WO2010023780A1 - Manganese dry battery - Google Patents
Manganese dry battery Download PDFInfo
- Publication number
- WO2010023780A1 WO2010023780A1 PCT/JP2009/001744 JP2009001744W WO2010023780A1 WO 2010023780 A1 WO2010023780 A1 WO 2010023780A1 JP 2009001744 W JP2009001744 W JP 2009001744W WO 2010023780 A1 WO2010023780 A1 WO 2010023780A1
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- WIPO (PCT)
- Prior art keywords
- positive electrode
- material mixture
- electrode material
- weight
- content
- Prior art date
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- 239000011572 manganese Substances 0.000 title claims abstract description 42
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 41
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 98
- 239000000203 mixture Substances 0.000 claims abstract description 74
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000007774 positive electrode material Substances 0.000 claims abstract description 71
- 239000003792 electrolyte Substances 0.000 claims abstract description 60
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 43
- 239000011734 sodium Substances 0.000 claims abstract description 43
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 38
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 38
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 239000011701 zinc Substances 0.000 claims abstract description 9
- 239000006258 conductive agent Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 35
- 239000000243 solution Substances 0.000 description 34
- 229910052799 carbon Inorganic materials 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000005259 measurement Methods 0.000 description 19
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 14
- 239000012535 impurity Substances 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 238000011088 calibration curve Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011575 calcium Substances 0.000 description 7
- 239000002655 kraft paper Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- 239000011592 zinc chloride Substances 0.000 description 7
- 235000005074 zinc chloride Nutrition 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000012491 analyte Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000009616 inductively coupled plasma Methods 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000123 paper Substances 0.000 description 5
- 239000012488 sample solution Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 4
- 229910001297 Zn alloy Inorganic materials 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 4
- 239000003729 cation exchange resin Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229910001453 nickel ion Inorganic materials 0.000 description 4
- 230000002093 peripheral effect Effects 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 4
- 229910001948 sodium oxide Inorganic materials 0.000 description 4
- 239000005028 tinplate Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000000159 acid neutralizing agent Substances 0.000 description 3
- 239000005456 alcohol based solvent Substances 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000004993 emission spectroscopy Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000003978 Ipomoea coccinea Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- 238000007796 conventional method Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
-
- 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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/045—Cells with aqueous electrolyte characterised by aqueous electrolyte
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
-
- 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
Definitions
- the present invention relates to a manganese dry battery, and specifically relates to improvements to a positive electrode material mixture and an electrolyte in a manganese dry battery.
- Patent Citation 1 proposes that in order to reduce the amount of alkali metal and the like contained in the electrolyte to be adsorbed into pores in manganese dioxide in the process of assembling a battery, and thereby to improve the discharge performance, the content of alkali metal or alkaline earth metal in the electrolyte, calculated as sulfate, be 0.3% by weight or less.
- Patent Citation 2 proposes that in order to suppress the corrosion of the negative electrode can due to impurities such as nickel contained in the manganese dioxide serving as a positive electrode active material, manganese dioxide in which the contents of nickel, cobalt, and copper are 0.04% by weight or less, 0.03% by weight or less, and 0.03% by weight or less, respectively, be used as a positive electrode active material.
- Patent Citation 1 if the content of nickel contained in the manganese dioxide as an impurity is high, the battery voltage may be lowered during storage and the storage characteristics may be deteriorated. In Patent Citation 2, if the content of sodium contained in the electrolyte as an impurity is high, the battery voltage may be lowered during storage and the storage characteristics may be deteriorated. The influence of impurities present inside a battery exerted on the storage characteristics of the battery has not been thoroughly studied. Japanese Laid-Open Patent Publication No. 2001-189157 Japanese Laid-Open Patent Publication No. Hei 8-83611
- the present invention intends to solve the above-described conventional problem and provide a highly reliable manganese dry battery with excellent storage characteristics.
- the present invention is directed to a manganese dry battery comprising a positive electrode material mixture including manganese dioxide, a negative electrode can including zinc, a separator layer disposed between the positive electrode material mixture and the negative electrode can, and an electrolyte, wherein the content of nickel in the positive electrode material mixture is 0.04% by weight or less, and the content of sodium in the electrolyte is 0.8% by weight or less.
- the positive electrode material mixture comprises a mixture of the manganese dioxide, a conductive agent, and the electrolyte, and the content of the manganese dioxide in the positive electrode material mixture is 40 to 60% by weight.
- the manganese dioxide is preferably at least one selected from natural manganese dioxide and electrolytic manganese dioxide.
- the content of nickel in the natural manganese dioxide is preferably 0.11% by weight or less.
- the content of sodium in the electrolytic manganese dioxide is preferably 0.4% by weight or less.
- V 1 - V 2 is equal to or less than 50, where V 1 represents an open-circuit voltage (mV) at 20 degrees Celsius in an initial state, and V 2 represents an open-circuit voltage (mV) at 20 degrees Celsius after storage in an environment of 50 degrees Celsius for 2 months.
- the manganese dry battery of the present invention is of size D, and T 2 /T 1 is equal to or more than 0.85, where T 1 represents a duration of continuous discharge in an initial state, and T 2 represents a duration of continuous discharge after storage in an environment of 50 degrees Celsius for 2 months, the continuous discharge being performed at a constant resistance of 2.2 ohms in an environment of 20 degrees Celsius until the closed-circuit voltage reaches 0.9 V.
- Fig. 1 is a partially sectioned front view of a manganese dry battery in an embodiment of the present invention.
- the present inventors have conducted intensive studies on the influence of impurities present inside a battery exerted on the storage characteristics of the battery, and as a result, found that: nickel contained in the manganese dioxide and sodium contained in the electrolyte have a significant influence on the storage characteristics of the battery; and the deterioration of the storage characteristics of the battery can be suppressed by reducing the content of nickel in the manganese dioxide and the content of sodium in the electrolyte to be 0.04% by weight or less and 0.8% by weight or less, respectively.
- the present invention relates to a manganese dry battery comprising a positive electrode material mixture including manganese dioxide, a negative electrode can including zinc, a separator layer disposed between the positive electrode material mixture and the negative electrode can, and an electrolyte.
- the present invention is characterized in that the content of nickel in the positive electrode material mixture is 0.04% by weight or less, and the content of sodium in the electrolyte is 0.8% by weight or less.
- the aforementioned contents of nickel in the manganese dioxide and sodium in the electrolyte are the values in the battery in an initial state (e.g., within 1 week after the production of the battery). In the subsequent state, the aforementioned contents of nickel and sodium remain almost unchanged even after the storage of the battery.
- the dendrites of sodium oxide thus formed may pierce the separator, causing internal short circuit.
- the content of nickel in the positive electrode material mixture exceeds 0.04% by weight and the content of sodium in the electrolyte exceeds 0.8% by weight, a weak discharge occurs as a result of the internal short circuit due to the dendrites of sodium oxide piercing the separator, and thus the pH in the vicinity of the separator shifts to a more acidic region.
- nickel in the nickel oxide in the manganese dioxide tends to be leached into the electrolyte in the form of nickel ions.
- the leached nickel ions migrate to the negative electrode and deposit on the surface of the negative electrode can containing zinc, the deposited nickel and the zinc form a local battery. Consequently, the zinc is consumed by the reaction with nickel, resulting in a significant drop in battery voltage.
- the content of nickel in the positive electrode material mixture is preferably 0 to 0.25% by weight.
- the content of sodium in the electrolyte is preferably 0 to 0.53% by weight.
- the nickel contained in the positive electrode material mixture is derived from the nickel present in the manganese dioxide as an impurity.
- manganese dioxide for example, electrolytic manganese dioxide (EMD) and natural manganese dioxide (NMD) may be used. Since NMD contains a large amount of impurities, it is preferable to quantitatively analyze the NMD beforehand to check the quality thereof.
- the content of nickel in NMD is preferably 0.11% by weigh or less, and more preferably 0.08% by weight or less. In a general manganese dry battery, the content of manganese dioxide in the positive electrode material mixture is 40 to 60% by weight.
- the manganese dioxide includes NMD alone, as long as the content of nickel in the NMD and the content of manganese dioxide in the positive electrode material mixture are within the aforementioned range, the content of nickel in the positive electrode material mixture is kept lower than or equal to 0.04% by weight.
- the amount of nickel contained in EMD as an impurity is small as compared with that in NMD.
- EMD obtained by a conventional method it is very unlikely that the content of nickel exceeds 0.11% by weight. It is preferable, however, to quantitatively analyze the EMD beforehand to check the quality thereof.
- the content of nickel in NMD can be determined, for example, by dissolving the NMD with acid, filtering the dissolved NMD to separate insoluble matter, and then subjecting the insoluble matter to inductively coupled plasma emission spectrometry (hereinafter referred to as ICP emission spectrometry).
- ICP emission spectrometry inductively coupled plasma emission spectrometry
- An exemplary method of preparing an aqueous zinc chloride solution serving as the electrolyte is a method using a solution obtained by treating an etching waste fluid produced in the production process of a print circuit board (i.e., a hydrochloric acid solution containing cupric chloride) with activated carbon (Japanese Laid-Open Patent Publication No. Hei 6-145829).
- a print circuit board i.e., a hydrochloric acid solution containing cupric chloride
- activated carbon Japanese Laid-Open Patent Publication No. Hei 6-145829
- a preferred water for use in the electrolyte is, for example, water treated by passing city water or industrial water (hard water) through reverse osmotic membrane (RO membrane) or cation ion exchange resin.
- the RO membrane has a property to remove impurities such as ions or salts contained in water.
- the ion removal capability of the ion exchange resin is higher than that of the RO membrane.
- Either the RO membrane or the ion exchange resin may be selected appropriately according to the production costs, or alternatively, both of them may be used in combination.
- the ion exchange resin for example, H-type strong acid cation exchange resin for replacing sodium ions with hydrogen ions may be used.
- Na-type strong acid cation exchange resin is used in a general water softener for making soft water from hard water, in which the mineral content in water is replaced with sodium, resulting in a higher content of sodium in the water. Therefore, care should be taken when using a water softener.
- the sodium contained in the electrolyte in a manganese dry battery is derived from sodium contained in EMD.
- EMD sodium contained in EMD.
- the content of sodium in the EMD is preferably 0.4% by weight or less, and more preferably 0.2% by weight or less.
- the content of sodium in the EMD can be adjusted within the aforementioned range by, for example, performing sufficient washing with water or washing with pressurized steam after the aforementioned neutralization process using an aqueous sodium hydroxide solution.
- water it is preferable to use water treated by ion exchange resin or RO membrane as described above.
- a neutralization agent of other than basic sodium salt such as sodium hydroxide may be used.
- potassium hydroxide, ammonium chloride, or ammonium hydroxide may be used in the neutralization process.
- the content of sodium in the EMD can be determined, for example, by dissolving the EMD with acid, filtering the dissolved EMD to separate insoluble matter, and then subjecting the insoluble matter to atomic absorption spectrophotometry. It should be noted that the amount of sodium contained in the NMD as an impurity is usually as low as approximately 0.1% by weight or less, and it is very unlikely that the content of sodium exceeds 0.4% by weight. It is preferable, however, to quantitatively analyze the NMD beforehand to check the quality thereof.
- the content of sodium in the electrolyte in the manganese dry battery of the present invention can be determined, for example, by sampling the electrolyte included in the positive electrode material mixture or the separator and subjecting the sample to atomic absorption spectrophotometry.
- the separator layer disposed between the positive electrode material mixture and the negative electrode can, for example, kraft paper with a paste layer formed on one surface thereof by applying a paste on the surface and drying the paste may be used.
- the paste for example, a paste prepared by dissolving a binder mainly composed of cross-linked starch and polyvinyl acetate in an alcohol-based solvent may be used.
- the separator layer may be composed of a paste layer alone.
- the present invention is applicable not only to a paper-lined type manganese dry battery including a separator layer made of kraft paper with a paste layer formed on one surface thereof but also to a paste type manganese dry battery including a separator layer composed of a paste layer alone.
- the negative electrode can, for example, a zinc alloy containing a small amount of lead (content of lead: 0.05 to 0.6% by weight) may be used.
- Fig. 1 is a partially sectioned front view of a D-size manganese dry battery (R20) of the present invention.
- a cylindrical positive electrode material mixture 1 is housed in a bottomed cylindrical negative electrode can 4 made of zinc.
- a separator 3 is disposed between the positive electrode material mixture 1 and the negative electrode can 4.
- the separator 3 for example, kraft paper on which a paste prepared by dissolving a binder mainly composed of cross-linked starch and polyvinyl acetate in an alcohol-based solvent is applied and dried is used.
- the separator 3 is arranged such that the surface with the paste applied thereon faces the negative electrode can 4.
- a carbon rod 2 obtained by sintering carbon powder is inserted.
- a positive electrode material mixture for example, a mixture of a powdered manganese dioxide, a powdered conductive agent such as acetylene black, and an electrolyte is used.
- the content of manganese dioxide in the positive electrode material mixture 1 is preferably 40 to 60% by weight.
- EMD, NMD, or a mixture of these is used.
- NMD is inexpensive as compared to EMD but low in purity. Accordingly, in order to design a battery for low production costs, it suffices if the blending ratio by weight of NMD to EMD is, for example, 100:0 to 70:30; in order to design a battery for high performance, it suffices if the blending ratio by weight of NMD to EMD is, for example, 0:100 to 30:70; and in order to design a battery for good cost performance taking into consideration the balance between production costs and high performance, it suffices if the blending ratio by weight of NMD to EMD is, for example, 40:60 to 60:40.
- the weight ratio of the manganese dioxide to the conducive agent included in the positive electrode material mixture is preferably within a range of 3:1 to 7:1.
- the weight ratio of the manganese dioxide and the conducive agent to the electrolyte included in the positive electrode material mixture is preferably within a range of 1.0:1 to 1.7:1.
- the average particle size of manganese dioxide powder is, for example, 20 to 50 micrometers.
- the specific surface area of acetylene black powder is, for example, 40 to 100 m 2 /g.
- an aqueous solution containing zinc chloride is used. A small amount of ammonium chloride may be added into the electrolyte.
- a gasket 5 made of resin has a hole in the center thereof, and the columnar carbon rod 2 is inserted through the hole.
- a sealant made of polybutene or the like is applied for ensuring the sealing.
- a circular kraft board 9 having an aperture is placed on top of the positive electrode material mixture 1, and the carbon rod 2 is inserted through the aperture of the kraft board 9.
- the opening of the negative electrode can 4 is covered with the gasket 5, and a cap-like positive electrode terminal 11 made of tin plate having a projection in the center thereof and a planar flange around the projection.
- the top end of the carbon rod 2 is fitted into the recess formed on the back side of the projection of the positive electrode terminal 11 and electrically connected thereto.
- a bottom paper 13 is disposed between the two.
- a seal ring 7 is disposed on the outer surface of the planar periphery of a negative electrode terminal 6.
- a resin tube 8 made of a heat-shrinkable resin film is provided on the outer peripheral surface of the negative electrode can 4.
- the upper end of the resin tube 8 covers the upper surface of the peripheral portion of the gasket 5, and the lower end of the resin tube 8 covers the lower surface of the seal ring 7.
- a tubular outer metal jacket 10 made of tin plate is provided on the outside of the resin tube 8, with the bottom end thereof being bent inward so as to cover the seal ring 7.
- the upper end of the outer metal jacket 10 is curled inward, and the edge of the upper end thereof is crimped onto the positive electrode terminal 11 with the insulation ring 12 interposed therebetween, whereby the manganese dry battery is hermetically sealed.
- the content of nickel in the positive electrode material mixture 1 (a mixture of the positive electrode active material, the conductive agent, and the electrolyte) is 0.04% by weight or less, and the content of sodium in the electrolyte included in the positive electrode material mixture 1 and the separator 3 is 0.8% by weight or less. Therefore, a highly reliable manganese dry battery with excellent storage characteristics in which the drop in battery voltage caused by internal short circuit is suppressed can be obtained. Specifically, the manganese dry battery thus obtained has excellent storage characteristics as follows.
- the manganese dry battery is of size D.
- the aforementioned open-circuit voltage of the battery varies mainly depending on the type of manganese dioxide (EMD, NMD, or a mixture of these), and the blending ratios of the manganese dioxide and the conductive agent.
- EMD electronic medical device
- NMD non-metallic dimethyl methacrylate
- the difference between the open-circuit voltages of the battery before and after storage i.e., the drop in voltage
- the potential at the negative electrode is approximately equal to that of zinc since the content of lead in the zinc alloy is small.
- the difference in the composition of the zinc alloy e.g., content of lead
- T 1 represents a duration of continuous discharge in an initial state
- T 2 represents a duration of continuous discharge after storage in an environment of 50 degrees Celsius for 2 months, the continuous discharge being performed at a constant resistance of 2.2 ohms in an environment of 20 degrees Celsius until the closed-circuit voltage reaches 0.9 V.
- the continuous discharge is performed with respect to the manganese dry battery of size D.
- the ratio of the discharge capacity after 2-month storage in an environment of 50 degrees Celsius to the initial discharge capacity is 85% or more.
- the gas permeability of the carbon rod 2 is preferably 0.5 cm 3 or less.
- the gas permeability of the carbon rod 2 can be determined, for example, by applying air pressure of 4 kg/cm 2 (0.39 MPa) to the carbon rod for 60 minutes, and measuring the amount of air passed though the carbon rod during this 60 minutes.
- the rate of fitting of the carbon rod 2 into the hole of the gasket 5 is preferable 1.01 to 1.07 in order to ensure good sealing and reduce the amount of oxygen in the battery, and thereby to inhibit the oxidation of sodium.
- the rate of fitting of the carbon rod 2 into the hole of the gasket 5 as herein used is a value determined by dividing the diameter of the carbon rod 2 by the diameter of the hole of the gasket 5 before fitting with the carbon rod 2. When the rate of fitting of the carbon rod 2 into the hole of the gasket 5 exceeds 1.07, the gasket 5 will have a crack, and consequently the sealing may deteriorate.
- the rate of fitting of the carbon rod 2 into the hole of the gasket 5 is below 1.01, oxygen may enter inside the battery through the narrow clearance between the carbon rod 2 and the gasket 5.
- the diameter of the hole of the gasket 5 is, for example, 7.5 to 7.9 mm.
- the diameter of the carbon rod 2 is, for example, 7.95 to 8.05 mm.
- the aforementioned preferred ranges of the gas permeability and the rate of fitting of the carbon rod are not limited to a D-size battery. In any size of battery other than D-size, the gas permeability and the rate of fitting of the carbon rod are preferably within the aforementioned ranges.
- FIG. 1 is a partially sectioned front view of the D-size manganese dry battery (R20) of the present invention.
- the cylindrical positive electrode material mixture 1 was housed in the bottomed cylindrical negative electrode can 4 made of a zinc alloy containing 0.4% by weight lead. At this time, the separator 3 was disposed between the positive electrode material mixture 1 and the negative electrode can 4.
- the bottom paper 13 was disposed between the bottom of the positive electrode material mixture 1 and the negative electrode can 4, so that the electrical insulation between the two was ensured.
- the separator 3 kraft paper on which a paste prepared by dissolving a binder mainly composed of cross-linked starch and polyvinyl acetate in an alcohol-based solvent was applied and dried was used. The separator 3 was arranged such that the surface with the paste applied thereon faced the negative electrode can 4. Subsequently, the circular kraft board 9 having an aperture was placed on top of the positive electrode material mixture 1. Thereafter, the carbon rod 2 (diameter: 8.0 mm, and gas permeability: 0.2 cm 3 ) obtained by sintering carbon powder was inserted in the center of the positive electrode material mixture 1.
- the positive electrode material mixture 1 a material prepared by mixing manganese dioxide, acetylene black, and electrolyte in a weight ratio of 45:10:45 was used.
- the gasket 5 made of polyolefin-based resin having a hole (diameter: 7.8 mm) in the center thereof was prepared.
- the gasket 5 was fitted with the carbon rod 2 such that the carbon rod 2 was inserted through the hole of the gasket.
- polybutene was applied as a sealant to the fitting portion between the gasket 5 and the carbon rod 2.
- the cap-like positive electrode terminal 11 made of tin plate having a projection in the center thereof and a planar flange around the projection was prepared.
- the top end of the carbon rod 2 was fitted with the recess in the center of the positive electrode terminal 11.
- the insulation ring 12 made of resin was placed on the planer flange of the positive electrode terminal 11.
- the seal ring 7 was disposed on the outer surface of the planar periphery of the negative electrode terminal 6.
- the resin tube 8 made of a heat-shrinkable resin film for ensuring the insulation was provided, and shrunk by heat such that the upper end thereof covered the upper surface of the peripheral portion of the gasket 5, and the lower end thereof covered the lower surface of the seal ring 7.
- the tubular outer metal jacket 10 made of tin plate was provided on the outside of the resin tube 8. The bottom end of the outer jacket 10 was bent inward, and the upper end thereof was curled inward, with the edge of the upper end thereof being crimped onto the insulation ring 12.
- the manganese dioxide used for the positive electrode active material a mixture of 80 parts by weight of natural manganese dioxide (NMD) and 20 parts by weight of electrolytic manganese dioxide (EMD) was used.
- NMD natural manganese dioxide
- EMD electrolytic manganese dioxide
- NMDs 1 to 6 as shown in Table 1 were used.
- manufacturer A represents Quintal S.A.
- manufacturer B represents Erachem Europe S.A.
- EMD one manufactured by Guizhou Redstar Developing Dalong Manganese Industry Co., Ltd. was used.
- sodium hydrogen carbonate (NaHCO 3 ) was used as a neutralizer, but after neutralization, the EMD was sufficiently washed with water.
- electrolytes 1 to 5 as shown in Table 2 were used.
- the electrolytes 1 to 5 were prepared as follows. First, the electrolytes 1 to 3 were prepared by adding a predetermined amount of water that had been passed through cation exchange resin into each of different lot numbers of aqueous 40% by weight zinc chloride solutions manufactured by Nagai Metal Traders Sdn Bhd, heating the aqueous zinc chloride solution to a temperature from 45 to 50 degrees Celsius, adding a predetermined amount of ammonium chloride followed by stirring, and then further adding water that had been passed through cation exchange resin, so that the concentration of zinc chloride and the concentration of ammonium chloride in the electrolyte were 30% by weight and 1% by weight, respectively.
- potassium chloride was added into the electrolyte 1, so that the concentration of potassium in the electrolyte was 1.00 ppm, whereby the potassium-rich electrolyte 4 was prepared.
- Calcium chloride was added into the electrolyte 1, so that the concentration of calcium in the electrolyte was 1.00 ppm, whereby the calcium-rich electrolyte 5 was prepared.
- the content of each element contained in the NMD, EMD, and electrolyte shown in Tables 1 and 2 was determined using atomic absorption spectrophotometry or ICP emission spectrometry.
- the combination of NMD and electrolyte was changed as shown in Table 3.
- the storage characteristics of each battery were evaluated in the following manner.
- the emission intensity at an analytical wavelength of each element was measured using an ICP emission spectrometer (VISTA-RL available from VARIAN, Inc.), to give a calibration curve showing the relationship between an emission intensity and a concentration of each element.
- ICP emission spectrometer VISTA-RL available from VARIAN, Inc.
- the filter paper and the insoluble matter A 1 obtained in the above were placed in a platinum crucible and subjected to drying and ashing, to which alkali salt (e.g., sodium carbonate) was then added, subsequently heat-fused, and thereafter dissolved with water and acid.
- alkali salt e.g., sodium carbonate
- the resultant solution was filtered and separated into an insoluble matter B 1 and a solution B 2 (including the washing fluid) which was a filtrate.
- the solution B 2 was diluted to a fixed volume to give a measurement solution B 3 .
- Standard solutions with the same amount of alkali salt as used above added thereto solutions of Co, Ni, and Cu; concentration: 1 mg/ml each
- concentration of each element in the unknown measurement solution B 3 was determined.
- the amount of each element in the measurement solution A 3 and the amount of each element in the measurement solution B 3 were summed to give a content of each element in the positive electrode material mixture. It should be noted that in these examples, the measurement on the measurement solution B 3 was performed since the positive electrode material mixture included NMD containing a large amount of impurities. In the case where a positive electrode material mixture that does not include NMD is used (i.e., in the case where EMD is used alone as the positive electrode active material), it is not necessary to perform the measurement on the measurement solution B 3 .
- the resultant filtrate (including the washing fluid) was placed in a full measure flask (200 ml). To the flask, 5 ml of 6 mol/L hydrochloric acid was added and then water was added up to the marked line to dilute the filtrate containing hydrochloric acid with water, whereby a sample solution was obtained.
- an ICP emission spectrometer (VISTA-RL available from VARIAN, Inc.) was used to create a calibration curve showing the relationship between an emission intensity and a concentration, and using the calibration curve, the concentration of the analyte element (Ca) was determined by a standard addition method.
- the evaluation results are shown in Table 3.
- the drops in battery voltage during storage were less than 50 mV, and the capacity retention rates were 85% or more, indicating that the storage characteristics were excellent.
- the capacity retention rates were below 85%, indicating that the storage characteristics were deteriorated.
- the batteries of Comparative Examples 7, 11, and 12 in which the content of sodium in the electrolyte was as high as more than 0.8% by weight, the storage characteristics were significantly deteriorated.
- Examples 14 to 17 and Comparative Examples 19 to 32>> In preparing the positive electrode material mixture, a mixture of 50 parts by weight of NMD and 50 parts by weight of EMD was used as the positive electrode active material. As shown in Table 4, the combination of NMD and electrolyte was changed. Batteries were fabricated in the same manner as in Example 1 except the above. The batteries were evaluated in the same manner as described above. The evaluation results are shown in Table 4.
- the drops in battery voltage during storage were less than 50 mV, and the capacity retention rates were 85% or more, indicating that the storage characteristics were excellent.
- the capacity retention rates were below 85%, indicating that the storage characteristics were deteriorated.
- the batteries of Comparative Examples 21, 22, 25 to 28, 31, and 32 in which the content of sodium in the electrolyte was as high as more than 0.8% by weight, the storage characteristics were significantly deteriorated.
- the manganese dry battery of the present invention is suitably used as a power source for electronic devices such as information devices and portable devices.
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Abstract
A manganese dry battery of the present invention includes a positive electrode material mixture including manganese dioxide, a negative electrode can including zinc, a separator layer disposed between the positive electrode material mixture and the negative electrode can; and an electrolyte. The content of nickel in the positive electrode material mixture is 0.04% by weight or less, and the content of sodium in the electrolyte is 0.8% by weight or less. The present invention provides a highly reliable manganese dry battery with excellent storage characteristics in which the drop in battery voltage during storage is suppressed.
Description
The present invention relates to a manganese dry battery, and specifically relates to improvements to a positive electrode material mixture and an electrolyte in a manganese dry battery.
Conventionally, various studies have been conducted for the purpose of improving the performance of a manganese dry battery. For example, Patent Citation 1 proposes that in order to reduce the amount of alkali metal and the like contained in the electrolyte to be adsorbed into pores in manganese dioxide in the process of assembling a battery, and thereby to improve the discharge performance, the content of alkali metal or alkaline earth metal in the electrolyte, calculated as sulfate, be 0.3% by weight or less.
However, in Patent Citation 1, if the content of nickel contained in the manganese dioxide as an impurity is high, the battery voltage may be lowered during storage and the storage characteristics may be deteriorated. In Patent Citation 2, if the content of sodium contained in the electrolyte as an impurity is high, the battery voltage may be lowered during storage and the storage characteristics may be deteriorated. The influence of impurities present inside a battery exerted on the storage characteristics of the battery has not been thoroughly studied.
Japanese Laid-Open Patent Publication No. 2001-189157
Japanese Laid-Open Patent Publication No. Hei 8-83611
The present invention intends to solve the above-described conventional problem and provide a highly reliable manganese dry battery with excellent storage characteristics.
The present invention is directed to a manganese dry battery comprising a positive electrode material mixture including manganese dioxide, a negative electrode can including zinc, a separator layer disposed between the positive electrode material mixture and the negative electrode can, and an electrolyte, wherein the content of nickel in the positive electrode material mixture is 0.04% by weight or less, and the content of sodium in the electrolyte is 0.8% by weight or less.
Preferably, the positive electrode material mixture comprises a mixture of the manganese dioxide, a conductive agent, and the electrolyte, and the content of the manganese dioxide in the positive electrode material mixture is 40 to 60% by weight.
The manganese dioxide is preferably at least one selected from natural manganese dioxide and electrolytic manganese dioxide.
The content of nickel in the natural manganese dioxide is preferably 0.11% by weight or less.
The content of sodium in the electrolytic manganese dioxide is preferably 0.4% by weight or less.
The manganese dioxide is preferably at least one selected from natural manganese dioxide and electrolytic manganese dioxide.
The content of nickel in the natural manganese dioxide is preferably 0.11% by weight or less.
The content of sodium in the electrolytic manganese dioxide is preferably 0.4% by weight or less.
It is preferable in the manganese dry battery of the present invention that V1 - V2 is equal to or less than 50, where V1 represents an open-circuit voltage (mV) at 20 degrees Celsius in an initial state, and V2 represents an open-circuit voltage (mV) at 20 degrees Celsius after storage in an environment of 50 degrees Celsius for 2 months.
It is preferable in the manganese dry battery of the present invention that the manganese dry battery is of size D, and T2/T1 is equal to or more than 0.85, where T1 represents a duration of continuous discharge in an initial state, and T2 represents a duration of continuous discharge after storage in an environment of 50 degrees Celsius for 2 months, the continuous discharge being performed at a constant resistance of 2.2 ohms in an environment of 20 degrees Celsius until the closed-circuit voltage reaches 0.9 V.
According to the present invention, it is possible to provide a highly reliable manganese dry battery with excellent storage characteristics in which the drop in battery voltage during storage is suppressed.
The present inventors have conducted intensive studies on the influence of impurities present inside a battery exerted on the storage characteristics of the battery, and as a result, found that: nickel contained in the manganese dioxide and sodium contained in the electrolyte have a significant influence on the storage characteristics of the battery; and the deterioration of the storage characteristics of the battery can be suppressed by reducing the content of nickel in the manganese dioxide and the content of sodium in the electrolyte to be 0.04% by weight or less and 0.8% by weight or less, respectively.
Specifically, the present invention relates to a manganese dry battery comprising a positive electrode material mixture including manganese dioxide, a negative electrode can including zinc, a separator layer disposed between the positive electrode material mixture and the negative electrode can, and an electrolyte. The present invention is characterized in that the content of nickel in the positive electrode material mixture is 0.04% by weight or less, and the content of sodium in the electrolyte is 0.8% by weight or less.
By doing this, it is possible to provide a highly reliable manganese dry battery with excellent storage characteristics in which the drop in battery voltage during storage is suppressed. It should be noted that the aforementioned contents of nickel in the manganese dioxide and sodium in the electrolyte are the values in the battery in an initial state (e.g., within 1 week after the production of the battery). In the subsequent state, the aforementioned contents of nickel and sodium remain almost unchanged even after the storage of the battery.
Specifically, the present invention relates to a manganese dry battery comprising a positive electrode material mixture including manganese dioxide, a negative electrode can including zinc, a separator layer disposed between the positive electrode material mixture and the negative electrode can, and an electrolyte. The present invention is characterized in that the content of nickel in the positive electrode material mixture is 0.04% by weight or less, and the content of sodium in the electrolyte is 0.8% by weight or less.
By doing this, it is possible to provide a highly reliable manganese dry battery with excellent storage characteristics in which the drop in battery voltage during storage is suppressed. It should be noted that the aforementioned contents of nickel in the manganese dioxide and sodium in the electrolyte are the values in the battery in an initial state (e.g., within 1 week after the production of the battery). In the subsequent state, the aforementioned contents of nickel and sodium remain almost unchanged even after the storage of the battery.
When the content of nickel in the positive electrode material mixture exceeds 0.04% by weight, an increased amount of nickel oxide is present in the positive electrode material mixture, and nickel will be leached into the electrolyte in the form of nickel ions. When this occurs, the hydrogen overvoltage of zinc in the negative electrode can is reduced, leading to corrosion of the negative electrode can. Due to this corrosion, the internal resistance is increased, and the discharge performance after storage is deteriorated.
When the content of sodium in the electrolyte exceeds 0.8% by weight, sodium ions present in the positive electrode material mixture react on the surface of the negative electrode can in an electron-rich state, with oxygen present inside the battery. As a result, dendrites of sodium oxide with electrical conductivity are produced. The dendrites of sodium oxide thus formed may pierce the separator, causing internal short circuit.
When the content of nickel in the positive electrode material mixture exceeds 0.04% by weight and the content of sodium in the electrolyte exceeds 0.8% by weight, a weak discharge occurs as a result of the internal short circuit due to the dendrites of sodium oxide piercing the separator, and thus the pH in the vicinity of the separator shifts to a more acidic region. As such, nickel in the nickel oxide in the manganese dioxide tends to be leached into the electrolyte in the form of nickel ions. When the leached nickel ions migrate to the negative electrode and deposit on the surface of the negative electrode can containing zinc, the deposited nickel and the zinc form a local battery. Consequently, the zinc is consumed by the reaction with nickel, resulting in a significant drop in battery voltage.
When the content of sodium in the electrolyte exceeds 0.8% by weight, sodium ions present in the positive electrode material mixture react on the surface of the negative electrode can in an electron-rich state, with oxygen present inside the battery. As a result, dendrites of sodium oxide with electrical conductivity are produced. The dendrites of sodium oxide thus formed may pierce the separator, causing internal short circuit.
When the content of nickel in the positive electrode material mixture exceeds 0.04% by weight and the content of sodium in the electrolyte exceeds 0.8% by weight, a weak discharge occurs as a result of the internal short circuit due to the dendrites of sodium oxide piercing the separator, and thus the pH in the vicinity of the separator shifts to a more acidic region. As such, nickel in the nickel oxide in the manganese dioxide tends to be leached into the electrolyte in the form of nickel ions. When the leached nickel ions migrate to the negative electrode and deposit on the surface of the negative electrode can containing zinc, the deposited nickel and the zinc form a local battery. Consequently, the zinc is consumed by the reaction with nickel, resulting in a significant drop in battery voltage.
The smaller the content of nickel is, the smaller the amount of nickel oxide present in the positive electrode material mixture, and therefore a smaller amount of nickel ions leaches into the electrolyte. The content of nickel in the positive electrode material mixture is preferably 0 to 0.25% by weight.
The smaller the content of sodium is, the more unlikely the dendrites of sodium oxide with electrical conductivity are produced, and therefore the internal short circuit is prevented. The content of sodium in the electrolyte is preferably 0 to 0.53% by weight.
The smaller the content of sodium is, the more unlikely the dendrites of sodium oxide with electrical conductivity are produced, and therefore the internal short circuit is prevented. The content of sodium in the electrolyte is preferably 0 to 0.53% by weight.
The nickel contained in the positive electrode material mixture is derived from the nickel present in the manganese dioxide as an impurity. For the manganese dioxide, for example, electrolytic manganese dioxide (EMD) and natural manganese dioxide (NMD) may be used. Since NMD contains a large amount of impurities, it is preferable to quantitatively analyze the NMD beforehand to check the quality thereof.
The content of nickel in NMD is preferably 0.11% by weigh or less, and more preferably 0.08% by weight or less.
In a general manganese dry battery, the content of manganese dioxide in the positive electrode material mixture is 40 to 60% by weight. Even in the case where the manganese dioxide includes NMD alone, as long as the content of nickel in the NMD and the content of manganese dioxide in the positive electrode material mixture are within the aforementioned range, the content of nickel in the positive electrode material mixture is kept lower than or equal to 0.04% by weight.
The amount of nickel contained in EMD as an impurity is small as compared with that in NMD. In EMD obtained by a conventional method, it is very unlikely that the content of nickel exceeds 0.11% by weight. It is preferable, however, to quantitatively analyze the EMD beforehand to check the quality thereof.
The content of nickel in NMD can be determined, for example, by dissolving the NMD with acid, filtering the dissolved NMD to separate insoluble matter, and then subjecting the insoluble matter to inductively coupled plasma emission spectrometry (hereinafter referred to as ICP emission spectrometry). The nickel content in the positive electrode material mixture is determined in the similar manner.
The content of nickel in NMD is preferably 0.11% by weigh or less, and more preferably 0.08% by weight or less.
In a general manganese dry battery, the content of manganese dioxide in the positive electrode material mixture is 40 to 60% by weight. Even in the case where the manganese dioxide includes NMD alone, as long as the content of nickel in the NMD and the content of manganese dioxide in the positive electrode material mixture are within the aforementioned range, the content of nickel in the positive electrode material mixture is kept lower than or equal to 0.04% by weight.
The amount of nickel contained in EMD as an impurity is small as compared with that in NMD. In EMD obtained by a conventional method, it is very unlikely that the content of nickel exceeds 0.11% by weight. It is preferable, however, to quantitatively analyze the EMD beforehand to check the quality thereof.
The content of nickel in NMD can be determined, for example, by dissolving the NMD with acid, filtering the dissolved NMD to separate insoluble matter, and then subjecting the insoluble matter to inductively coupled plasma emission spectrometry (hereinafter referred to as ICP emission spectrometry). The nickel content in the positive electrode material mixture is determined in the similar manner.
Sodium enters the electrolyte in the process of preparing the electrolyte. An exemplary method of preparing an aqueous zinc chloride solution serving as the electrolyte is a method using a solution obtained by treating an etching waste fluid produced in the production process of a print circuit board (i.e., a hydrochloric acid solution containing cupric chloride) with activated carbon (Japanese Laid-Open Patent Publication No. Hei 6-145829). According to this method, sodium that had been contained in the etching waste fluid remains in the prepared aqueous zinc chloride solution. Therefore, it is preferable to quantitatively analyze the aqueous zinc chloride solution by atomic absorption spectrophotometry and the like beforehand to check the quality thereof. The content of sodium in the etching waste fluid is preferably 0.5% by weigh or less, and more preferably 0.1% by weight or less.
A preferred water for use in the electrolyte is, for example, water treated by passing city water or industrial water (hard water) through reverse osmotic membrane (RO membrane) or cation ion exchange resin. The RO membrane has a property to remove impurities such as ions or salts contained in water. The ion removal capability of the ion exchange resin is higher than that of the RO membrane. Either the RO membrane or the ion exchange resin may be selected appropriately according to the production costs, or alternatively, both of them may be used in combination. As the ion exchange resin, for example, H-type strong acid cation exchange resin for replacing sodium ions with hydrogen ions may be used. It should be noted that Na-type strong acid cation exchange resin is used in a general water softener for making soft water from hard water, in which the mineral content in water is replaced with sodium, resulting in a higher content of sodium in the water. Therefore, care should be taken when using a water softener.
Further, there may be a case where the sodium contained in the electrolyte in a manganese dry battery is derived from sodium contained in EMD. For example, when a known aqueous solution of sodium hydroxide or sodium hydrogen carbonate is used as a neutralization agent in a neutralization process in preparing EMD, sodium remains in the EMD. In order to surely reduce the content of sodium in the electrolyte to be equal to or less than 0.8% by weight, the content of sodium in the EMD is preferably 0.4% by weight or less, and more preferably 0.2% by weight or less. The content of sodium in the EMD can be adjusted within the aforementioned range by, for example, performing sufficient washing with water or washing with pressurized steam after the aforementioned neutralization process using an aqueous sodium hydroxide solution. As for the water, it is preferable to use water treated by ion exchange resin or RO membrane as described above. As for the neutralization agent, in order to reduce the content of sodium in the EMD, for example, a neutralization agent of other than basic sodium salt such as sodium hydroxide may be used. Specifically, potassium hydroxide, ammonium chloride, or ammonium hydroxide may be used in the neutralization process. The content of sodium in the EMD can be determined, for example, by dissolving the EMD with acid, filtering the dissolved EMD to separate insoluble matter, and then subjecting the insoluble matter to atomic absorption spectrophotometry.
It should be noted that the amount of sodium contained in the NMD as an impurity is usually as low as approximately 0.1% by weight or less, and it is very unlikely that the content of sodium exceeds 0.4% by weight. It is preferable, however, to quantitatively analyze the NMD beforehand to check the quality thereof.
The content of sodium in the electrolyte in the manganese dry battery of the present invention can be determined, for example, by sampling the electrolyte included in the positive electrode material mixture or the separator and subjecting the sample to atomic absorption spectrophotometry.
It should be noted that the amount of sodium contained in the NMD as an impurity is usually as low as approximately 0.1% by weight or less, and it is very unlikely that the content of sodium exceeds 0.4% by weight. It is preferable, however, to quantitatively analyze the NMD beforehand to check the quality thereof.
The content of sodium in the electrolyte in the manganese dry battery of the present invention can be determined, for example, by sampling the electrolyte included in the positive electrode material mixture or the separator and subjecting the sample to atomic absorption spectrophotometry.
For the separator layer disposed between the positive electrode material mixture and the negative electrode can, for example, kraft paper with a paste layer formed on one surface thereof by applying a paste on the surface and drying the paste may be used. As the paste, for example, a paste prepared by dissolving a binder mainly composed of cross-linked starch and polyvinyl acetate in an alcohol-based solvent may be used. Alternatively, the separator layer may be composed of a paste layer alone. The present invention is applicable not only to a paper-lined type manganese dry battery including a separator layer made of kraft paper with a paste layer formed on one surface thereof but also to a paste type manganese dry battery including a separator layer composed of a paste layer alone.
For the negative electrode can, for example, a zinc alloy containing a small amount of lead (content of lead: 0.05 to 0.6% by weight) may be used.
For the negative electrode can, for example, a zinc alloy containing a small amount of lead (content of lead: 0.05 to 0.6% by weight) may be used.
In the following, an embodiment of the manganese dry battery according to the present invention is described with reference to Fig. 1. Fig. 1 is a partially sectioned front view of a D-size manganese dry battery (R20) of the present invention.
A cylindrical positive electrode material mixture 1 is housed in a bottomed cylindrical negative electrode can 4 made of zinc. Aseparator 3 is disposed between the positive electrode material mixture 1 and the negative electrode can 4. As the separator 3, for example, kraft paper on which a paste prepared by dissolving a binder mainly composed of cross-linked starch and polyvinyl acetate in an alcohol-based solvent is applied and dried is used. The separator 3 is arranged such that the surface with the paste applied thereon faces the negative electrode can 4. Into the positive electrode material mixture 1, a carbon rod 2 (a positive electrode current collector) obtained by sintering carbon powder is inserted.
For the positive electrode material mixture 1, for example, a mixture of a powdered manganese dioxide, a powdered conductive agent such as acetylene black, and an electrolyte is used. The content of manganese dioxide in the positive electrode material mixture 1 is preferably 40 to 60% by weight. For the manganese dioxide, EMD, NMD, or a mixture of these is used.
A cylindrical positive electrode material mixture 1 is housed in a bottomed cylindrical negative electrode can 4 made of zinc. A
For the positive electrode material mixture 1, for example, a mixture of a powdered manganese dioxide, a powdered conductive agent such as acetylene black, and an electrolyte is used. The content of manganese dioxide in the positive electrode material mixture 1 is preferably 40 to 60% by weight. For the manganese dioxide, EMD, NMD, or a mixture of these is used.
NMD is inexpensive as compared to EMD but low in purity. Accordingly, in order to design a battery for low production costs, it suffices if the blending ratio by weight of NMD to EMD is, for example, 100:0 to 70:30; in order to design a battery for high performance, it suffices if the blending ratio by weight of NMD to EMD is, for example, 0:100 to 30:70; and in order to design a battery for good cost performance taking into consideration the balance between production costs and high performance, it suffices if the blending ratio by weight of NMD to EMD is, for example, 40:60 to 60:40.
The weight ratio of the manganese dioxide to the conducive agent included in the positive electrode material mixture is preferably within a range of 3:1 to 7:1. The weight ratio of the manganese dioxide and the conducive agent to the electrolyte included in the positive electrode material mixture is preferably within a range of 1.0:1 to 1.7:1. The average particle size of manganese dioxide powder is, for example, 20 to 50 micrometers. The specific surface area of acetylene black powder is, for example, 40 to 100 m2/g. For the electrolyte, an aqueous solution containing zinc chloride is used. A small amount of ammonium chloride may be added into the electrolyte.
The weight ratio of the manganese dioxide to the conducive agent included in the positive electrode material mixture is preferably within a range of 3:1 to 7:1. The weight ratio of the manganese dioxide and the conducive agent to the electrolyte included in the positive electrode material mixture is preferably within a range of 1.0:1 to 1.7:1. The average particle size of manganese dioxide powder is, for example, 20 to 50 micrometers. The specific surface area of acetylene black powder is, for example, 40 to 100 m2/g. For the electrolyte, an aqueous solution containing zinc chloride is used. A small amount of ammonium chloride may be added into the electrolyte.
A gasket 5 made of resin has a hole in the center thereof, and the columnar carbon rod 2 is inserted through the hole. To the contact portion between the carbon rod 2 and the hole of the gasket 5 and the contact portion between the groove provided on the lower surface of the periphery of the gasket 5 and the opening rim of the negative electrode can 4, a sealant made of polybutene or the like is applied for ensuring the sealing. A circular kraft board 9 having an aperture is placed on top of the positive electrode material mixture 1, and the carbon rod 2 is inserted through the aperture of the kraft board 9.
The opening of the negative electrode can 4 is covered with the gasket 5, and a cap-like positive electrode terminal 11 made of tin plate having a projection in the center thereof and a planar flange around the projection. The top end of the carbon rod 2 is fitted into the recess formed on the back side of the projection of the positive electrode terminal 11 and electrically connected thereto. On the planar flange of the positive electrode terminal 11, an insulation ring 12 made of resin is placed. In order to ensure the insulation between the bottom of the positive electrode material mixture 1 and the bottom of the negative electrode can 4, a bottom paper 13 is disposed between the two. A seal ring 7 is disposed on the outer surface of the planar periphery of a negative electrode terminal 6.
On the outer peripheral surface of the negative electrode can 4, a resin tube 8 made of a heat-shrinkable resin film is provided. The upper end of the resin tube 8 covers the upper surface of the peripheral portion of thegasket 5, and the lower end of the resin tube 8 covers the lower surface of the seal ring 7.
On the outer peripheral surface of the negative electrode can 4, a resin tube 8 made of a heat-shrinkable resin film is provided. The upper end of the resin tube 8 covers the upper surface of the peripheral portion of the
A tubular outer metal jacket 10 made of tin plate is provided on the outside of the resin tube 8, with the bottom end thereof being bent inward so as to cover the seal ring 7. The upper end of the outer metal jacket 10 is curled inward, and the edge of the upper end thereof is crimped onto the positive electrode terminal 11 with the insulation ring 12 interposed therebetween, whereby the manganese dry battery is hermetically sealed.
The content of nickel in the positive electrode material mixture 1 (a mixture of the positive electrode active material, the conductive agent, and the electrolyte) is 0.04% by weight or less, and the content of sodium in the electrolyte included in the positive electrode material mixture 1 and the separator 3 is 0.8% by weight or less. Therefore, a highly reliable manganese dry battery with excellent storage characteristics in which the drop in battery voltage caused by internal short circuit is suppressed can be obtained.
Specifically, the manganese dry battery thus obtained has excellent storage characteristics as follows.
The relational expression V1 - V2 < 50 or V1 - V2 = 50 is satisfied, where V1 represents an open-circuit voltage (mV) at 20 degrees Celsius in an initial state, and V2 represents an open-circuit voltage (mV) at 20 degrees Celsius after storage in an environment of 50 degrees Celsius for 2 months. Here, the manganese dry battery is of size D.
Specifically, the manganese dry battery thus obtained has excellent storage characteristics as follows.
The relational expression V1 - V2 < 50 or V1 - V2 = 50 is satisfied, where V1 represents an open-circuit voltage (mV) at 20 degrees Celsius in an initial state, and V2 represents an open-circuit voltage (mV) at 20 degrees Celsius after storage in an environment of 50 degrees Celsius for 2 months. Here, the manganese dry battery is of size D.
The aforementioned open-circuit voltage of the battery varies mainly depending on the type of manganese dioxide (EMD, NMD, or a mixture of these), and the blending ratios of the manganese dioxide and the conductive agent. On the other hand, the difference between the open-circuit voltages of the battery before and after storage (i.e., the drop in voltage) is 50 mV or less, irrespective of the type of manganese dioxide and the blending ratios of the manganese dioxide and the conductive agent. The potential at the negative electrode is approximately equal to that of zinc since the content of lead in the zinc alloy is small. As such, the difference in the composition of the zinc alloy (e.g., content of lead) has little or no influence on the open-circuit voltage. Even in the case of batteries of different sizes, when the types of manganese dioxide and the blending ratios of the manganese dioxide and the conductive agent are the same, these batteries demonstrate almost the same open-circuit voltages.
Further, the relational expression 0.85 < T2/T1 or 0.85 = T2/T1 is satisfied, where T1 represents a duration of continuous discharge in an initial state, and T2 represents a duration of continuous discharge after storage in an environment of 50 degrees Celsius for 2 months, the continuous discharge being performed at a constant resistance of 2.2 ohms in an environment of 20 degrees Celsius until the closed-circuit voltage reaches 0.9 V. Here, the continuous discharge is performed with respect to the manganese dry battery of size D. In other words, the ratio of the discharge capacity after 2-month storage in an environment of 50 degrees Celsius to the initial discharge capacity is 85% or more.
The gas permeability of the carbon rod 2 is preferably 0.5 cm3 or less. By using a carbon rod whose gas permeability is restricted as such, it is possible to suppress the intrusion of oxygen into the battery through the carbon rod 2 and reduce the amount of oxygen in the battery, and thereby to inhibit the oxidation of sodium. The gas permeability of the carbon rod 2 can be determined, for example, by applying air pressure of 4 kg/cm2 (0.39 MPa) to the carbon rod for 60 minutes, and measuring the amount of air passed though the carbon rod during this 60 minutes.
The rate of fitting of the carbon rod 2 into the hole of the gasket 5 is preferable 1.01 to 1.07 in order to ensure good sealing and reduce the amount of oxygen in the battery, and thereby to inhibit the oxidation of sodium. The rate of fitting of the carbon rod 2 into the hole of the gasket 5 as herein used is a value determined by dividing the diameter of the carbon rod 2 by the diameter of the hole of the gasket 5 before fitting with the carbon rod 2. When the rate of fitting of the carbon rod 2 into the hole of the gasket 5 exceeds 1.07, the gasket 5 will have a crack, and consequently the sealing may deteriorate. When the rate of fitting of the carbon rod 2 into the hole of the gasket 5 is below 1.01, oxygen may enter inside the battery through the narrow clearance between the carbon rod 2 and the gasket 5. The diameter of the hole of the gasket 5 is, for example, 7.5 to 7.9 mm. The diameter of the carbon rod 2 is, for example, 7.95 to 8.05 mm.
The aforementioned preferred ranges of the gas permeability and the rate of fitting of the carbon rod are not limited to a D-size battery. In any size of battery other than D-size, the gas permeability and the rate of fitting of the carbon rod are preferably within the aforementioned ranges.
The aforementioned preferred ranges of the gas permeability and the rate of fitting of the carbon rod are not limited to a D-size battery. In any size of battery other than D-size, the gas permeability and the rate of fitting of the carbon rod are preferably within the aforementioned ranges.
In the following, the mode of the present invention is specifically described with reference to examples, but the present invention is not limited to these examples.
<<Examples 1 to 13 and Comparative Examples 1 to 18>>
A D-size manganese dry battery (R20) of the present invention as shown in Fig. 1 was produced in the following manner. Fig. 1 is a partially sectioned front view of the D-size manganese dry battery (R20) of the present invention. The cylindrical positive electrode material mixture 1 was housed in the bottomed cylindrical negative electrode can 4 made of a zinc alloy containing 0.4% by weight lead. At this time, theseparator 3 was disposed between the positive electrode material mixture 1 and the negative electrode can 4. The bottom paper 13 was disposed between the bottom of the positive electrode material mixture 1 and the negative electrode can 4, so that the electrical insulation between the two was ensured. As the separator 3, kraft paper on which a paste prepared by dissolving a binder mainly composed of cross-linked starch and polyvinyl acetate in an alcohol-based solvent was applied and dried was used. The separator 3 was arranged such that the surface with the paste applied thereon faced the negative electrode can 4.
Subsequently, the circular kraft board 9 having an aperture was placed on top of the positive electrode material mixture 1. Thereafter, the carbon rod 2 (diameter: 8.0 mm, and gas permeability: 0.2 cm3) obtained by sintering carbon powder was inserted in the center of the positive electrode material mixture 1. As the positive electrode material mixture 1, a material prepared by mixing manganese dioxide, acetylene black, and electrolyte in a weight ratio of 45:10:45 was used.
<<Examples 1 to 13 and Comparative Examples 1 to 18>>
A D-size manganese dry battery (R20) of the present invention as shown in Fig. 1 was produced in the following manner. Fig. 1 is a partially sectioned front view of the D-size manganese dry battery (R20) of the present invention. The cylindrical positive electrode material mixture 1 was housed in the bottomed cylindrical negative electrode can 4 made of a zinc alloy containing 0.4% by weight lead. At this time, the
Subsequently, the circular kraft board 9 having an aperture was placed on top of the positive electrode material mixture 1. Thereafter, the carbon rod 2 (diameter: 8.0 mm, and gas permeability: 0.2 cm3) obtained by sintering carbon powder was inserted in the center of the positive electrode material mixture 1. As the positive electrode material mixture 1, a material prepared by mixing manganese dioxide, acetylene black, and electrolyte in a weight ratio of 45:10:45 was used.
The gasket 5 made of polyolefin-based resin having a hole (diameter: 7.8 mm) in the center thereof was prepared. The gasket 5 was fitted with the carbon rod 2 such that the carbon rod 2 was inserted through the hole of the gasket. In fitting the gasket 5 with the carbon rod 2, polybutene was applied as a sealant to the fitting portion between the gasket 5 and the carbon rod 2.
The cap-likepositive electrode terminal 11 made of tin plate having a projection in the center thereof and a planar flange around the projection was prepared. The top end of the carbon rod 2 was fitted with the recess in the center of the positive electrode terminal 11. On the planer flange of the positive electrode terminal 11, the insulation ring 12 made of resin was placed. The seal ring 7 was disposed on the outer surface of the planar periphery of the negative electrode terminal 6.
The cap-like
On the outer peripheral surface of the negative electrode can 4, the resin tube 8 made of a heat-shrinkable resin film for ensuring the insulation was provided, and shrunk by heat such that the upper end thereof covered the upper surface of the peripheral portion of the gasket 5, and the lower end thereof covered the lower surface of the seal ring 7. The tubular outer metal jacket 10 made of tin plate was provided on the outside of the resin tube 8. The bottom end of the outer jacket 10 was bent inward, and the upper end thereof was curled inward, with the edge of the upper end thereof being crimped onto the insulation ring 12.
In producing the foregoing manganese dry battery, as the manganese dioxide used for the positive electrode active material, a mixture of 80 parts by weight of natural manganese dioxide (NMD) and 20 parts by weight of electrolytic manganese dioxide (EMD) was used. As the NMD, NMDs 1 to 6 as shown in Table 1 were used. Here, in Table 1, manufacturer A represents Quintal S.A., and manufacturer B represents Erachem Europe S.A. As the EMD, one manufactured by Guizhou Redstar Developing Dalong Manganese Industry Co., Ltd. was used. In preparing the above EMD, sodium hydrogen carbonate (NaHCO3) was used as a neutralizer, but after neutralization, the EMD was sufficiently washed with water.
As the electrolyte, electrolytes 1 to 5 as shown in Table 2 were used. The electrolytes 1 to 5 were prepared as follows. First, the electrolytes 1 to 3 were prepared by adding a predetermined amount of water that had been passed through cation exchange resin into each of different lot numbers of aqueous 40% by weight zinc chloride solutions manufactured by Nagai Metal Traders Sdn Bhd, heating the aqueous zinc chloride solution to a temperature from 45 to 50 degrees Celsius, adding a predetermined amount of ammonium chloride followed by stirring, and then further adding water that had been passed through cation exchange resin, so that the concentration of zinc chloride and the concentration of ammonium chloride in the electrolyte were 30% by weight and 1% by weight, respectively.
Next, potassium chloride was added into the electrolyte 1, so that the concentration of potassium in the electrolyte was 1.00 ppm, whereby the potassium-rich electrolyte 4 was prepared. Calcium chloride was added into the electrolyte 1, so that the concentration of calcium in the electrolyte was 1.00 ppm, whereby the calcium-rich electrolyte 5 was prepared.
Next, potassium chloride was added into the electrolyte 1, so that the concentration of potassium in the electrolyte was 1.00 ppm, whereby the potassium-rich electrolyte 4 was prepared. Calcium chloride was added into the electrolyte 1, so that the concentration of calcium in the electrolyte was 1.00 ppm, whereby the calcium-
The content of each element contained in the NMD, EMD, and electrolyte shown in Tables 1 and 2 was determined using atomic absorption spectrophotometry or ICP emission spectrometry. The combination of NMD and electrolyte was changed as shown in Table 3.
The storage characteristics of each battery were evaluated in the following manner.
The storage characteristics of each battery were evaluated in the following manner.
(1) Measurement of Open-circuit Voltage Before and After Storage
With respect to a battery in an initial state and a battery after storage for 2 months in an environment of 50 degrees Celsius, the open-circuit voltage at 20 degrees Celsius was measured. The difference between the open-circuit voltage V1 of the battery in an initial state and the open-circuit voltage V2 of the battery after storage (the drop in voltage during storage), namely, the value V1 - V2 was calculated. When the drop in voltage during storage was 50 mV or less, the storage characteristic was judged as being excellent.
With respect to a battery in an initial state and a battery after storage for 2 months in an environment of 50 degrees Celsius, the open-circuit voltage at 20 degrees Celsius was measured. The difference between the open-circuit voltage V1 of the battery in an initial state and the open-circuit voltage V2 of the battery after storage (the drop in voltage during storage), namely, the value V1 - V2 was calculated. When the drop in voltage during storage was 50 mV or less, the storage characteristic was judged as being excellent.
(2) Measurement of Duration of Discharge Before and After Storage
With respect to a battery in an initial state and a battery after storage for 2 months in an environment of 50 degrees Celsius, the duration of discharge (the length of time from the start to the end of discharge) was measured by continuously discharge each of the batteries at a constant resistance of 2.2 ohms in an environment of 20 degrees Celsius until the closed-circuit voltage reaches 0.9 V. The rate of the duration of discharge T2 of the battery after storage to the duration of discharge T1 of the battery in an initial state, namely, the value T2/T1 x 100 (hereinafter referred to as a capacity retention rate (%)) was calculated. When the capacity retention rate was 85% or higher, the storage characteristic was judged as being excellent.
Here, in the above measurements of the open-circuit voltage and the duration of discharge, five batteries per each example were measured, and an average of the five was obtained.
With respect to a battery in an initial state and a battery after storage for 2 months in an environment of 50 degrees Celsius, the duration of discharge (the length of time from the start to the end of discharge) was measured by continuously discharge each of the batteries at a constant resistance of 2.2 ohms in an environment of 20 degrees Celsius until the closed-circuit voltage reaches 0.9 V. The rate of the duration of discharge T2 of the battery after storage to the duration of discharge T1 of the battery in an initial state, namely, the value T2/T1 x 100 (hereinafter referred to as a capacity retention rate (%)) was calculated. When the capacity retention rate was 85% or higher, the storage characteristic was judged as being excellent.
Here, in the above measurements of the open-circuit voltage and the duration of discharge, five batteries per each example were measured, and an average of the five was obtained.
(3) Analysis of Elements in Positive Electrode Material Mixture (Measurement of Contents of Co, Ni, and Cu in Positive Electrode Material Mixture)
After the passage of one week since a battery was assembled, the battery was disassembled to take out the positive electrode material mixture (including the electrolyte) from the battery. In a beaker, 6 g of the positive electrode material mixture thus taken out was placed, to which 20 ml of concentrated hydrochloric acid (35% or higher, for accurate analysis) was added. The beaker was lidded with a watch glass, and heated on a hot plate to dissolve the positive electrode material mixture. In order to confirm that the positive electrode material mixture was dissolved, after allowed to cool, a few drops of hydrogen peroxide were added thereto to check the reaction progress. Thereafter, the beaker was heated again to decompose the remaining hydrogen peroxide. An insoluble matter A1 (e.g., carbon) was filtered out using filter paper (5B), and a solution A2 (including the washing fluid) was obtained as a filtrate. The solution A2 thus obtained was placed in a full measure flask (200 ml), and then water was added into the flask up to the marked line to dilute the solution with water, whereby a measurement solution A3 was prepared.
After the passage of one week since a battery was assembled, the battery was disassembled to take out the positive electrode material mixture (including the electrolyte) from the battery. In a beaker, 6 g of the positive electrode material mixture thus taken out was placed, to which 20 ml of concentrated hydrochloric acid (35% or higher, for accurate analysis) was added. The beaker was lidded with a watch glass, and heated on a hot plate to dissolve the positive electrode material mixture. In order to confirm that the positive electrode material mixture was dissolved, after allowed to cool, a few drops of hydrogen peroxide were added thereto to check the reaction progress. Thereafter, the beaker was heated again to decompose the remaining hydrogen peroxide. An insoluble matter A1 (e.g., carbon) was filtered out using filter paper (5B), and a solution A2 (including the washing fluid) was obtained as a filtrate. The solution A2 thus obtained was placed in a full measure flask (200 ml), and then water was added into the flask up to the marked line to dilute the solution with water, whereby a measurement solution A3 was prepared.
From a solution of manganese chloride tetrahydrate (guaranteed reagent), a certain amount of the solution was sampled several times, the amount being determined such that the Mn concentration therein was equal to that in the measurement solution. To each of these solutions thus sampled, each of commercially available standard solutions (solutions of Co, Ni, and Cu; concentration: 1 mg/ml each) was added stepwise, thereby to give solutions for calibration curve A4 having different concentrations of analyte elements.
With respect to the measurement solution A3 and the solutions for calibration curve A4 thus prepared, the emission intensity at an analytical wavelength of each element was measured using an ICP emission spectrometer (VISTA-RL available from VARIAN, Inc.), to give a calibration curve showing the relationship between an emission intensity and a concentration of each element. Using the calibration curve thus obtained, the concentration of each element in the unknown measurement solution A3 was determined.
With respect to the measurement solution A3 and the solutions for calibration curve A4 thus prepared, the emission intensity at an analytical wavelength of each element was measured using an ICP emission spectrometer (VISTA-RL available from VARIAN, Inc.), to give a calibration curve showing the relationship between an emission intensity and a concentration of each element. Using the calibration curve thus obtained, the concentration of each element in the unknown measurement solution A3 was determined.
The filter paper and the insoluble matter A1 obtained in the above were placed in a platinum crucible and subjected to drying and ashing, to which alkali salt (e.g., sodium carbonate) was then added, subsequently heat-fused, and thereafter dissolved with water and acid. The resultant solution was filtered and separated into an insoluble matter B1 and a solution B2 (including the washing fluid) which was a filtrate. The solution B2 was diluted to a fixed volume to give a measurement solution B3. Standard solutions with the same amount of alkali salt as used above added thereto (solutions of Co, Ni, and Cu; concentration: 1 mg/ml each) were used to give a calibration curve. Using the calibration curve thus obtained, the concentration of each element in the unknown measurement solution B3 was determined.
The amount of each element in the measurement solution A3 and the amount of each element in the measurement solution B3 were summed to give a content of each element in the positive electrode material mixture. It should be noted that in these examples, the measurement on the measurement solution B3 was performed since the positive electrode material mixture included NMD containing a large amount of impurities. In the case where a positive electrode material mixture that does not include NMD is used (i.e., in the case where EMD is used alone as the positive electrode active material), it is not necessary to perform the measurement on the measurement solution B3.
(4) Analysis of Elements in Electrolyte (Measurement of Amounts of Na, K, and Ca in Electrolyte)
The battery was disassembled to take out the positive electrode material mixture (including the electrolyte) from the battery. In a Teflon (registered trademark) beaker, 5 g of the positive electrode material mixture thus taken out was placed. After 100 ml of pure water was added into the Teflon (registered trademark) beaker, the water containing the positive electrode material mixture in the beaker was left for 1 hour at a temperature of 80 degrees Celsius while being stirred occasionally. Thereafter, the water containing the positive electrode material mixture was allowed to cool, and then filtered through filter paper (5B). The resultant filtrate (including the washing fluid) was placed in a full measure flask (200 ml). To the flask, 5 ml of 6 mol/L hydrochloric acid was added and then water was added up to the marked line to dilute the filtrate containing hydrochloric acid with water, whereby a sample solution was obtained.
The battery was disassembled to take out the positive electrode material mixture (including the electrolyte) from the battery. In a Teflon (registered trademark) beaker, 5 g of the positive electrode material mixture thus taken out was placed. After 100 ml of pure water was added into the Teflon (registered trademark) beaker, the water containing the positive electrode material mixture in the beaker was left for 1 hour at a temperature of 80 degrees Celsius while being stirred occasionally. Thereafter, the water containing the positive electrode material mixture was allowed to cool, and then filtered through filter paper (5B). The resultant filtrate (including the washing fluid) was placed in a full measure flask (200 ml). To the flask, 5 ml of 6 mol/L hydrochloric acid was added and then water was added up to the marked line to dilute the filtrate containing hydrochloric acid with water, whereby a sample solution was obtained.
From the sample solution thus obtained, a certain amount of the solution was taken out the required number of times. Using these sample solutions thus taken out, one measurement solution with no analyte element (K, Na, or Ca) added to the sample solution, and measurement solutions with an analyte element (K, Na, or Ca) added at different concentrations to each of the sample solutions were prepared. With respect to K and Na, an atomic absorption spectrophotometer (SpectrAA-55B available from VARIAN, Inc.) was used to create a calibration curve showing the relationship between a concentration and an indicated value, and using the calibration curve, the concentrations of the analyte elements (K and Na) were determined by a standard addition method. With respect to Ca, an ICP emission spectrometer (VISTA-RL available from VARIAN, Inc.) was used to create a calibration curve showing the relationship between an emission intensity and a concentration, and using the calibration curve, the concentration of the analyte element (Ca) was determined by a standard addition method.
The evaluation results are shown in Table 3.
The evaluation results are shown in Table 3.
[Corrected under Rule 26 07.05.2009]
In the batteries of Examples 1 to 13, the drops in battery voltage during storage were less than 50 mV, and the capacity retention rates were 85% or more, indicating that the storage characteristics were excellent. In the batteries of Comparative Examples 1 to 6 and 13 to 18, in which the content of nickel in the positive electrode material mixture was as high as more than 0.04% by weight, the capacity retention rates were below 85%, indicating that the storage characteristics were deteriorated. In the batteries of Comparative Examples 7, 11, and 12, in which the content of sodium in the electrolyte was as high as more than 0.8% by weight, the storage characteristics were significantly deteriorated. In the batteries of Comparative Examples 8 to 10, in which the content of nickel in the positive electrode material mixture was as high as more than 0.04% by weight and the content of sodium in the electrolyte was as high as more than 0.8% by weight, the storage characteristics were remarkably deteriorated.
<<Examples 14 to 17 and Comparative Examples 19 to 32>>
In preparing the positive electrode material mixture, a mixture of 50 parts by weight of NMD and 50 parts by weight of EMD was used as the positive electrode active material. As shown in Table 4, the combination of NMD and electrolyte was changed. Batteries were fabricated in the same manner as in Example 1 except the above. The batteries were evaluated in the same manner as described above. The evaluation results are shown in Table 4.
In preparing the positive electrode material mixture, a mixture of 50 parts by weight of NMD and 50 parts by weight of EMD was used as the positive electrode active material. As shown in Table 4, the combination of NMD and electrolyte was changed. Batteries were fabricated in the same manner as in Example 1 except the above. The batteries were evaluated in the same manner as described above. The evaluation results are shown in Table 4.
[Corrected under Rule 26 07.05.2009]
In the batteries of Examples 14 to 17, the drops in battery voltage during storage were less than 50 mV, and the capacity retention rates were 85% or more, indicating that the storage characteristics were excellent. In the batteries of Comparative Examples 19 and 20, in which the content of nickel in the positive electrode material mixture was as high as more than 0.04% by weight, the capacity retention rates were below 85%, indicating that the storage characteristics were deteriorated. In the batteries of Comparative Examples 21, 22, 25 to 28, 31, and 32, in which the content of sodium in the electrolyte was as high as more than 0.8% by weight, the storage characteristics were significantly deteriorated. In the batteries of Comparative Examples 23, 24, 29, and 30, in which the content of nickel in the positive electrode material mixture was as high as more than 0.04% by weight and the content of sodium in the electrolyte was as high as more than 0.8% by weight, the storage characteristics were remarkably deteriorated.
The manganese dry battery of the present invention is suitably used as a power source for electronic devices such as information devices and portable devices.
Claims (7)
- A manganese dry battery, comprising: a positive electrode material mixture including manganese dioxide; a negative electrode can including zinc; a separator layer disposed between said positive electrode material mixture and said negative electrode can; and
an electrolyte,
wherein the content of nickel in said positive electrode material mixture is 0.04% by weight or less, and the content of sodium in said electrolyte is 0.8% by weight or less. - The manganese dry battery in accordance with claim 1, wherein said positive electrode material mixture comprises a mixture of the manganese dioxide, a conductive agent, and the electrolyte, and the content of the manganese dioxide in said positive electrode material mixture is 40 to 60% by weight.
- The manganese dry battery in accordance with claim 2, wherein said manganese dioxide is at least one selected from natural manganese dioxide and electrolytic manganese dioxide.
- The manganese dry battery in accordance with claim 3, wherein the content of nickel in said natural manganese dioxide is 0.11% by weight or less.
- The manganese dry battery in accordance with claim 3, wherein the content of sodium in said electrolytic manganese dioxide is 0.4% by weight or less.
- The manganese dry battery in accordance with claim 1, wherein V1 - V2 is equal to or less than 50, where V1 represents an open-circuit voltage (mV) at 20 degrees Celsius in an initial state, and V2 represents an open-circuit voltage (mV) at 20 degrees Celsius after storage in an environment of 50 degrees Celsius for 2 months.
- The manganese dry battery in accordance with claim 1, wherein the manganese dry battery is of size D, and T2/T1 is equal to or more than 0.85, where T1 represents a duration of continuous discharge in an initial state, and T2 represents a duration of continuous discharge after storage in an environment of 50 degrees Celsius for 2 months, the continuous discharge being performed at a constant resistance of 2.2 ohms in an environment of 20 degrees Celsius until the closed-circuit voltage reaches 0.9 V.
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| CN200980000351.XA CN101828284A (en) | 2008-08-29 | 2009-04-15 | Manganese dry battery |
| JP2009539564A JP2012501040A (en) | 2008-08-29 | 2009-04-15 | Manganese battery |
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| CN111211322A (en) * | 2020-01-13 | 2020-05-29 | 五邑大学 | Preparation method of high-performance calcium manganate energy storage electrode material |
| CN111864224A (en) * | 2019-11-26 | 2020-10-30 | 宁波丰银电池有限公司 | Zinc-manganese dry battery manufacturing process |
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| CN105932312B (en) * | 2016-05-13 | 2019-12-31 | 刘建纯 | Carbon battery with low gas evolution amount and preparation method thereof |
| CN106410130A (en) * | 2016-07-27 | 2017-02-15 | 中信大锰矿业有限责任公司大新锰矿分公司 | Method for improving zinc-sheet corrosion resistance of natural discharging manganese powder |
| JP6627984B2 (en) * | 2016-09-27 | 2020-01-08 | トヨタ自動車株式会社 | Method and apparatus for producing SiC single crystal, and seed shaft used for producing SiC single crystal |
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- 2009-04-15 WO PCT/JP2009/001744 patent/WO2010023780A1/en active Application Filing
- 2009-04-15 JP JP2009539564A patent/JP2012501040A/en active Pending
- 2009-04-15 CN CN200980000351.XA patent/CN101828284A/en active Pending
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| JPH0384858A (en) * | 1989-08-28 | 1991-04-10 | Toshiba Battery Co Ltd | Manufacture of organic solvent cell |
| JPH0883611A (en) * | 1994-09-12 | 1996-03-26 | Toshiba Battery Co Ltd | Manganese dry battery |
| JP2001189157A (en) * | 1999-10-21 | 2001-07-10 | Hitachi Maxell Ltd | Manganese battery |
| EP1715535A1 (en) * | 2003-12-25 | 2006-10-25 | Toshiba Battery Co., Ltd. | Method for producing anode can for battery and manganese dry battery using such anode can for battery |
| US20080171266A1 (en) * | 2007-01-15 | 2008-07-17 | Fumio Kato | Alkaline dry battery |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111864224A (en) * | 2019-11-26 | 2020-10-30 | 宁波丰银电池有限公司 | Zinc-manganese dry battery manufacturing process |
| CN111211322A (en) * | 2020-01-13 | 2020-05-29 | 五邑大学 | Preparation method of high-performance calcium manganate energy storage electrode material |
| CN111211322B (en) * | 2020-01-13 | 2022-08-09 | 五邑大学 | Preparation method of high-performance calcium manganate energy storage electrode material |
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| Publication number | Publication date |
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| CN101828284A (en) | 2010-09-08 |
| JP2012501040A (en) | 2012-01-12 |
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