the remaining rate after storage.
- the reduction reaction of manganese dioxide by hydrogen can be suppressed, and the residual rate after storage can be further improved.
- FIG. 2 is a diagram showing a partial cross-sectional view of an alkaline battery. Arrows A to D in the figure indicate paths through which hydrogen gas staying in the closed space 10 during storage reacts with electrolytic manganese dioxide contained in the positive electrode 2. Is shown respectively. Hereinafter, the description will be made sequentially.
- Table 3 shows an alkaline battery in which the potential of electrolytic manganese dioxide (EMD) is fixed at 305 mV, and the volume of the closed space 10 with respect to the internal volume of the battery is set to 6.0%, 4.4%, and 2.0%, respectively.
- EMD electrolytic manganese dioxide
- AA alkaline batteries 13 to 15 and 21 to 29 in which the height ratio of negative electrode 3 / positive electrode 2 was changed in the range of 0.96 to 1.08 were prepared. 1 shows the results of measuring the discharge performance after storage and the ratio (residual rate) of the discharge performance after storage to the initial discharge performance, respectively.
- the remaining ratio improves as the height ratio of the negative electrode 3 / the positive electrode 2 becomes larger than 1.00 in any size of the closed space 10, and becomes smaller than 1.00. It can be seen that the residual rate decreases. That is, by making the height of the negative electrode 3 housed in the battery case 1 higher than the height of the positive electrode 2, the oxidation-reduction reaction between hydrogen gas and manganese dioxide in the path indicated by the arrow A in FIG. Thereby, the remaining rate after storage can be further improved.
- the path indicated by the arrow B is when the hydrogen gas staying in the closed space 10 enters the positive electrode 2 and reacts with manganese dioxide.
- the positive electrode 2 is formed by mixing electrolytic manganese dioxide powder, which is a positive electrode active material, with graphite powder, alkaline electrolyte, or the like, which is a conductive agent, and then performing pressure molding.
- electrolytic manganese dioxide powder which is a positive electrode active material
- graphite powder, alkaline electrolyte, or the like which is a conductive agent
- Table 4 shows the size of AA cells in which the MnO 2 density was changed in the range of 2.55 to 2.70 g / cm 3 with respect to the alkaline battery (MnO 2 density: 2.40 g / cm 3 ) 25 shown in Table 3.
- the alkaline alkaline batteries 30 and 31 were produced, and the results of measuring the initial discharge performance, the discharge performance after storage, and the ratio of the discharge performance after storage to the initial discharge performance (residual rate) for each battery are shown. is there.
- MnO 2 density in the present invention refers to the ratio of the weight of manganese dioxide (MnO 2 ) contained in the electrolytic manganese dioxide constituting the positive electrode 2 to the volume of the positive electrode 2.
- MnO 2 density can be measured, for example, by the following method.
- the volume of the positive electrode 2 is calculated by measuring the outer diameter, inner diameter, and height of the positive electrode 2 through X-ray fluoroscopy. Then, after disassembling the battery, taking out all of the positive electrode 2 and sufficiently dissolving it with acid, the manganese in the aqueous solution is obtained by ICP emission analysis (high frequency inductively coupled plasma emission spectroscopy) from the aqueous solution obtained by filtering out the insoluble matter. The content of (Mn) is examined, and the content is converted into the amount of manganese dioxide (MnO 2 ) to determine the weight of manganese dioxide contained in the positive electrode 2. In this way, “MnO 2 density” may be obtained.
- ICP emission analysis high frequency inductively coupled plasma emission spectroscopy
- the path indicated by the arrow C is when hydrogen gas staying in the closed space 10 penetrates the separator 4 and enters the positive electrode 2 facing the negative electrode 3 to react with manganese dioxide.
- the separator 4 is composed of a porous film that can hold an alkaline electrolyte.
- the permeability of the separator 4 within a range that does not impair the holding amount of the alkaline electrolyte, It can be expected that the penetration into the positive electrode 2 is suppressed, thereby suppressing the redox reaction between hydrogen gas and manganese dioxide.
- Table 5 shows that the permeability of the separator 4 is 10.0 to 4.0 cc / cm 2 / sec with respect to the alkaline battery 25 shown in Table 3 (air permeability of the separator 4: 14.8 cc / cm 2 / sec) 25.
- AA alkaline batteries 32 to 34 with different ranges were prepared, and for each battery, the initial discharge performance, the discharge performance after storage, and the ratio of the discharge performance after storage to the initial discharge performance (residual rate), respectively. The measurement results are shown.
- the remaining rate after storage can be further improved by setting the air permeability of the separator 4 in the range of 4.0 to 10.0 cc / cm 2 / sec.
- the air permeability of the separator 4 is less than 4.0 cc / cm 2 / sec, the retained amount of the alkaline electrolyte is decreased, and the discharge capacity is decreased, which is not preferable.
- air permeability in the present invention refers to the volume of air that can permeate per certain area and time of the separator 4. Further, the “air permeability” can be measured with a Frazier type tester in accordance with, for example, JIS L-1096-6.27 “General textile test method-Breathability”.
- the path indicated by the arrow D is when hydrogen gas staying in the closed space 10 enters the inside of the positive electrode 2 from the surface of the positive electrode 2 on the gasket 5 side and reacts with manganese dioxide.
- the positive electrode 2 is formed from a molded body (for example, a positive electrode pellet that is pressure-molded into a hollow cylinder) obtained by pressure-molding a positive electrode mixture in which electrolytic manganese dioxide powder, graphite powder, alkaline electrolyte, and the like are mixed.
- Table 6 shows an AA alkaline battery in which a protective film made of asphalt or polyvinyl alcohol (PVA) is formed on the surface of the positive electrode 2 with respect to the alkaline battery 25 (no protective film on the surface of the positive electrode 2) 25 shown in Table 3. 35 and 36 are prepared, and the results of measuring the initial discharge performance, the discharge performance after storage, and the ratio (residual ratio) of the discharge performance after storage to the initial discharge performance are shown for each battery.
- PVA polyvinyl alcohol
- the formation of the protective film on the surface of the positive electrode 2 can be performed by the following method.
- the protective film made of asphalt can be formed by thermally melting asphalt and applying the molten asphalt to the surface of the positive electrode 2.
- the protective film made of polyvinyl alcohol can be formed by dissolving polyvinyl alcohol in water and applying the aqueous solution to the surface of the positive electrode 2. It is not preferable to apply a solution in which polyvinyl alcohol is dissolved in an organic solvent because manganese dioxide is reduced and the remaining rate after storage is reduced.
- a resin or rubber may be applied to the surface of the positive electrode 2 in the form of an aqueous emulsion.
- the gelled negative electrode 3 is separated from the separator 4 and the gasket 5 when a vibration or impact is applied to the battery by bringing the tip of the separator 4 into contact with the gasket 5 for a predetermined length.
- the contact gas is prevented from leaking into the positive electrode 2 from between the two, but by shortening the contact length within a range where the gelled negative electrode 3 does not leak into the positive electrode 2, the hydrogen gas staying in the closed space 10 is reduced. Therefore, it is easier to escape to the outside, and it can be expected to suppress the oxidation-reduction reaction between hydrogen gas and manganese dioxide.
- Table 7 shows that the gasket contact length of the separator 4 is shortened to a range of 2.5 to 1.0 mm with respect to the alkaline battery 25 shown in Table 3 (the gasket contact length of the separator 4 is 3.5 mm).
- AA alkaline batteries 37 and 38 were prepared, and the results of measuring the initial discharge performance, the discharge performance after storage, and the ratio of the discharge performance after storage to the initial discharge performance (residual rate) for each battery are shown. It is a thing.
- the gasket contact length of the separator 4 As shown in Table 7, by setting the gasket contact length of the separator 4 in the range of 1.0 to 2.5 mm, the remaining rate after storage can be further improved. In addition, when the gasket contact length of the separator 4 is less than 1.0 mm, it is not possible to sufficiently prevent leakage of the gelled negative electrode 3 to the positive electrode 2 side when vibration or impact is applied to the battery. Absent.
- Table 8 shows the size of the AA battery in which the MnO 2 density, the separator air permeability, and the gasket contact length are set in combination with values in a range in which each of the alkaline batteries 25 shown in Table 3 can be effective.
- the alkaline batteries 39 to 42 were prepared, and the results of measuring the initial discharge performance, the discharge performance after storage, and the ratio of the discharge performance after storage to the initial discharge performance (residual rate) for each battery are shown. .
- the MnO 2 density, separator air permeability, and gasket contact length are appropriately combined with values within the range where each can exert its effect, thereby improving the remaining rate after storage more effectively. Can be made.
- this invention produces the effect that the reduction
- the distance between the negative electrode 3 containing the alkaline electrolyte and the gasket 5 is close (in some cases, contact), there is a concern that the gasket 5 is degraded by hydrolysis with the alkaline electrolyte. .
- deterioration of the gasket 5 due to the electrolytic solution may be prevented by providing a coating layer 11 on the surface of the gasket 5 on the negative electrode 3 side.
- the leakage resistance of the gasket 5 can be improved.
- the coating layer 11 on the surface of the gasket 5 the effect of allowing hydrogen gas staying in the closed space 10 to pass through the gasket 5 and escaping to the outside is reduced, but the volume of the closed space 10 is originally reduced.
- the reduction reaction of manganese dioxide by hydrogen gas is suppressed, and thus the provision of the coating layer 11 does not impair the effect of the present invention to improve the storage characteristics.
- the coating layer 11 can be formed, for example, by dissolving a material such as a synthetic resin, rubber, or asphalt in an organic solvent, applying it to the surface of the gasket 5 and then drying it. Alternatively, it may be formed by applying and drying in the form of an aqueous emulsion.
- the alkaline battery of the present invention has high discharge performance and storage characteristics, and can be used for a wide range of electronic devices using a dry battery as a power source.
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- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
Description
2 正極
3 負極
4 セパレータ
5 ガスケット
6 負極集電子
7 負極端子板(封口板)
9 封口ユニット
10 閉空間
11 コーティング層
Claims (6)
- 正極及び負極がセパレータを介して電池ケース内に収納されてなるアルカリ電池であって、
前記電池ケースの開口部は、ガスケットを介して封口板で封口されており、
前記正極は電解二酸化マンガンを含み、該電解二酸化マンガンの電位は、酸化水銀(Hg/HgO)の参照電極に対して、275~320mVの範囲にあり、
前記負極は亜鉛を含み、
前記電池ケース内における前記正極及び負極と前記ガスケットとの間に形成された閉空間の容積は、前記電池ケース及び前記封口板で形成された電池内容積に対して、2.0~6.0%の範囲にある、アルカリ電池。 - 前記電池ケース内に収納された前記負極の高さは、前記正極の高さよりも高くなっている、請求項1に記載のアルカリ電池。
- 前記正極中の二酸化マンガンの密度は、2.55~2.70g/cm3の範囲にある、請求項1に記載のアルカリ電池。
- 前記セパレータの通気度は、4.0~10.0cc/cm2/secの範囲にある、請求項1に記載のアルカリ電池。
- 前記正極の前記ガスケット側表面に保護膜が形成されている、請求項1に記載のアルカリ電池。
- 前記セパレータの端部が前記ガスケットに当接する長さは、1.0~2.5mmの範囲にある、請求項1に記載のアルカリ電池。
Priority Applications (3)
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EP09820355.7A EP2337129B1 (en) | 2008-10-17 | 2009-05-08 | Alkali battery |
CN200980000558.7A CN101803083B (zh) | 2008-10-17 | 2009-05-08 | 碱性电池 |
JP2009544079A JP4493059B2 (ja) | 2008-10-17 | 2009-05-08 | アルカリ電池 |
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JP2008-269023 | 2008-10-17 | ||
JP2008269023 | 2008-10-17 |
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US (1) | US7820326B2 (ja) |
EP (1) | EP2337129B1 (ja) |
JP (1) | JP4493059B2 (ja) |
CN (1) | CN101803083B (ja) |
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WO2022137629A1 (ja) * | 2020-12-21 | 2022-06-30 | パナソニックIpマネジメント株式会社 | アルカリ乾電池 |
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US9040196B2 (en) | 2010-10-07 | 2015-05-26 | Panasonic Intellectual Property Management Co., Ltd. | Alkaline primary battery |
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EP2337129B1 (en) | 2017-01-18 |
JP4493059B2 (ja) | 2010-06-30 |
US7820326B2 (en) | 2010-10-26 |
EP2337129A1 (en) | 2011-06-22 |
US20100099028A1 (en) | 2010-04-22 |
EP2337129A4 (en) | 2016-01-13 |
CN101803083B (zh) | 2015-07-22 |
CN101803083A (zh) | 2010-08-11 |
JPWO2010044176A1 (ja) | 2012-03-08 |
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