WO2022130682A1 - 水系一次電池 - Google Patents
水系一次電池 Download PDFInfo
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- WO2022130682A1 WO2022130682A1 PCT/JP2021/029089 JP2021029089W WO2022130682A1 WO 2022130682 A1 WO2022130682 A1 WO 2022130682A1 JP 2021029089 W JP2021029089 W JP 2021029089W WO 2022130682 A1 WO2022130682 A1 WO 2022130682A1
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- WO
- WIPO (PCT)
- Prior art keywords
- negative electrode
- atoms
- positive electrode
- electrolytic solution
- mass
- Prior art date
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- 239000008151 electrolyte solution Substances 0.000 claims abstract description 54
- 239000007773 negative electrode material Substances 0.000 claims abstract description 27
- 239000011701 zinc Substances 0.000 claims abstract description 27
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 25
- 150000001923 cyclic compounds Chemical class 0.000 claims abstract description 24
- 239000000654 additive Substances 0.000 claims abstract description 13
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- -1 phthalimide compound Chemical class 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 125000004429 atom Chemical group 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical group 0.000 claims description 6
- BYXYCUABYHCYLY-UHFFFAOYSA-N isoindole-1,3-dione;potassium Chemical compound [K].C1=CC=C2C(=O)NC(=O)C2=C1 BYXYCUABYHCYLY-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000001246 bromo group Chemical group Br* 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 abstract description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 26
- 239000000843 powder Substances 0.000 description 17
- 229910001297 Zn alloy Inorganic materials 0.000 description 15
- 239000002245 particle Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000004745 nonwoven fabric Substances 0.000 description 8
- 239000006258 conductive agent Substances 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- 239000003349 gelling agent Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- SPAMRUYRVYMHPV-UHFFFAOYSA-N 3a,4,5,7a-tetrahydroisoindole-1,3-dione Chemical class C1=CCCC2C(=O)NC(=O)C21 SPAMRUYRVYMHPV-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 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 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical class C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/606—Polymers containing aromatic main chain polymers
- H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
-
- 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
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/244—Zinc electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present disclosure relates to an aqueous primary battery including an aqueous electrolytic solution.
- the recommended period for use without discharge is set to 10 years at the maximum.
- One of the reasons for setting the recommended usage period is an increase in battery internal pressure.
- zinc contained in the negative electrode of an aqueous primary cell gradually reacts with water to generate a trace amount of hydrogen gas at any time. When this gas is accumulated in the battery for a long period of time, the internal pressure of the battery rises, which causes liquid leakage.
- Patent Document 1 has a zinc alloy powder and an electrolytic solution, and has a negative electrode material to which 0.001 to 5.0 parts by weight of polyoxyethylene alkyl ether phosphate ester is added to 100 parts by weight of the zinc alloy powder.
- Patent Document 2 describes a positive electrode containing at least one of manganese dioxide powder and nickel oxyhydroxide powder, a negative electrode containing zinc alloy powder, a separator disposed between the positive electrode and the negative electrode, an alkaline electrolytic solution, and the like.
- An alkaline dry battery comprising a metal case containing iron as a main component and a battery case composed of a zinc-containing layer formed on the inner surface of the metal case and containing a positive electrode, a negative electrode, a separator, and an alkaline electrolytic solution.
- the negative electrode is further adsorbed on the surface of the zinc alloy powder while it is not discharged, and at the start of discharge, it is swiftly removed from the surface of the zinc alloy powder without hindering the movement of ions in the alkaline electrolytic solution.
- One aspect of the present disclosure comprises a positive electrode, a negative electrode, a separator arranged between the positive electrode and the negative electrode, and an electrolytic solution of the positive electrode, the negative electrode, and an aqueous solution contained in the separator.
- the negative electrode and / or the electrolytic solution contains an additive, the negative electrode contains a negative electrode active material, the negative electrode active material contains zinc, the additive contains a cyclic compound, and the cyclic compound is.
- the present invention relates to an aqueous primary battery having a first ring containing an ⁇ N—CO— structure and a second ring that shares at least two atoms with the first ring.
- leakage can be suppressed even when a water-based primary battery containing zinc in the negative electrode active material and an aqueous electrolytic solution is stored for a long period of time.
- FIG. 1 is a front view showing a part of an alkaline dry battery according to an embodiment of the present disclosure as a cross section.
- the aqueous primary battery according to the embodiment of the present disclosure includes a positive electrode, a negative electrode, a separator arranged between the positive electrode and the negative electrode, and an electrolytic solution of an aqueous solution contained in the positive electrode, the negative electrode, and the separator (hereinafter, simply electrolytic solution). Also referred to as a liquid).
- the water-based primary battery generally includes a primary battery having an aqueous electrolytic solution.
- the electrolytic solution of the aqueous solution contains water as the main component of the solvent.
- the main component of the solvent means a component that occupies 50% by mass or more, 70% by mass or more, and further 90% by mass or more of the solvent.
- the negative electrode contains a negative electrode active material, and the negative electrode active material contains zinc. Zinc reacts little by little with water in the electrolytic solution to generate a small amount of hydrogen gas at any time.
- a water-based primary battery is stored for a long period of time, hydrogen gas is accumulated in the battery and the internal pressure of the battery rises.
- the gas in the battery is released to the outside by, for example, the operation of the safety valve provided in the battery or the formation of a gap in the sealing portion such as the crimped portion. At that time, liquid leakage may occur.
- the negative electrode and / or the electrolytic solution contains an additive.
- Additives include cyclic compounds.
- the cyclic compound has a first ring containing an -N-CO- structure (ie, an amide bond) and a second ring that shares at least two atoms with the first ring.
- CO in the -N-CO- structure is a carbonyl group.
- the shared atom is a constituent atom of the first ring and is also a constituent atom of the second ring.
- Cyclic compounds are thought to generate anions in the electrolyte.
- the negative charge of the anion is localized to nitrogen in the -N-CO- structure. Since the negative charge of nitrogen contained in the first ring has a large electrical interaction with the metal, the anion of the cyclic compound is easily adsorbed on the zinc surface.
- the second ring adjacent to the first ring adsorbed on the zinc surface can be a barrier to the formation of hydrogen gas and zinc complex ions (Zn ( OH ) 42- ) due to the reaction between zinc and water.
- the anion of the cyclic compound may form a complex ( Zn (MA) 4-2- (where MA is the anion of the cyclic compound)) with zinc ion in the electrolytic solution.
- this complex is bulky and exists in the vicinity of the negative electrode active material.
- Such a complex can be a sufficient barrier to protect the zinc surface and is considered to have an action of reducing the dissolving activity of zinc. As a result, the increase in battery internal pressure due to the generation of hydrogen gas is suppressed, and liquid leakage is suppressed.
- the cyclic compound may have only a first ring and a second ring, and may further have one or more (that is, three or more in total) rings.
- the cyclic compound may have, for example, a total of 2 to 4 rings or 2 to 3 rings.
- the first ring and the second ring are independently 5-membered, 6-membered or 7-membered rings, respectively, in terms of structural stability.
- the second ring may be an aliphatic ring or an aromatic ring.
- the aliphatic ring can be a cycloalkane, a cycloalkene, or the like.
- the aromatic ring is, for example, a benzene ring and may be part of a fused ring or a polycycle.
- the second ring may be part of a fused ring such as naphthalene or anthracene.
- the cyclic compound may be, for example, at least one selected from the group consisting of the following phthalimide compounds, phthalimidine compounds and tetrahydrophthalimide compounds. These cyclic compounds are easily ionized in the electrolytic solution and generate negatively charged anions localized in nitrogen.
- the phthalimide compound has a general formula (1):
- X1 to X4 are independently hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms or alkyl groups having 1 to 3 carbon atoms, and Y1 is hydrogen. It is represented by an atom or an alkali metal atom.).
- the phthalimidine compound has the general formula (2) :.
- X5 to X8 are independently hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms or alkyl groups having 1 to 3 carbon atoms, and Y2 is hydrogen. It is an atom or an alkali metal atom.).
- the tetrahydrophthalimide compound has a general formula (3) :.
- Y3 is a hydrogen atom or an alkali metal atom.
- X1 to X8 can be, for example, a methyl group, an ethyl group, an n-propyl group, or the like independently of each other.
- the cyclic compound may be, for example, at least one selected from the group consisting of phthalimide and phthalimide potassium. These are desirable because they are commercially available.
- the amount of the cyclic compound contained in the battery is not particularly limited, but for example, 0.005 parts by mass or more and 0.05 parts by mass or less per 100 parts by mass of the negative electrode active material is an appropriate amount, and 0.01 parts by mass or more. , 0.05 parts by mass or less, 0.015 parts by mass or more, and 0.04 parts by mass or less.
- the negative electrode and / or the electrolytic solution may contain at least one selected from the group consisting of phthalic acid, ammonia and ammonium carbonate, in addition to the cyclic compound.
- the amount of phthalic acid contained in the battery is, for example, preferably 0.1% by mass or less per 100 parts by mass of the negative electrode active material.
- the amount of ammonia and ammonium carbonate contained in the battery is preferably, for example, 0.001% by mass or less in total per 100 parts by mass of the negative electrode active material.
- Typical examples of water-based primary batteries include manganese dry batteries and alkaline dry batteries (alkaline manganese dry batteries). These contain manganese dioxide as a positive electrode.
- the manganese dry cell has a zinc can containing a positive electrode as a negative electrode, and has a carbon rod inserted in the positive electrode.
- Alkaline batteries have a gel-like negative electrode contained in a tubular positive electrode.
- the form of the water-based primary battery is not particularly limited, but may be a cylindrical battery, a flat battery, a square battery, a coin battery, or the like.
- Zinc powder, zinc alloy powder, etc. are used as the negative electrode active material.
- the zinc alloy may contain at least one selected from the group consisting of, for example, tin, indium, bismuth and aluminum.
- the indium content in the zinc alloy is, for example, 0.01 to 0.1% by mass.
- the bismuth content in the zinc alloy is, for example, 0.003 to 0.02% by mass.
- the aluminum content in the zinc alloy is, for example, 0.001 to 0.03% by mass.
- the proportion of elements other than zinc in the zinc alloy is preferably 0.025 to 0.08% by mass from the viewpoint of corrosion resistance.
- the negative electrode active material is usually used in powder form.
- the average particle size (D50) of the negative electrode active material powder is, for example, 100 to 200 ⁇ m, preferably 110 to 160 ⁇ m.
- the average particle size (D50) is the median diameter in the volume-based particle size distribution.
- the average particle size is determined by using, for example, a laser diffraction / scattering type particle distribution measuring device.
- the alkaline dry cell according to the embodiment of the present disclosure will be further described with reference to the drawings.
- the present invention is not limited to the following embodiments. Further, it can be appropriately changed as long as it does not deviate from the range in which the effect of the present invention is exhibited. Furthermore, it can be combined with other embodiments.
- FIG. 1 is a front view having a cross section of the horizontal half of the alkaline dry battery according to the embodiment of the present disclosure.
- FIG. 1 shows an example of a cylindrical battery having an inside-out type structure.
- the alkaline dry cell comprises a hollow cylindrical positive electrode 2, a gel-like negative electrode 3 arranged in the hollow portion of the positive electrode 2, a separator 4 arranged between them, and an electrolytic solution. These are housed in a bottomed cylindrical battery case 1 that also serves as a positive electrode terminal. An alkaline aqueous solution is used as the electrolytic solution.
- the positive electrode 2 is arranged in contact with the inner wall of the battery case 1.
- the positive electrode 2 contains manganese dioxide and an electrolytic solution.
- the hollow portion of the positive electrode 2 is filled with the gel-like negative electrode 3 via the separator 4.
- the negative electrode 3 usually contains an electrolytic solution and a gelling agent in addition to the negative electrode active material containing zinc.
- the separator 4 has a bottomed cylindrical shape and contains an electrolytic solution.
- the separator 4 is composed of a cylindrical separator 4a and a bottom paper 4b.
- the separator 4a is arranged along the inner surface of the hollow portion of the positive electrode 2 and separates the positive electrode 2 and the negative electrode 3.
- the separator arranged between the positive electrode and the negative electrode means a cylindrical separator 4a.
- the bottom paper 4b is arranged at the bottom of the hollow portion of the positive electrode 2, and separates the negative electrode 3 from the battery case 1.
- the opening of the battery case 1 is sealed by the sealing unit 9.
- the sealing unit 9 includes a gasket 5, a negative electrode terminal plate 7 that also serves as a negative electrode terminal, and a negative electrode current collector 6.
- the negative electrode current collector 6 is inserted in the negative electrode 3.
- the gasket 5 is provided with a safety valve having an annular thin-walled portion 5a.
- the negative electrode current collector 6 has a nail shape having a head and a body portion, the body portion is inserted into a through hole provided in the central cylinder portion of the gasket 5, and the head portion of the negative electrode current collector 6 is a negative electrode terminal. It is welded to the flat portion in the center of the plate 7.
- the open end of the battery case 1 is crimped to the flange of the peripheral edge of the negative electrode terminal plate 7 via the outer peripheral end of the gasket 5.
- the outer surface of the battery case 1 is covered with an exterior label 8.
- alkaline batteries The details of alkaline batteries will be described below.
- the negative electrode is obtained by mixing a negative electrode active material containing zinc (powder of zinc, zinc alloy, etc.), a gelling agent, and an electrolytic solution.
- the additive may be contained only in the electrolytic solution, but even in that case, since the negative electrode contains the electrolytic solution, it can be said that the negative electrode contains the additive.
- the gelling agent is not particularly limited, but for example, a water-absorbent polymer or the like can be used.
- a water-absorbent polymer examples include polyacrylic acid and sodium polyacrylate.
- the amount of the gelling agent contained in the negative electrode is, for example, 0.5 to 2.5 parts by mass per 100 parts by mass of the negative electrode active material.
- the negative electrode current collector preferably contains copper, and may be made of an alloy containing copper and zinc, for example, brass. If necessary, the negative electrode current collector may be plated with tin plating or the like.
- the positive electrode usually contains a conductive agent and an electrolytic solution in addition to manganese dioxide, which is a positive electrode active material. Further, the positive electrode may further contain a binder, if necessary.
- manganese dioxide electrolytic manganese dioxide is preferable.
- crystal structure of manganese dioxide include ⁇ -type, ⁇ -type, ⁇ -type, ⁇ -type, ⁇ -type, ⁇ -type, ⁇ -type, and Ramsderite-type.
- Manganese dioxide is used in the form of powder.
- the average particle size (D50) of manganese dioxide is, for example, 25 to 60 ⁇ m from the viewpoint of easily ensuring the filling property of the positive electrode and the diffusivity of the electrolytic solution in the positive electrode.
- the conductive agent examples include carbon black such as acetylene black and conductive carbon materials such as graphite.
- carbon black such as acetylene black
- conductive carbon materials such as graphite.
- the conductive agent may be in the form of fibers or the like, but is preferably in the form of powder.
- the average particle size (D50) of the conductive agent is, for example, 3 to 20 ⁇ m.
- the content of the conductive agent in the positive electrode is, for example, 3 to 10 parts by mass, preferably 5 to 9 parts by mass with respect to 100 parts by mass of manganese dioxide.
- the positive electrode can be obtained, for example, by pressure-molding a positive electrode mixture containing a positive electrode active material, a conductive agent, an electrolytic solution, and if necessary, a binder into pellets.
- the positive electrode mixture may be once made into flakes or granules, classified if necessary, and then pressure-molded into pellets.
- the separator examples include cellulose and polyvinyl alcohol.
- the separator may be a non-woven fabric mainly using fibers of the above material, or may be a microporous film such as cellophane or polyolefin.
- a non-woven fabric and a microporous film may be used in combination.
- the non-woven fabric include a non-woven fabric mainly composed of cellulose fibers and polyvinyl alcohol fibers, a non-woven fabric mainly composed of rayon fibers and polyvinyl alcohol fibers, and the like.
- the thickness of the separator is, for example, 100 to 300 ⁇ m.
- the separator preferably has the above-mentioned thickness as a whole, and if the sheets constituting the separator are thin, a plurality of sheets may be stacked to have the above-mentioned thickness.
- the electrolytic solution is contained in the positive electrode, the negative electrode and the separator.
- As the electrolytic solution for example, an alkaline aqueous solution containing potassium hydroxide is used.
- the concentration of potassium hydroxide in the electrolytic solution is preferably 20 to 50% by mass.
- the electrolytic solution may further contain zinc oxide.
- the concentration of zinc oxide in the electrolytic solution is, for example, 1 to 5% by mass.
- gasket examples of the material of the gasket include polyamide, polyethylene, polypropylene and the like.
- the gasket can be obtained, for example, by injection molding into a predetermined shape using the above-mentioned material.
- Gaskets usually have a thin wall for explosion protection.
- the thin portion is preferably formed in an annular shape from the viewpoint of facilitating breakage.
- the gasket 5 of FIG. 1 has an annular thin-walled portion 5a. From the viewpoint of making it easy to break the thin portion when the internal pressure rises, the gasket material is preferably 6,10-nylon, 6,12-nylon, and polypropylene.
- Battery case for example, a bottomed cylindrical metal case is used.
- metal case for example, a nickel-plated steel plate is used.
- Example 1 The AA cylindrical alkaline dry cell (LR6) shown in FIG. 1 was produced according to the following procedures (1) to (3).
- the flake-shaped positive electrode mixture is crushed into granules, which are classified by a sieve of 10 to 100 mesh, and 11 g of the obtained granules are pressure-molded into a predetermined hollow cylindrical shape having an outer diameter of 13.65 mm. , Two positive electrode pellets were prepared.
- Negative Electrode A zinc alloy powder (average particle size (D50) 130 ⁇ m) as a negative electrode active material, an electrolytic solution, and a gelling agent were mixed to obtain a gel-like negative electrode 3.
- the electrolytic solution is the same as the electrolytic solution used in the production of the positive electrode.
- zinc alloy a zinc alloy (ZnBiAlIn) containing 0.02% by mass of indium, 0.01% by mass of bismuth, and 0.005% by mass of aluminum was used.
- the gelling agent a mixture of crosslinked branched polyacrylic acid and highly crosslinked chain polyacrylate sodium was used.
- the electrolytic solution contained potassium hydroxide (concentration 35% by mass) and zinc oxide (concentration 2% by mass), and an alkaline aqueous solution containing phthalimide potassium was used as an additive.
- the amount of phthalimide potassium was adjusted to 0.025 parts by mass per 100 parts by mass of the negative electrode active material.
- the separator 4 is configured by using a cylindrical separator 4a and a bottom paper 4b.
- a non-woven fabric sheet (basis weight 28 g / m 2 ) was used, which was mainly composed of rayon fiber and polyvinyl alcohol fiber having a mass ratio of 1: 1.
- the thickness of the non-woven fabric sheet used for the bottom paper 4b was 0.27 mm.
- the separator 4a was formed by triple-wrapping a non-woven fabric sheet having a thickness of 0.09 mm.
- a sealing unit is installed in the opening of the battery case 1 to seal the opening of the battery case 1, but here, for the following evaluation, the opening is not sealed and the opening is opened.
- Alkaline dry cell A1 in the state of being in a fresh state was produced.
- Example 2 Alkaline dry batteries A2 were produced in the same manner as in Example 1 except that phthalimide was used as an additive in the preparation of the electrolytic solution.
- Comparative Example 1 Alkaline dry cell B1 was prepared and evaluated in the same manner as in Example 1 except that phthalimide potassium was not used in the preparation of the electrolytic solution.
- Comparative Example 2 An alkaline dry cell B2 was prepared in the same manner as in Example 1 except that a polyoxyethylene alkyl ether phosphoric acid ester (denoted as a phosphoric acid ester in Table 1) was used instead of phthalimide potassium in the preparation of the electrolytic solution. ,evaluated.
- the present disclosure can be applied to water-based primary batteries in which the negative electrode active material contains zinc and an aqueous electrolytic solution is provided, for example, alkaline batteries, manganese batteries, and the like.
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Abstract
Description
負極は、亜鉛を含む負極活物質(亜鉛、亜鉛合金などの粉末)と、ゲル化剤と、電解液とを混合することにより得られる。添加剤は、電解液だけに含ませてもよいが、その場合でも負極は電解液を含むため、負極は添加剤を含むといえる。
ゲル状負極に挿入される負極集電体の材質としては、例えば、金属、合金などが挙げられる。負極集電体は、好ましくは、銅を含み、例えば、真鍮などの銅および亜鉛を含む合金製であってもよい。負極集電体は、必要により、スズメッキなどのメッキ処理がされていてもよい。
正極は、通常、正極活物質である二酸化マンガンに加え、導電剤および電解液を含む。また、正極は、必要に応じて、さらに結着剤を含有してもよい。
セパレータの材質としては、例えば、セルロース、ポリビニルアルコールなどが例示できる。セパレータは、上記材料の繊維を主体として用いた不織布であってもよく、セロファンやポリオレフィン系などの微多孔質フィルムであってもよい。不織布と微多孔質フィルムとを併用してもよい。不織布としては、セルロース繊維およびポリビニルアルコール繊維を主体として混抄した不織布、レーヨン繊維およびポリビニルアルコール繊維を主体として混抄した不織布などが例示できる。
電解液は、正極、負極およびセパレータ中に含まれる。電解液としては、例えば、水酸化カリウムを含むアルカリ水溶液が用いられる。電解液中の水酸化カリウムの濃度は、20~50質量%が好ましい。電解液に、さらに酸化亜鉛を含ませてもよい。電解液中の酸化亜鉛の濃度は、例えば、1~5質量%である。
ガスケットの材質としては、ポリアミド、ポリエチレン、ポリプロピレンなどが挙げられる。ガスケットは、例えば、上記材質を用いて所定の形状に射出成型することにより得られる。ガスケットは、通常、防爆用の薄肉部を有する。薄肉部は、破断を容易にする観点から環状に形成されていることが好ましい。図1のガスケット5は、環状の薄肉部5aを有する。内圧上昇時に薄肉部を破断しやすくする観点から、ガスケットの材質は、6,10-ナイロン、6,12-ナイロン、およびポリプロピレンが好ましい。
電池ケースには、例えば、有底円筒形の金属ケースが用いられる。金属ケースには、例えば、ニッケルめっき鋼板が用いられる。正極と電池ケースとの間の密着性を良くするためには、金属ケースの内面を炭素被膜で被覆した電池ケースを用いるのが好ましい。
下記の(1)~(3)の手順に従って、図1に示す単3形の円筒形アルカリ乾電池(LR6)を作製した。
正極活物質である電解二酸化マンガン粉末(平均粒径(D50)35μm)に、導電剤である黒鉛粉末(平均粒径(D50)8μm)を加え、混合物を得た。電解二酸化マンガン粉末および黒鉛粉末の質量比は92.4:7.6とした。電解二酸化マンガン粉末は、比表面積が41m2/gであるものを用いた。混合物に電解液を加え、充分に攪拌した後、フレーク状に圧縮成形して、正極合剤を得た。混合物および電解液の質量比は100:1.5とした。
負極活物質である亜鉛合金粉末(平均粒径(D50)130μm)と、電解液と、ゲル化剤とを混合し、ゲル状の負極3を得た。電解液は、正極の作製で用いた電解液と同じである。
電解液には、水酸化カリウム(濃度35質量%)および酸化亜鉛(濃度2質量%)を含み、添加剤としてフタルイミドカリウムを含むアルカリ水溶液を用いた。フタルイミドカリウムの量は、負極活物質100質量部あたり0.025質量部となるように調整した。
ニッケルめっき鋼板製の有底円筒形の電池ケース(外径13.80mm、円筒部の肉厚0.15mm、高さ50.3mm)の内面に、日本黒鉛(株)製のバニーハイトを塗布して厚み約10μmの炭素被膜を形成し、電池ケース1を得た。電池ケース1内に正極ペレットを縦に2個挿入した後、加圧して、電池ケース1の内壁に密着した状態の正極2を形成した。有底円筒形のセパレータ4を正極2の内側に配置した後、上記電解液を注入し、セパレータ4に含浸させた。この状態で所定時間放置し、電解液をセパレータ4から正極2へ浸透させた。その後、6gのゲル状負極3を、セパレータ4の内側に充填した。
電解液の調製において、添加剤として、フタルイミドカリウムの代わりに、フタルイミドを用いたこと以外、実施例1と同様にしてアルカリ乾電池A2を作製した。
電解液の調製において、フタルイミドカリウムを用いなかったこと以外、実施例1と同様にしてアルカリ乾電池B1を作製し、評価した。
電解液の調製において、フタルイミドカリウムの代わりに、ポリオキシエチレンアルキルエーテルリン酸エステル(表1にはリン酸エステルと表記)を用いたこと以外、実施例1と同様にしてアルカリ乾電池B2を作製し、評価した。
上記で作製した電池A1、A2、B1およびB2を、それぞれ流動パラフィンに浸漬し、その状態で70℃で1月間保存し、保存期間中に電池から発生するガスを捕集した。電池B1から発生したガス量を100%としたときの電池A1、A2およびB2のガス量の割合を表1に示す。
2 正極
3 負極
4 有底円筒形のセパレータ
4a 円筒型のセパレータ
4b 底紙
5 ガスケット
5a 薄肉部
6 負極集電体
7 負極端子板
8 外装ラベル
9 封口ユニット
Claims (5)
- 正極と、負極と、前記正極と前記負極との間に配されたセパレータと、前記正極、前記負極および前記セパレータ中に含まれる水溶液の電解液と、を備え、
前記負極および/または前記電解液は、添加剤を含み、
前記負極は、負極活物質を含み、
前記負極活物質は、亜鉛を含み、
前記添加剤は、環式化合物を含み、
前記環式化合物は、-N-CO-構造を含む第1の環と、前記第1の環と少なくとも2つの原子を共有する第2の環と、を有する、水系一次電池。 - 前記環式化合物は、
一般式(1):
一般式(2):
一般式(3):
- 前記環式化合物は、フタルイミドおよびフタルイミドカリウムからなる群より選択される少なくとも1種である、請求項2に記載の水系一次電池。
- 前記環式化合物の量は、前記負極活物質100質量部あたり0.005質量部以上、0.05質量部以下である、請求項1~3のいずれか1項に記載の水系一次電池。
- 前記水系一次電池は、アルカリ乾電池またはマンガン乾電池である、請求項1~4のいずれか1項に記載の水系一次電池。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2004022216A (ja) * | 2002-06-13 | 2004-01-22 | Matsushita Electric Ind Co Ltd | 電池 |
JP2006024407A (ja) * | 2004-07-07 | 2006-01-26 | Matsushita Electric Ind Co Ltd | 有機電解液電池 |
JP2006173096A (ja) * | 2004-11-18 | 2006-06-29 | Matsushita Electric Ind Co Ltd | 有機電解質電池 |
WO2020166138A1 (ja) * | 2019-02-13 | 2020-08-20 | パナソニックIpマネジメント株式会社 | アルカリ乾電池 |
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- 2021-08-05 JP JP2022569703A patent/JPWO2022130682A1/ja active Pending
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2004022216A (ja) * | 2002-06-13 | 2004-01-22 | Matsushita Electric Ind Co Ltd | 電池 |
JP2006024407A (ja) * | 2004-07-07 | 2006-01-26 | Matsushita Electric Ind Co Ltd | 有機電解液電池 |
JP2006173096A (ja) * | 2004-11-18 | 2006-06-29 | Matsushita Electric Ind Co Ltd | 有機電解質電池 |
WO2020166138A1 (ja) * | 2019-02-13 | 2020-08-20 | パナソニックIpマネジメント株式会社 | アルカリ乾電池 |
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