WO2010067493A1 - アルカリ乾電池 - Google Patents
アルカリ乾電池 Download PDFInfo
- Publication number
- WO2010067493A1 WO2010067493A1 PCT/JP2009/005119 JP2009005119W WO2010067493A1 WO 2010067493 A1 WO2010067493 A1 WO 2010067493A1 JP 2009005119 W JP2009005119 W JP 2009005119W WO 2010067493 A1 WO2010067493 A1 WO 2010067493A1
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- WO
- WIPO (PCT)
- Prior art keywords
- zinc
- negative electrode
- mass
- alkaline
- dry battery
- Prior art date
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- 239000011701 zinc Substances 0.000 claims abstract description 142
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 139
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 135
- 239000004094 surface-active agent Substances 0.000 claims abstract description 29
- 239000003792 electrolyte Substances 0.000 claims description 53
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 25
- 239000000835 fiber Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- 239000013078 crystal Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 238000002074 melt spinning Methods 0.000 claims description 5
- 238000004804 winding Methods 0.000 claims description 5
- 229910052977 alkali metal sulfide Inorganic materials 0.000 claims description 4
- 238000005476 soldering Methods 0.000 claims description 4
- 238000003466 welding Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 150000003568 thioethers Chemical class 0.000 claims 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 10
- 239000008151 electrolyte solution Substances 0.000 abstract description 8
- 239000011796 hollow space material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 36
- 239000000203 mixture Substances 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 13
- 239000008188 pellet Substances 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000155 melt Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- QPPQHRDVPBTVEV-UHFFFAOYSA-N isopropyl dihydrogen phosphate Chemical compound CC(C)OP(O)(O)=O QPPQHRDVPBTVEV-UHFFFAOYSA-N 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- -1 Sulfide ions Chemical class 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- FANSKVBLGRZAQA-UHFFFAOYSA-M dipotassium;sulfanide Chemical compound [SH-].[K+].[K+] FANSKVBLGRZAQA-UHFFFAOYSA-M 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002472 indium compounds Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 230000009993 protective function Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 150000003751 zinc Chemical class 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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
- H01M6/08—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with cup-shaped 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
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
- H01M4/12—Processes of manufacture of consumable metal or alloy electrodes
-
- 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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/045—Cells with aqueous electrolyte characterised by aqueous electrolyte
-
- 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
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0014—Alkaline electrolytes
-
- 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
- H01M4/42—Alloys based on zinc
-
- 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
-
- 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 an alkaline battery.
- alkaline battery (alkaline manganese battery) using manganese dioxide for the positive electrode, zinc for the negative electrode, and an alkaline aqueous solution for the electrolyte is widely used as a power source for various devices because it is versatile and inexpensive.
- Some commercially available alkaline batteries use zinc gel in which zinc powder is dispersed in a gel alkaline electrolyte in which a gel component (polyacrylic acid or the like) is dissolved as a negative electrode.
- the negative electrode using zinc gel has insufficient electrical bonding / contact degree (conducting network) between zinc powders, and the ionic conductivity of the gel alkaline electrolyte is also low. For this reason, in the negative electrode using a zinc gel, the zinc utilization rate at the time of high rate discharge tends to become low.
- Patent Documents 1 to 3 a zinc porous body (ribbon, wool, foam metal, etc.) is used for the negative electrode to improve the conductive network, and at the same time, an alkali with high ion conductivity that does not contain a gel component. Techniques have been proposed that employ an electrolytic solution to increase the zinc utilization rate.
- the alkaline dry battery of the present invention comprises a bottomed cylindrical battery case, a hollow cylindrical positive electrode, a negative electrode disposed in a hollow portion of the positive electrode, and the positive electrode and the negative electrode.
- the theoretical capacity of MnO 2 contained in the positive electrode is 308 mAh / g
- the theoretical capacity of Zn contained in the negative electrode is 820 mAh / g.
- the calculated capacity balance of the negative electrode / positive electrode was 0.9 or more and 1.1 or less.
- an alkaline battery having excellent high rate discharge characteristics and excellent medium to low rate discharge characteristics.
- FIG. 4 is a chart showing discharge characteristics of dry batteries according to Example 2 and Comparative Examples 2 and 3; It is a graph which shows the kind of surfactant.
- 6 is a chart showing discharge characteristics of dry batteries according to Example 3 and Comparative Examples 2 and 4; 6 is a chart showing discharge characteristics of dry batteries according to Example 4 and Comparative Example 2. 6 is a chart showing discharge characteristics of dry batteries according to Example 5 and Comparative Example 2.
- 6 is a chart showing discharge characteristics of dry batteries according to Example 6 and Comparative Example 2.
- 7 is a chart showing discharge characteristics of dry batteries according to Example 7 and Comparative Example 2.
- 6 is a chart showing discharge characteristics of dry batteries according to Example 8 and Comparative Example 2. It is a graph which shows the discharge characteristic of the dry battery which concerns on Example 9 and Comparative Examples 2 and 5.
- FIG. 1 is a chart showing discharge characteristics of dry batteries according to Example 6 and Comparative Example 2.
- FIG. 2 The configuration of an alkaline battery using zinc gel is as shown in FIG. 2.
- a negative electrode 103 made of zinc gel is arranged inside a hollow cylindrical positive electrode pellet 102 arranged in a battery case 101 with a separator 104 interposed therebetween.
- Such an alkaline battery has an insufficient electrical connection / contact degree (conducting network) between zinc powders and a low ion conductivity of the gel alkaline electrolyte. Therefore, as described above, it is considered to use a porous zinc body for the negative electrode.
- An alkaline battery using a zinc porous body as a negative electrode has excellent high-rate discharge characteristics.
- the alkaline dry battery of Embodiment 1 includes a bottomed cylindrical battery case, a hollow cylindrical positive electrode, a negative electrode disposed in a hollow portion of the positive electrode, a separator disposed between the positive electrode and the negative electrode, an alkaline
- the negative electrode contains a zinc porous body, and in the alkaline electrolyte, a surfactant having an average molecular weight of 120 or more and 350 or less is 0.1% relative to the mass of zinc in the negative electrode.
- the negative electrode / positive electrode capacity balance is calculated with the theoretical capacity of MnO 2 contained in the positive electrode being 308 mAh / g and the theoretical capacity of Zn contained in the negative electrode being 820 mAh / g. , 0.9 or more and 1.1 or less.
- Examples of the zinc porous body include those made of ribbons, foams, compressed fibers, filaments, threads or strands described in Patent Documents 1 to 3.
- the surfactant of this embodiment is soluble in an alkaline electrolyte (a high concentration potassium hydroxide aqueous solution of 30% by mass or more) and at the same time is adsorbed on the zinc reaction surface at the end of discharge to passivate. This provides a moderate protection function to prevent the above.
- the average molecular weight of the surfactant is 350 or less from the viewpoint of solubility in an alkaline electrolyte, and the average molecular weight of the surfactant is 120 or more from the viewpoint of providing a protective function for the zinc surface.
- the addition amount of the surfactant is less than 0.1% by mass with respect to the zinc mass, it becomes difficult to obtain a sufficient passivation suppression effect, and the addition amount is more than 2% by mass with respect to the zinc mass. If the amount is too large, the ionic conductivity of the alkaline electrolyte may decrease.
- the average molecular weight of the surfactant can be calculated from the chemical formula or can be measured by mass spectrometry (MS).
- MS mass spectrometry
- the alkaline electrolyte extracted from the dry battery is evaporated to dryness, or the alkaline electrolyte is chloroform or There is a method of performing solvent extraction using dimethyl sulfoxide and analyzing the extracted components by LC / MS or GC / MS.
- the capacity balance of the negative electrode / positive electrode calculated from the theoretical capacity of MnO 2 contained in the positive electrode being 308 mAh / g and the theoretical capacity of Zn contained in the negative electrode being 820 mAh / g is 0.9 or more and 1.1. It is as follows.
- the negative electrode / positive electrode capacity balance is usually larger than 1.1. This is because the utilization rate of the gelled negative electrode is extremely lower than the utilization rate of the positive electrode, and therefore, it is necessary to store in the battery in excess of the theoretical value.
- the capacity balance of the negative electrode / positive electrode can be 1.1 or less, more than the conventional one. It is possible to increase the capacity of the battery by storing the positive electrode material in the battery. Moreover, by setting the capacity balance of the negative electrode / positive electrode to 0.9 or more, a necessary and sufficient zinc material can be accommodated in the battery, and it is also possible to obtain an alkaline dry battery having a large capacity.
- a zinc porous body is used as the negative electrode active material, and the conductive network in the negative electrode is remarkably improved as compared with the conventional system using zinc gel. For this reason, even when the amount of the surfactant added is as large as 1% by mass or more and 2% by mass or less with respect to the zinc mass, the high-rate discharge characteristics are not hindered. It is possible to improve the discharge characteristic at a low rate most effectively. That is, in the present invention, it is more desirable that the amount of the surfactant added is in the range of 1% by mass to 2% by mass with respect to the mass of zinc.
- the alkali electrolyte contains an alkali metal sulfide salt in an amount of 0.01% by mass to 1% by mass with respect to the mass of zinc.
- Sulfide ions (S 2 ⁇ ) generated by the dissolution of alkali metal sulfide in the electrolyte also adsorb on the zinc surface and exhibit the effect of complementing the suppression of passivation by the surfactant. If the amount of the alkali metal sulfide salt is 0.01% by mass or more with respect to the mass of zinc, a sufficient effect can be obtained, and if it is 1% by mass or less with respect to the mass of zinc, an alkaline electrolyte can be obtained. Therefore, satisfactory battery characteristics can be easily obtained.
- lithium hydroxide is contained in the alkaline electrolyte in an amount of 0.1% by mass to 2% by mass with respect to the mass of zinc.
- the zinc oxide particles (needle crystals) of the negative electrode discharge product are refined, and surface passivation is delayed and suppressed. Tend to. Therefore, the function of the surfactant in the present invention can be further supplemented, and the medium to low rate discharge characteristics can be further enhanced. If the addition amount of lithium hydroxide is 0.1% by mass or more with respect to the mass of zinc, a sufficient effect can be obtained. If the addition amount is 2% by mass or less with respect to the mass of zinc, ion conduction of the alkaline electrolyte is achieved. It is easy to obtain satisfactory battery characteristics.
- the porous zinc body used in this embodiment is preferably formed of zinc having an average crystal grain size of 20 ⁇ m or more and 100 ⁇ m or less. Since the discharge (oxidation) reaction of the zinc porous body proceeds mainly at the grain boundaries (interfaces between crystals) on the zinc surface, controlling the crystal grain size to an appropriate size improves discharge characteristics. Is very important. If the crystal grain size is as small as less than 20 ⁇ m, the initial electrode reactivity is high, but isolation of the crystal grains within the electrode tends to occur when oxidation outside the zinc crystal grains proceeds at the end of discharge. For this reason, it is difficult to take out the final capacity in the medium to low rate discharge.
- the average crystal grain size of zinc metal is in the range of 20 ⁇ m to 100 ⁇ m.
- the average crystal grain size of zinc metal is a value obtained by averaging the crystal grain size shown in the photograph by enlarging the surface of the zinc porous body with an optical microscope or an electron microscope. (The measurement method will be described in detail later.)
- the size of such an average crystal grain size is adjusted by adjusting the rate at which molten zinc is solidified during the production of the zinc porous body, or by subjecting the zinc porous body to heat treatment. It is possible to control to an appropriate range by applying.
- the negative electrode is preferably formed by winding a zinc porous sheet that is a sheet-shaped zinc porous body.
- a zinc porous body for the negative electrode of an alkaline dry battery, it is necessary to form the porous body into a cylindrical shape or a cylindrical shape.
- a method is conceivable in which a predetermined amount of a porous zinc body is placed in a hollow portion of a cylindrical outer mold and then directly compression-molded with a piston-shaped inner mold.
- burrs and whiskers of the porous zinc body are squeezed into the clearance between the outer mold and the inner mold, resulting in frequent mass production problems.
- a method of obtaining a cylindrical (columnar) negative electrode by winding a zinc porous sheet molded into a flat plate has an advantage in cost and the like.
- a structure in which a current collector is provided in the central part to collect the negative electrode Is desirable.
- the zinc porous sheet is wound around a metal current collecting pin connected by either welding or soldering, and the current collecting pin is substantially at the center of the negative electrode in a cross section perpendicular to the central axis of the battery case. It is desirable to have a structure located in The discharge reaction (oxidation) of zinc in the alkaline battery proceeds from the outer periphery of the negative electrode facing the positive electrode toward the center, so the position where the negative electrode is collected is a cross section perpendicular to the central axis of the battery case. In principle, it is appropriate to be approximately the center of the negative electrode.
- a metal current collecting pin is connected to one end of the zinc porous body sheet by either welding or soldering, and the sheet is wound using this pin as a starting point (winding core). This is the easiest in the process.
- a current collection pin exists in the circle
- the porous zinc sheet used in this case is preferably formed of an aggregate of zinc fibers having a diameter of 50 ⁇ m to 500 ⁇ m and a length of 10 mm to 300 mm.
- the zinc porous body sheet needs to have a mechanical strength that maintains the shape as the negative electrode and a sufficient surface area for the discharge reaction to proceed smoothly.
- the diameter of the zinc fiber By setting the diameter of the zinc fiber to 50 ⁇ m or more and the length to 10 mm or more, it is possible to obtain mechanical strength that maintains the shape of the negative electrode.
- the surface area required for reaction is securable by making the diameter of a zinc fiber into 2000 micrometers or less, Preferably it is 500 micrometers or less, and length is 300 mm or less.
- the zinc fibers as described above can be produced inexpensively and efficiently by the melt spinning method.
- the melt spinning method is a general term for a method of thinning a metal from a melt at once, and more specifically, is classified into a melt extrusion method, a rotating liquid method, a melt drawing method, a jet quenching method, and the like.
- the melt extrusion method it is extruded into the cooling fluid from the nozzle pores, in the rotating liquid method, the melt is injected into the rotating water stream, and in the melt drawing method, it is discharged into the gas or the atmosphere and jet quenching is performed.
- metal fibers are manufactured by spraying onto a rotating metal drum and cooling each of them. At this time, it is possible to obtain metal fibers having a desired diameter and length by changing the nozzle diameter and spraying conditions.
- the mass ratio x / y of the alkaline electrolyte to zinc is It is desirable to design the battery so as to satisfy 1.0 ⁇ x / y ⁇ 1.5.
- the x / y value is usually set to a range of less than 1.0 in an alkaline dry battery having a gelled negative electrode using a general zinc powder.
- the alkaline dry battery according to Embodiment 1 has a positive electrode made of a hollow cylindrical positive electrode mixture pellet 2 and a negative electrode 3 made of a zinc porous sheet.
- the positive electrode material mixture pellet 2 and the negative electrode 3 are separated by a separator 4.
- the bottomed cylindrical battery case 8 is made of a nickel-plated steel plate.
- a graphite coating film is formed inside the battery case 8.
- the alkaline dry battery shown in FIG. 1 can be manufactured as follows. That is, first, a plurality of hollow cylindrical positive electrode mixture pellets (positive electrodes) 2 containing a positive electrode active material such as manganese dioxide are inserted into the battery case 8 and are brought into close contact with the inner surface of the battery case 8 by pressurization.
- a positive electrode active material such as manganese dioxide
- the negative electrode 3 is inserted inside the separator 4 and filled with an alkaline electrolyte.
- the negative electrode 3 is prepared in advance by winding a porous sheet of zinc which is a negative electrode active material.
- the zinc porous sheet is formed by compressing zinc fibers having a diameter of 50 ⁇ m to 500 ⁇ m and a length of 10 mm to 300 mm.
- the alkaline electrolyte is composed of an aqueous potassium hydroxide solution, to which at least one of an anionic surfactant having an average molecular weight of 120 or more and 350 or less and a quaternary ammonium salt type cationic surfactant is added. Accordingly, indium compounds, bismuth compounds, tin compounds and the like are added.
- the negative electrode 3 has a cylindrical shape, and a metal current collecting pin 6 is installed on the central axis thereof.
- the head of the current collecting pin 6 protrudes on the zinc porous body sheet and has a concave portion opened upward.
- the negative electrode relay portion 10 is fitted in the concave portion of the current collecting pin 6.
- the negative electrode relay portion 10 is integrated as a negative electrode terminal structure 9 together with a resin sealing plate 5 and a bottom plate 7 that also serves as a negative electrode terminal. At this time, the negative electrode relay portion 10 is inserted into the concave portion of the head portion of the current collecting pin 6 and the current collecting pin 6 and the bottom plate 7 are electrically connected.
- the negative electrode terminal structure 9 is inserted into the opening end of the battery case 8. Then, the opening end portion of the battery case 8 is caulked to the peripheral edge portion of the bottom plate 7 via the end portion of the sealing plate 5 so that the opening portion of the battery case 8 is brought into close contact.
- the alkaline dry battery in this embodiment can be obtained.
- Example 1 -Fabrication of positive electrode- The positive electrode was produced as follows. Electrolytic manganese dioxide and graphite are mixed at a weight ratio of 94: 6, and 1 part by weight of an electrolyte (39% by weight potassium hydroxide aqueous solution containing 2% by weight of ZnO) is mixed with 100 parts by weight of the mixed powder. Then, the mixture was uniformly stirred and mixed with a mixer to regulate the particle size. And the obtained granular material was pressure-molded using the hollow cylinder type
- electrolytic manganese dioxide used was HH-TF manufactured by Tosoh Corporation, and graphite used was SP-20 manufactured by Nippon Graphite Industries Co., Ltd.
- Zinc fibers (average diameter: 100 ⁇ m, average length: 20 mm, manufactured by Akao Aluminum Co., Ltd.) obtained by the melt spinning method were compressed with a flat pressure press to obtain a nonwoven sheet.
- This zinc fiber sheet was a zinc porous body sheet having spaces communicating with each other, and the zinc fiber sheet was cut into a rectangle having a predetermined size.
- the zinc fiber sheet was wound like a roll cake around the current collecting pin.
- a negative electrode composed of a substantially cylindrical zinc porous body was produced.
- the current collecting pin is substantially located on the central axis of the cylinder, and the diameter of the cylinder is about 1 mm smaller than the inner diameter of the positive electrode mixture pellet.
- the positive electrode mixture pellet obtained as described above was inserted so as to cover the inner wall surface of the battery case made of a nickel-plated steel sheet, and then a separator was further inserted.
- a separator a vinylon-lyocell composite nonwoven fabric manufactured by Kuraray Co., Ltd. was used.
- the negative electrode relay portion of the negative electrode terminal structure was fitted into the concave portion of the head of the current collecting pin connected to the negative electrode, thereby connecting the negative electrode and the negative electrode terminal structure.
- the columnar negative electrode was inserted into the hollow part of the positive electrode mixture pellet, and was inserted up to about half of the length direction of the column. At this time, a separator was interposed between the positive electrode and the negative electrode.
- Comparative Example 1 The dry battery Y according to Comparative Example 1 was produced in the same manner as in Example 1 except that the alkaline electrolyte according to Example 1 was not added with a surfactant in the alkaline electrolyte.
- Comparative Example 2 In the dry battery Z according to Comparative Example 2, a conventional gel alkaline electrolyte in which zinc powder was dispersed was used as the negative electrode.
- a gel alkaline electrolyte 54 parts by weight of a 33% by weight aqueous potassium hydroxide solution (containing 2% by weight of ZnO), 0.7 parts by weight of crosslinked polyacrylic acid, and 1.4 parts by weight of crosslinked sodium polyacrylate The mixture was used, and the zinc mass and alkaline electrolyte mass in the battery were the same as in Example 1. Other than that was produced in the same manner as in Example 1.
- FIG. 3 shows the evaluation results of the alkaline dry batteries according to Example 1 and Comparative Examples 1 and 2.
- the dry battery Y according to Comparative Example 1 using the porous zinc body as the negative electrode is superior in the high-rate pulse discharge characteristics to the dry battery Z according to Comparative Example 2 using zinc gel as the negative electrode, but has a low rate and a medium rate. Discharge characteristics are inferior.
- the alkaline dry battery A according to Example 1 using a zinc porous body for the negative electrode and adding a surfactant to the alkaline electrolyte has superior high-rate pulse discharge characteristics as compared to the dry battery Z, and low-rate and medium-rate discharge. The characteristics are also excellent. This is because the high-rate pulse discharge characteristics are improved because a zinc porous body is used for the negative electrode, and since the surfactant is added to the alkaline electrolyte, the low-rate and medium-rate discharge characteristics are also improved. is there.
- Example 2 Comparative Example 3
- the dry batteries according to Example 2 and Comparative Example 3 were produced in the same manner as in Example 1 except that the amount of isopropyl phosphate (surfactant) added in the alkaline electrolyte in Example 1 was changed.
- the evaluation results of the discharge characteristics of the dry batteries B2 to B6 according to Example 2 and the dry batteries B1 and B7 according to Comparative Example 3 are shown in FIG.
- Dry battery B1 with a small amount of added surfactant has discharge characteristics somewhat similar to dry battery Y of Comparative Example 1, and the medium and low rate characteristics are not improved.
- the dry battery B7 in which the amount of the surfactant added is too large has substantially the same discharge characteristics as the dry battery Z of Comparative Example 2, and no improvement in the discharge characteristics is observed.
- all of the dry batteries B2 to B6 have greatly improved high rate discharge characteristics and also improved medium rate and low rate discharge characteristics. In particular, when the addition amount is in the range of 1% by mass to 2% by mass, the medium-rate and low-rate discharge characteristics are greatly improved.
- Example 3 Comparative Example 4
- the dry batteries according to Example 3 and Comparative Example 4 were produced in the same manner as in Example 1 except that the type of surfactant in the alkaline electrolyte in Example 1 was changed.
- C6 and C11 having a large molecular weight were not completely dissolved in the alkaline electrolyte but suspended, they were used as they were to prepare a dry battery.
- FIG. 6 shows the evaluation results of the discharge characteristics of the dry cells C2 to C5, C8 to C10 according to Example 3, and the dry cells C1, C6, C7, and C11 according to Comparative Example 4.
- the addition amount of the surfactant is 1.2% by mass with respect to the zinc of the negative electrode.
- the dry cells C2 to C5 and C8 to C10 of Example 3 have high high-rate discharge characteristics, and the low-rate and medium-rate discharge characteristics are also improved compared to the dry battery Z.
- the dry cells C1 and C7 of Comparative Example 4 have a molecular weight that is too small and the adsorption / protection function on the zinc surface is poor, and the dry cells C6 and C11 have a molecular weight that is too large to dissolve sufficiently in the electrolyte solution.
- the low-rate and medium-rate discharge characteristics are inferior, for example, by inhibiting the reaction.
- the average molecular weight is 120 or more and 350 or less, the discharge characteristics are improved by adding to the alkaline electrolyte regardless of the type of the surfactant.
- Example 4 The dry battery according to Example 4 was produced in the same manner as the dry battery A of Example 1 except that potassium sulfide (K 2 S) was further added to the alkaline electrolyte with respect to the dry battery A of Example 1.
- K 2 S potassium sulfide
- FIG. 7 shows the evaluation results of the discharge characteristics of the dry batteries D1 to D6 according to this example.
- the addition amount of K 2 S is indicated by a percentage by weight relative to the zinc negative electrode.
- the discharge characteristics are improved as compared with the dry battery A.
- the dry battery D1 with a small amount of K 2 S added has the same discharge characteristics as the dry battery A.
- the discharge characteristics are slightly inferior to the dry battery A. This is considered to be because the ionic conductivity in the alkaline electrolyte is lowered when too much K 2 S is added.
- the discharge characteristics of the dry battery D6 are superior to the dry battery Z of Comparative Example 2.
- Example 5 The dry battery according to Example 5 was produced in the same manner as the dry battery A of Example 1 except that lithium hydroxide (LiOH) was further added to the alkaline electrolyte with respect to the dry battery A of Example 1.
- LiOH lithium hydroxide
- FIG. 8 shows the evaluation results of the discharge characteristics of the dry batteries E1 to E6 according to this example.
- the addition amount of LiOH is shown by the mass% with respect to zinc of a negative electrode.
- the discharge characteristics are improved as compared with the dry battery A.
- the dry battery E1 with a small amount of LiOH added has the same discharge characteristics as the dry battery A.
- the dry battery E6 with a large amount of LiOH added the discharge characteristics are slightly inferior to the dry battery A. This is presumably because the ionic conductivity in the alkaline electrolyte is lowered when too much LiOH is added.
- the discharge characteristics of the dry battery E6 are superior to the dry battery Z of Comparative Example 2.
- Example 6 A dry battery according to Example 6 was produced in the same manner as in Example 1 except that the crystal grain size of zinc forming the zinc porous body in Example 1 was variously changed. The crystal grain size was adjusted by changing the temperature of the molten zinc and the temperature of the spraying atmosphere when the zinc fiber was produced by melt spinning, and by annealing the zinc fiber in an Ar gas atmosphere. The diameter and length of the zinc fiber were the same as the diameter and length of the zinc fiber used in the dry battery A.
- the crystal grain size of zinc was measured from a micrograph. That is, the surface of the zinc porous body is magnified with an optical microscope, a photograph is taken, and the crystal grain size in the photograph is measured. The magnification of the microscope was adjusted so that several tens or more of the area surrounded by the grain boundaries appeared in one photograph.
- Draw a plurality of straight lines arbitrarily in the micrograph select straight lines having intersections with 10 or more grain boundaries, and from the intersections of the straight lines and the first grain boundaries in 10 consecutive grain boundaries, The distance to the intersection of the straight line and the tenth grain boundary was measured, and a value r obtained by dividing the distance by 9 was obtained. Two or more such straight lines were selected to obtain r, and the average value of these r was taken as the crystal grain size of zinc metal forming the zinc porous body.
- the change range of the average crystal grain size of zinc is as shown in FIG.
- the evaluation results of the discharge characteristics of the dry batteries F1 to F6 according to Example 6 are shown in FIG.
- the dry batteries F1 to F6 have improved discharge characteristics.
- the discharge characteristics are good when the average crystal grain size is in the range of 20 ⁇ m to 100 ⁇ m.
- Example 7 The dry battery according to Example 7 was produced in the same manner as in Example 1 except that the diameter or length of the zinc fiber in Example 1 was changed. The change range of the diameter and length of the zinc fiber is as shown in FIG. The evaluation results of the discharge characteristics of the dry batteries G1 to G10 according to Example 7 are shown in FIG.
- the dry batteries G1 to G10 Compared with the dry battery Z of Comparative Example 2, all of the dry batteries G1 to G10 have improved discharge characteristics. Particularly, the discharge characteristics are good when the diameter is in the range of 50 ⁇ m to 500 ⁇ m, and the length is 10 mm to 300 mm. When it is below, the discharge characteristics are good.
- Example 8 In the dry battery according to Example 8, in the dry battery A of Example 1, the mass x [g] of alkaline electrolyte per dry battery and the mass y [g] of zinc contained in the negative electrode are constant x + y. It was produced in the same manner as in Example 1 except that it was changed under the conditions. The change range of x and y is the value of x / y as shown in FIG. The evaluation results of the discharge characteristics of the dry batteries H1 to H5 according to Example 8 are shown in FIG.
- Example 9 Comparative Example 5
- the amount of the positive electrode and the amount of the negative electrode per dry cell in the dry battery A of Example 1 were changed under the condition that the total volume of both was constant. Except for this, it was produced in the same manner as in Example 1.
- the negative electrode / positive electrode capacity balance calculated with the theoretical capacity of MnO 2 contained in the positive electrode as 308 mAh / g and the theoretical capacity of Zn contained in the negative electrode as 820 mAh / g is used as an index. Changed.
- the range of change between the amount of the positive electrode and the amount of the negative electrode is as shown in FIG.
- the evaluation results of the discharge characteristics of the dry batteries J2 to J4 according to Example 9 and the dry batteries J1 and J5 according to Comparative Example 5 are shown in FIG.
- the dry battery Z of Comparative Example 2 has a capacity balance value of negative electrode / positive electrode larger than 1.1, but in comparison with this, the dry battery of this example having a capacity balance in the range of 0.9 to 1.1 is Discharge characteristics are good.
- the dry battery J1 of Comparative Example 5 having a capacity balance smaller than 0.9 and the dry battery J5 having a capacity balance larger than 1.1 have substantially the same discharge characteristics as the dry battery Z.
- the fixing method of the current collecting pins to the zinc fiber sheet is not limited to soldering, but may be welding or a combination of both.
- a zinc porous body made of a ribbon, a foamed zinc porous body, a compressed porous fiber, a filament, a thread, or a strand described in Patent Documents 1 to 3 may be used. Good.
- the zinc fiber sheet was made from pure zinc, but it may be made from a zinc alloy containing a small amount of elements such as indium, bismuth, aluminum, calcium and magnesium from the viewpoint of corrosion protection.
- the type of the surfactant is not limited to those listed in the examples, and any surfactant having an average molecular weight of 120 to 350 may be used.
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Abstract
Description
実施形態1のアルカリ乾電池は、有底円筒形の電池ケースに、中空円筒状の正極と、正極の中空部分に配置されている負極と、正極と負極との間に配置されたセパレータと、アルカリ電解液とを収容しており、前記負極は亜鉛多孔体を含んでおり、アルカリ電解液には、平均分子量が120以上350以下である界面活性剤が負極中の亜鉛質量に対して0.1質量%以上2質量%以下含まれており、正極に含まれるMnO2の理論容量を308mAh/g、負極に含まれるZnの理論容量を820mAh/gとして計算される、負極/正極の容量バランスが、0.9以上1.1以下である構成を備えているものである。亜鉛多孔体としては、特許文献1乃至3に記載されているリボンからなるもの、発泡状のもの、圧縮されたファイバ、フィラメント、スレッドまたはストランドからなるものを例として挙げることができる。
実施形態1に係るアルカリ乾電池について図1を参照して説明する。
-正極の作製-
正極は、次のように作製した。電解二酸化マンガン及び黒鉛を重量比94:6の割合で混合し、この混合粉100重量部に対して電解液(ZnOを2重量%含有する39重量%の水酸化カリウム水溶液)1重量部を混合させた後、ミキサーで均一に攪拌・混合を行って一定粒度に整粒した。そして得られた粒状物を中空円筒型を用いて加圧成形して正極合剤ペレットとした。ここで、電解二酸化マンガンは東ソー株式会社製のHH-TF、黒鉛は日本黒鉛工業株式会社製のSP-20を用いた。
溶融紡糸法によって得られた亜鉛繊維(平均直径:100μm、平均長さ:20mm、アカオアルミ株式会社製)を平圧プレスで圧縮して不織布状のシートとした。この亜鉛繊維シートは互いに連通する空間を内部に有する亜鉛多孔体シートであって、この亜鉛繊維シートを所定寸法の長方形に切断した。
上記のようにして得られた正極合剤ペレットをニッケルめっき鋼板からなる電池ケースの内壁面を覆うように挿入した後、セパレータをさらに挿入した。セパレータは株式会社クラレ製のビニロン-リヨセル複合不織布を用いた。
比較例1に係る乾電池Yは、実施例1に係るアルカリ乾電池において、アルカリ電解液に界面活性剤を添加していないこと以外は実施例1と同様にして作製された。
比較例2に係る乾電池Zには、従来のゲル状アルカリ電解液に亜鉛粉を分散させたものを負極として用いた。ゲル状アルカリ電解液として、33重量%の水酸化カリウム水溶液(ZnOを2重量%含有)54重量部、架橋型ポリアクリル酸0.7重量部、架橋型ポリアクリル酸ナトリウム1.4重量部を混合したものを用い、電池内の亜鉛質量およびアルカリ電解液質量は実施例1と同じにした。それ以外は実施例1と同様にして作製した。
(1)低レート放電特性評価
作製した乾電池を用いて、21℃の恒温雰囲気下において、100mAの定電流で1時間/日の割合で放電を行った。このときに電池電圧が0.9Vに達するまでの合計の放電時間を測定した。この時間が長いほど低レート放電特性が優れていると判定される。
作製した乾電池を用いて、21℃の恒温雰囲気下において、250mAの定電流で1時間/日の割合で放電を行った。このときに電池電圧が0.9Vに達するまでの合計の放電時間を測定した。この時間が長いほど中レート放電特性が優れていると判定される。
作製した乾電池を用いて、21℃の恒温雰囲気下において、1.5Wで2秒間放電し、その後0.65Wで28秒放電する工程(パルス放電)を1サイクルとし、1時間当たり10サイクルのペースでパルス放電を行った。このときに閉路電圧が1.05Vに達するまでの時間を測定した。なお、この評価は、ANSI C18.1Mに定められた放電試験の方法を準用している。
実施例2、比較例3に係る乾電池は、実施例例1におけるアルカリ電解液中のリン酸イソプロピル(界面活性剤)の添加量を変更した点以外は実施例1と同様にして作製された。実施例2に係る乾電池B2からB6、および比較例3に係る乾電池B1、B7の放電特性の評価結果を図4に示す。
実施例3、比較例4に係る乾電池は、実施例1におけるアルカリ電解液中の界面活性剤の種類を変更したこと以外は、実施例1と同様にして作製された。界面活性剤の種類は、図5に示す11種類であり、C1からC6まではアニオン性界面活性剤であり、C7からC11まではカチオン性界面活性剤である。なお、分子量が大きいC6,C11は完全にはアルカリ電解液に溶解せず懸濁していたが、そのまま使用して乾電池を作製した。実施例3に係る乾電池C2からC5、C8からC10、および比較例4に係る乾電池C1、C6、C7、C11の放電特性の評価結果を図6に示す。C1からC11の全ての乾電池において界面活性剤の添加量は、負極の亜鉛に対して1.2質量%としている。
実施例4に係る乾電池は、実施例1の乾電池Aに対してさらに硫化カリウム(K2S)をアルカリ電解液に添加したこと以外は、実施例1の乾電池Aと同様にして作製された。
実施例5に係る乾電池は、実施例1の乾電池Aに対してさらに水酸化リチウム(LiOH)をアルカリ電解液に添加したこと以外は、実施例1の乾電池Aと同様にして作製された。
実施例6に係る乾電池は、実施例1における亜鉛多孔体を形成する亜鉛の結晶粒径を種々に変更したこと以外は実施例1と同様にして作製された。結晶粒径は、亜鉛繊維を溶融紡糸により作製する際に溶融亜鉛の温度や噴霧雰囲気の温度を変更することにより、また亜鉛繊維をArガス雰囲気下でアニールすることにより調整した。なお、亜鉛繊維の径、長さは乾電池Aに用いられた亜鉛繊維の径、長さと同等とした。
実施例7に係る乾電池は、実施例1における亜鉛繊維の直径または長さを変更したこと以外は実施例1と同様にして作製された。亜鉛繊維の直径、長さの変更範囲は図10に示すとおりである。実施例7に係る乾電池G1からG10の放電特性の評価結果を図10に示す。
実施例8に係る乾電池は、実施例1の乾電池Aにおいて1本の乾電池当たりのアルカリ電解液の質量x[g]と負極に含まれる亜鉛の質量y[g]とを、x+yが一定となる条件の下で変更していったこと以外は実施例1と同様にして作製された。xとyとの変更範囲は、x/yの値で図11に示すとおりのものである。実施例8に係る乾電池H1からH5の放電特性の評価結果を図11に示す。
実施例9および比較例5に係る乾電池は、実施例1の乾電池Aにおける1本の乾電池当たりの正極の量と負極の量とを、両者の体積の合計が一定となる条件の下で変更したこと以外は実施例1と同様にして作製された。正極の量と負極の量とに関しては、正極に含まれるMnO2の理論容量を308mAh/g、負極に含まれるZnの理論容量を820mAh/gとして計算される負極/正極の容量バランスを指標として変更を行った。正極の量と負極の量との変更範囲は、負極/正極の容量バランスの値で図12に示すとおりのものである。実施例9に係る乾電池J2からJ4及び比較例5に係る乾電池J1、J5の放電特性の評価結果を図12に示す。
上記の実施形態および実施例は本発明の例示であって、本発明はこれらの例に限定されない。例えば、いくつかの実施例を組み合わせてもよい。例えば実施例2,4を組み合わせたり、実施例5,6を組み合わせたりすることが考えられるし、他の実施例の組み合わせを行ってもよい。
2 正極合剤ペレット
3 負極
4 セパレータ
5 樹脂製封口板
6 集電ピン
7 底板
8 電池ケース
9 負極端子構造体
10 負極中継部
Claims (10)
- 有底円筒形の電池ケースに、中空円筒状の正極と、該正極の中空部分に配置されている負極と、前記正極と負極との間に配置されたセパレータと、アルカリ電解液とを収容しており、
前記負極は亜鉛多孔体を含んでおり、
前記アルカリ電解液には、平均分子量が120以上350以下である界面活性剤が前記負極中の亜鉛質量に対して0.1質量%以上2質量%以下含まれており、
前記正極に含まれるMnO2の理論容量を308mAh/g、前記負極に含まれるZnの理論容量を820mAh/gとして計算される、負極/正極の容量バランスが、0.9以上1.1以下である、アルカリ乾電池。 - 前記界面活性剤の含有量が前記負極中の亜鉛質量に対して1質量%以上2質量%以下である、請求項1に記載のアルカリ乾電池。
- 前記アルカリ電解液には、さらにアルカリ金属の硫化物塩が前記負極中の亜鉛質量に対して0.01質量%以上1質量%以下含まれている、請求項1に記載のアルカリ乾電池。
- 前記アルカリ電解液には、さらに水酸化リチウムが前記負極中の亜鉛質量に対して0.1質量%以上2質量%以下含まれている、請求項1に記載のアルカリ乾電池。
- 前記亜鉛多孔体を形成する亜鉛の平均結晶粒径が、20μm以上100μm以下である、請求項1に記載のアルカリ乾電池。
- 前記負極は、シート形状の前記亜鉛多孔体を捲回して形成されている、請求項1に記載のアルカリ乾電池。
- シート形状の前記亜鉛多孔体である亜鉛多孔体シートは、溶接およびはんだづけの少なくとも一方によって該亜鉛多孔体シートに接続された金属からなる集電ピンを起点に捲回されており、
前記集電ピンは、前記電池ケースの中心軸に対して垂直な断面における前記負極の略中心に位置している、請求項6に記載のアルカリ乾電池。 - シート形状の前記亜鉛多孔体である亜鉛多孔体シートが、直径50μm以上500μm以下、長さ10mm以上300mm以下の亜鉛繊維の集合体により形成されている、請求項6に記載のアルカリ乾電池。
- 前記亜鉛繊維が溶融紡糸法によって作製されたものである、請求項8に記載のアルカリ乾電池。
- 前記アルカリ電解液の質量をx[g]、前記負極に含まれる亜鉛の質量をy[g]とするとき、1.0<x/y<1.5 を満たす、請求項1に記載のアルカリ乾電池。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010541963A JPWO2010067493A1 (ja) | 2008-12-12 | 2009-10-02 | アルカリ乾電池 |
CN2009801443659A CN102210052A (zh) | 2008-12-12 | 2009-10-02 | 碱性干电池 |
US13/054,723 US20110123847A1 (en) | 2008-12-12 | 2009-10-02 | Alkaline battery |
EP09831602A EP2367225A4 (en) | 2008-12-12 | 2009-10-02 | ALKALINE DRY BATTERY |
Applications Claiming Priority (2)
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JP2008-317587 | 2008-12-12 | ||
JP2008317587 | 2008-12-12 |
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WO2010067493A1 true WO2010067493A1 (ja) | 2010-06-17 |
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PCT/JP2009/005119 WO2010067493A1 (ja) | 2008-12-12 | 2009-10-02 | アルカリ乾電池 |
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US (1) | US20110123847A1 (ja) |
EP (1) | EP2367225A4 (ja) |
JP (1) | JPWO2010067493A1 (ja) |
CN (1) | CN102210052A (ja) |
WO (1) | WO2010067493A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10868340B2 (en) | 2018-03-23 | 2020-12-15 | Kabushiki Kaisha Toshiba | Secondary battery, battery pack, vehicle, and stationary power supply |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104201360B (zh) * | 2014-07-28 | 2016-09-21 | 宁波倍特瑞能源科技有限公司 | 一种碱性干电池及其制备方法 |
EP4097786A1 (en) | 2020-05-22 | 2022-12-07 | Duracell U.S. Operations, Inc. | Seal assembly for a battery cell |
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JPH06196155A (ja) * | 1992-12-22 | 1994-07-15 | Fuji Elelctrochem Co Ltd | 電池の負極亜鉛缶 |
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- 2009-10-02 US US13/054,723 patent/US20110123847A1/en not_active Abandoned
- 2009-10-02 EP EP09831602A patent/EP2367225A4/en not_active Withdrawn
- 2009-10-02 CN CN2009801443659A patent/CN102210052A/zh active Pending
- 2009-10-02 WO PCT/JP2009/005119 patent/WO2010067493A1/ja active Application Filing
- 2009-10-02 JP JP2010541963A patent/JPWO2010067493A1/ja not_active Withdrawn
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JPH06196155A (ja) * | 1992-12-22 | 1994-07-15 | Fuji Elelctrochem Co Ltd | 電池の負極亜鉛缶 |
JP2002531923A (ja) * | 1998-12-01 | 2002-09-24 | エヴァレディー バッテリー カンパニー インコーポレイテッド | 電気化学的電池用の電極構成 |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US10868340B2 (en) | 2018-03-23 | 2020-12-15 | Kabushiki Kaisha Toshiba | Secondary battery, battery pack, vehicle, and stationary power supply |
Also Published As
Publication number | Publication date |
---|---|
JPWO2010067493A1 (ja) | 2012-05-17 |
EP2367225A4 (en) | 2012-07-25 |
US20110123847A1 (en) | 2011-05-26 |
CN102210052A (zh) | 2011-10-05 |
EP2367225A1 (en) | 2011-09-21 |
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