CN1163993C - Core of alkali storage battery and battery using the core - Google Patents
Core of alkali storage battery and battery using the core Download PDFInfo
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- CN1163993C CN1163993C CNB998154083A CN99815408A CN1163993C CN 1163993 C CN1163993 C CN 1163993C CN B998154083 A CNB998154083 A CN B998154083A CN 99815408 A CN99815408 A CN 99815408A CN 1163993 C CN1163993 C CN 1163993C
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- Prior art keywords
- nickel
- graphite
- core body
- disperse
- battery
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- 239000003513 alkali Substances 0.000 title abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 174
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 120
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 115
- 239000010439 graphite Substances 0.000 claims abstract description 115
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 87
- 239000011149 active material Substances 0.000 claims abstract description 27
- 229910000990 Ni alloy Inorganic materials 0.000 claims abstract description 16
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 16
- 239000000956 alloy Substances 0.000 claims abstract description 16
- 229910001152 Bi alloy Inorganic materials 0.000 claims abstract description 4
- 229910000914 Mn alloy Inorganic materials 0.000 claims abstract description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000531 Co alloy Inorganic materials 0.000 claims abstract description 3
- 229910001313 Cobalt-iron alloy Inorganic materials 0.000 claims abstract description 3
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- LGRDPUAPARTXMG-UHFFFAOYSA-N bismuth nickel Chemical compound [Ni].[Bi] LGRDPUAPARTXMG-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011248 coating agent Substances 0.000 claims description 68
- 238000000576 coating method Methods 0.000 claims description 68
- 238000009792 diffusion process Methods 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 abstract description 37
- 239000010959 steel Substances 0.000 abstract description 37
- 238000007747 plating Methods 0.000 abstract description 25
- 239000002344 surface layer Substances 0.000 abstract 1
- 238000009713 electroplating Methods 0.000 description 30
- 239000000758 substrate Substances 0.000 description 30
- 238000000034 method Methods 0.000 description 19
- 238000000137 annealing Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005238 degreasing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005554 pickling Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 5
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000003490 calendering Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- -1 alkyl sodium sulphate Chemical compound 0.000 description 3
- 238000004873 anchoring Methods 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L sodium sulphate Substances [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 229940124530 sulfonamide Drugs 0.000 description 3
- 150000003456 sulfonamides Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 229940105329 carboxymethylcellulose Drugs 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000011536 re-plating Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 101000822695 Clostridium perfringens (strain 13 / Type A) Small, acid-soluble spore protein C1 Proteins 0.000 description 1
- 101000655262 Clostridium perfringens (strain 13 / Type A) Small, acid-soluble spore protein C2 Proteins 0.000 description 1
- 229910020598 Co Fe Inorganic materials 0.000 description 1
- 229910002519 Co-Fe Inorganic materials 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical class F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910003271 Ni-Fe Inorganic materials 0.000 description 1
- 229910003286 Ni-Mn Inorganic materials 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 101000655256 Paraclostridium bifermentans Small, acid-soluble spore protein alpha Proteins 0.000 description 1
- 101000655264 Paraclostridium bifermentans Small, acid-soluble spore protein beta Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 201000009240 nasopharyngitis Diseases 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- ZOAYTCFPBFZGJT-UHFFFAOYSA-L sodium silicon(4+) sulfate Chemical compound S(=O)(=O)([O-])[O-].[Na+].[Si+4] ZOAYTCFPBFZGJT-UHFFFAOYSA-L 0.000 description 1
- RTVVXRKGQRRXFJ-UHFFFAOYSA-N sodium;2-sulfobutanedioic acid Chemical compound [Na].OC(=O)CC(C(O)=O)S(O)(=O)=O RTVVXRKGQRRXFJ-UHFFFAOYSA-N 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
- H01M50/1243—Primary casings; Jackets or wrappings characterised by the material having a layered structure characterised by the internal coating on the casing
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Electroplating Methods And Accessories (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention provides an alkali storage battery core of thin steel superior in retaining active material, and a battery using the core. The core is made from thin steel plated with graphite-dispersed nickel or graphite-dispersed nickel alloy. The alloy plating preferably includes a nickel-cobalt alloy, nickel-cobalt iron alloy, nickel-manganese alloy, nickel-phosphorous-alloy or nickel-bismuth alloy. Since its surface layer contains nickel or nickel alloy and graphite, the core has irregularities in the surface, and it can retain active material adequately.
Description
Technical field
The present invention relates to a kind of core body of alkaline battery, relate in particular to a kind of at battery positive plate and negative plate in the core body that is used for battery lead plate that uses and the battery that uses this core body.
Background technology
Alkaline battery has been widely used as the power supply of the secondary cell of various device because its can reuse repeatedly, compact conformation and in light weight, so alkaline battery is both economical.
In general, alkaline battery comprise the positive plate that applies nickel hydroxide, coating hydrogen adsorbing alloy negative plate, be used to the housing separating the partition of positive plate and negative plate and be used to seal two battery lead plates.For the negative plate of alkaline battery, to use electronickelling and applied the perforated metal of hydrogen adsorbing alloy, the hole in the perforated metal is machine drilling.For positive plate, used the foaming nickel of coating nickel hydroxide.In order to form foaming nickel, for example, electroplate the Foamex sheet with nickel, and at high temperature with oxygenous gas treatment Foamex sheet so that Foamex volatilize.Thereby can obtain the supporter of high porosity.
In alkaline electrolyte solution, on above-mentioned perforated sheet, form high-resistance nickel oxide or nickel hydroxide, perforated plate soaks in alkaline solution for a long time simultaneously.Therefore, sheet resistance becomes very high.Except above-mentioned defective, when producing foaming nickel main body, also has other defective.For example, be difficult to select fine materials, and the manufacturing step complexity.Therefore, product will carry out very strict control and manufacturing cost during fabrication often increases.
For addressing the aforementioned drawbacks and provide the core body of high-performance and economy for battery, the inventor has researched and developed the plating core body main body that graphite is arranged as the disperse of electrode, it is stable to alkaline electrolyte solution, and high-resistance nickel oxide and nickel hydroxide can not form on the surface of core body.As a result, the inventor finds that by being used for electroplating the nickel that disperse has graphite on the core body of pole plate, core body can form the convex-concave surface with good anchoring effect, so that fixing active material.
Summary of the invention
In battery body component according to the present invention, positive and negative pole plate forms by adhesion activity material on as tabular current-collector.Two battery lead plates separate with partition and are sealed in the housing of alkaline battery.Store in the battery of nickel at this, sheet metal has the nickel of graphite and nickel alloy that disperse has graphite to electroplate with disperse, so that form convex-concave surface.Thus, core body has the fixedly good characteristic of active material.
For nickel alloy layer, nickel-cobalt alloy layer, nickel-cobalt-iron alloy layer, nickel-manganese alloy layer, nickel-phosphor alloy layer or nickel-bismuth alloy layer are preferred.
Preferably have under the nickel coating of graphite or the nickel alloy coating that disperse has graphite diffusion layer or nickel dam are set in disperse.
Preferred disperse has the nickel dam of graphite or nickel alloy layer that disperse has graphite to comprise the graphite of 0.1-25wt%.
Representative solution of the present invention can be summarized as follows:
(1) a kind of core body that is used for alkaline battery, wherein, this battery comprises: active material is sticked to as the positive plate and the negative plate that form on the core body of tabular collector body; And the housing that is used to seal these two battery lead plates, described core body is characterised in that, is formed with the nickel coating that disperse has graphite on sheet metal.
(2) a kind of core body that is used for alkaline battery, wherein, this battery comprises: active material is sticked to as the positive plate and the negative plate that form on the core body of tabular collector body; And the housing that is used to seal these two battery lead plates, described core body is characterised in that, is formed with the nickel alloy coating that disperse has graphite on sheet metal.
(3) a kind of battery that uses the core body of alkaline battery, this battery comprises: active material is sticked to as the positive plate and the negative plate that form on the core body of tabular collector body; And the housing that is used to seal these two battery lead plates, described core body is characterised in that, is formed with the nickel coating that disperse has graphite on sheet metal.
(4) a kind of battery that uses the core body of alkaline battery, this battery comprises: active material is sticked to as the positive plate and the negative plate that form on the core body of tabular collector body; And the housing that is used to seal these two battery lead plates, described core body is characterised in that, is formed with the nickel alloy coating that disperse has graphite on sheet metal.
Embodiment
The preparation mild steel plate, and carry out disperse thereon and have the nickel of graphite or nickel alloy that disperse has graphite to electroplate, so that form the core body of alkaline battery.Form positive plate by coating hydroxide slurry material on core body.The slurry that comprises hydrogen adsorbing alloy by coating on another core body forms negative plate.The present invention will be described in detail below.
[used steel plate]
Common cold-rolled steel sheet especially contains the al-killed continuously casting steel of low-carbon (LC), as according to steel plate of the present invention.Can use ultra-low carbon steel, interpolation niobium or the non-aging steel of titanium and the stainless steel of chromium content 3-18wt% of carbon content less than 0.003wt%.These steel plates can be bored a hole in advance.
[substrate nickel coating]
Preferably on steel plate, form nickel coating as surface treated steel plate.This nickel coating is called " substrate nickel ".The purpose of substrate nickel is to keep enough corrosion resistancies after steel plate forms core body.
For substrate nickel electroplating bath, can use generally to be used for the groove that nickel is electroplated, as Watt groove, sulfonamides groove, fluoric acid salt bath or chloride groove.Nickel is electroplate with electroplates type and electroless-plating type.Although the electroless-plating type also can be used, it also is more useful electroplating type energy control flume condition and thickness of coating.Under the situation of electroplating type, preferred current density is 3-80A/dm
2And comprise air is blown into air agitator step in the groove, so that form uniform electrodeposited coating.In this groove, the pH value is 40-60 ℃ in acidic region and the temperature of 3.5-5.5 preferably.
For the plating of substrate nickel, can use the tarnish of not using organic additive and electroplate, reach semi-glossy plating or the gloss plating of using organic additive.The thickness of nickel coating is preferably 0.5-5 μ m.
If the thickness of nickel coating is less than 0.5 μ m, the coating on the steel plate is not enough to provide the outstanding corrosion resistance as the substrate nickel coating.If the thickness of nickel coating is greater than 5 μ m, the effect of substrate nickel coating is saturated aspect corrosion resistance, and is disadvantageous on price.Thereby preferably on two surfaces of steel plate, form the substrate nickel coating and have essential corrosion resistance.The thickness of nickel coating is preferably 0.5-5 μ m.
[diffusion layer]
Except the substrate nickel coating, preferably after heat treatment, on the integral body of substrate nickel coating or part, form diffusion layer, peel off from base steel plates to prevent nickel coating.
The heat treatment of carrying out with anaerobic voltinism or restitutive protection's gas is preferred, to avoid forming oxide skin(coating) on the surface of diffusion layer.For nonoxidizing gas, be preferred such as the inactive gas of nitrogen, argon gas, helium etc.On the other hand, the reducibility gas such as hydrogen, ammonia pyrolysis gas body (hydrogen 75%, nitrogen 25%) is preferred.For heat treatment, can use box method for annealing or continuous annealing method.In box method for annealing, soaking temperature preferably is equal to or greater than 450 ℃ in heat treatment.For the processing time, temperature retention time is relatively short and be relatively long in box method for annealing in continuous annealing method.Generally speaking, temperature retention time in continuous annealing method be 30 seconds-2 minutes and in box method for annealing for 6-15 hour.
[forming nickel (alloy) coating that disperse has graphite]
For disperse the nickel electroplating bath of graphite is arranged, the alloy groove (forming the nickel alloy coating that disperse has graphite) of considering to adopt the nickel electroplating bath (forming the nickel coating that disperse has graphite) that contains disperse graphite or containing disperse graphite and comprise nickel and other metal such as cobalt, manganese, iron, phosphorus.By the graphite as high conductive agent is added into electroplating bath, form the coating that disperse has graphite.Convex precipitation in the coating plays the anchoring effect that is used for fixing active material in the battery.
Native graphite and electrographite all might be as being used for graphite of the present invention.The preferred fine-grain graphite that uses, its 50% accumulative total particle diameter is equal to or less than 10 μ m and preferably is equal to or less than 5 μ m.Compare with the thickness of coating, if particle diameter is relatively large, the graphite that is adhered to just is removed easily.
Graphon also is preferred.Graphon is the graphitization product of carbon black.Average grain diameter is very small, for example is about 0.1 μ m or littler.
Because graphite surface is hydrophobic, even graphite also is not easy disperse when tank diameter.Therefore, preferably use interfacial agent (graphite disperse means) to force disperse.For the graphite disperse means, the activating agent of any kind of, for example cationic systems agent, anion systematization agent, nonionic systematization agent or hybrid system agent all can be used.Consider the outstanding adhesiveness between electroplating steel plate and the coating and the embrittlement image of coating, preferably such as the cation interfacial active agent of benzene sulfonic acid or the agent of sulfuric ester system activity, for example, conducts such as preferred alkyl sodium sulphate, 12 silicon sodium sulphate, olefinic sodium sulphate, alkyl naphthalene sodium sulphate, dialkyl group sodium 2-sulfo-succinic acid are according to graphite disperse means of the present invention.
At the diffusion method that is used for fine-grain graphite is delivered into electroplating bath, powdered graphite with mix with the water-reducible graphite disperse means of scheduled volume, use emulsifier or ultrasonic cleaner to carry out disperse at last such as homogenizer.In the method, preferred graphite granule is got wet so that carry out disperse with a spot of alcohol etc.After the good graphite of disperse, in electroplating bath, add graphite and stir.The content of disperse means is 5-10wt% with respect to graphite.The ultimate density of graphite in electroplating bath preferably is controlled in the scope of 1-100g/L.If concentration is less than 1g/L, the content of graphite in coating is not enough to show anchoring effect.If concentration is greater than 100g/L, the flowability of electroplating bath becomes even worse, and produces various troubles because of powdered graphite adheres to electroplating device.Bonding for preventing graphite granule, in electroplating bath, add the disperse means of 2-10ml/L in advance.
The electroplating bath that contains disperse graphite circulates with pump, thereby makes the bottom of electroplating bath obtain circulation, and is blown into air by the opening portion that is arranged on the electrolyte tank bottom and stirs.If correctly keep the disperse condition, the graphite of 0.1-25wt%, the graphite of preferred 1-10wt% can be delivered in the coating.If the content of graphite of wishing to increase in the coating has the coating of graphite to form disperse, just preferably reduce current density.
Example of the present invention is below described.
[example 1]
Thickness be 60 μ m through annealing and stable cold-rolled steel sheet with the steel plate that acts on plating.This steel plate carries out anode treatment (5A/dm under 75 ℃ in the solution that contains 30g/L NaOH
2* 10 seconds) and cathode treatment (5A/dm
2* 10 seconds) to carry out degreasing.Then, this steel plate was immersed in the solution that comprises 50g/L sulfuric acid 15 seconds, to carry out pickling.Under following condition, use Watt groove with air agitator, this steel plate is carried out nickel electroplate, thereby form the substrate nickel coating.For anode, use the nickel rondelle that is inserted in the titanium cage that links to each other with Polypropylene Bag.The control electroplating time is to form the coating of 2.0 μ m.
[the plating condition of substrate nickel]
[groove composition]
Nickelous sulfate 300g/L
Nickel chloride 55g/L
Boric acid 45g/L
[plating condition]
Groove temperature: 45 ± 2 ℃
pH： 4.2±0.2
Current density: 20A/dm
2
Then, in atmosphere (nitrogen 94%, hydrogen 6%), under 550 ℃, substrate nickel electroplating steel plate is carried out heat diffusion treatment and reach 8 hours.Measuring the Ni-Fe thickness of diffusion layer of having handled with the glow discharge emission spectrometer is 2.6 μ m.
[temper rolling]
The thermal diffusion steel plate is carried out temper rolling to prevent stretcher strain.
[disperse has the nickel of graphite to electroplate]
And then under following condition, carrying out disperse in disperse has the nickel groove of graphite has the nickel of graphite to electroplate.Also there is the nickel groove of graphite to carry out air stirring to disperse.Identical when anode is electroplated with substrate nickel with the cathode treatment condition.For disperse the nickel electroplating processes of graphite is arranged, the content of graphite of disperse changes by control electroplating time and the content of graphite that adds in the electroplating bath in coating.
[disperse has the nickel of graphite to electroplate condition]
[groove composition]
Nickelous sulfate 300g/L
Nickel chloride 45g/L
Boric acid 45g/L
Graphite 1g/L
Disperse means 5ml/L
Remove to cheat agent (lauryl sodium sulfate) 2.0ml/L
[plating condition]
Groove temperature: 60 ± 2 ℃
pH： 4.3±0.2
Current density: 15A/dm
2
[method of disperse graphite in groove]
The method of disperse graphite is as described below in groove.4ml dilutes with the 1L softened water at commercially available benzene sulfonic acid sodium salt (graphite disperse means).The 1kg micro powder graphite is mixed into the solution (mixing material) that has diluted.For improving the flowability of mixing material, add the 1L softened water again.By using the ultrasonic dispersion device, fully mix liquid.For micro powder graphite, use the micro powder graphite ASSP (50% accumulative total diameter is 6 μ m) that makes by Japanese graphite Industrial Co., Ltd.
By viewgraph of cross-section, can see that graphite is fully by disperse with the sem observation electroplate.Further, the content of graphite in the coating is measured (JIS G1211) with the infrared ray absorbing method.
Relation between the content of graphite in the coating that content of graphite that is added in the observation electroplating bath and disperse have graphite can find out that the addition of disperse means is under the situation of constant in electroplating bath, and both are the relations that are directly proportional.That is to say, be 5-100g/L with respect to the addition of graphite in the electroplating bath, and it is 0.1-2.5% that disperse has the content of graphite in the coating of graphite.
Before disperse means content reached 10ml/L, the addition of disperse means and disperse had the content of graphite in the coating of graphite to be directly proportional.If disperse means content is greater than 10ml/L, disperse has the content of graphite in the coating of graphite just saturated.
[example 2-6]
Under the condition identical with embodiment 1, thickness, disperse means addition and the disperse of the thickness by changing the substrate nickel coating, the nickel coating that disperse has graphite has the content of graphite in the coating of graphite, prepares several surface treated steel plates.
Produce core body by the steel plate of having handled being carried out the processing similar to example 1.Then, on core body, apply active material.The character of each core body and the measurement result of characteristic are shown in the table 1.
[example 7]
Thickness is the extremely low al-killed cold-rolled steel sheet of the carbon content of the 100 μ m steel plate that acts on plating.Steel plate is carried out degreasing, pickling and substrate nickel electroplating processes.
After substrate nickel was electroplated, the recrystallization annealing of steel plate and the heat diffusion treatment of nickel coating were handled in continuous annealing furnace simultaneously.In the atmosphere identical, under 780 ℃, annealed 1 minute with example 1.The diffusion thickness of measuring Fe-Ni alloy coating with the glow discharge emission spectrometer is 2.8 μ m.After annealing and stabilisation calendering, carrying out disperse under following condition has the nickel-cobalt of graphite-the ferroalloy plating.And in electroplating bath, also carry out air stirring.Anode is identical with the condition that cathode treatment condition and substrate nickel are electroplated.The method of disperse graphite is similar to example 1.
[groove composition]
Nickelous sulfate 300g/L
Nickel chloride 45g/L
Boric acid 45g/L
Cobaltous sulfate 5g/L
Ferric sulfate 5g/L
Graphite 30g/L
Disperse means 5ml/L
[plating condition]
Groove temperature: 60 ± 2 ℃
pH： 4.3±0.2
Current density: 15A/dm
2
By disperse the alloy plating of graphite is arranged, obtain the nickel alloy coating that disperse has graphite, wherein cobalt content is 2.3wt%, and iron content is 1wt%, and content of graphite is 0.7wt%.
On the steel plate of having handled, apply active material, form the core body similar to example 1.Its character and characteristic are shown in the table 1.
[example 8]
With example 1 similarly, be that the steel plate of 60 μ m carries out degreasing, pickling and substrate nickel and electroplates to thickness.After substrate nickel is electroplated, under the condition identical, carry out DIFFUSION TREATMENT with example 1.After carrying out stabilisation calendering processing, carrying out disperse under following condition has the nickel of graphite-the manganese alloy plating.And in electroplating bath, also carry out air stirring.Anode is identical with the condition that cathode treatment condition and substrate nickel are electroplated.The method of disperse graphite is identical with example 1.
[groove composition]
Sulfonamides nickel 280g/L
Nickel chloride 5g/L
Boric acid 33g/L
Manganese sulfate 15g/L
Graphite 40g/L
Disperse means 10ml/L
Remove to cheat agent 2.0ml/L
[plating condition]
Groove temperature: 60 ± 2 ℃
pH： 4.0±0.2
Current density: 10A/dm
2
By disperse the alloy plating of graphite is arranged, obtain the nickel alloy coating that disperse has graphite, wherein manganese content is 0.7wt%, and content of graphite is 10wt%.
On the steel plate of having handled, apply active material, form the core body similar to example 1.Its character and characteristic are shown in the table 1.
[example 9]
With example 1 similarly, be that the steel plate of 60 μ m carries out degreasing, pickling and substrate nickel and electroplates to thickness.After substrate nickel is electroplated, under the condition identical, carry out DIFFUSION TREATMENT with example 1.After carrying out stabilisation calendering processing, carrying out disperse under following condition has the nickel-phosphor alloy of graphite to electroplate.And in electroplating bath, also carry out air stirring.Anode is identical with the condition that cathode treatment condition and substrate nickel are electroplated.The method of disperse graphite is identical with example 1.
[groove composition]
Sulfonamides nickel 280g/L
Nickel chloride 45g/L
Boric acid 45g/L
Phosphoric acid 5g/L
Graphite 15g/L
Disperse means 4ml/L
[plating condition]
Groove temperature: 65 ± 2 ℃
pH： 1.2±0.2
Current density: 15A/dm
2
By disperse the composite plating of graphite is arranged, obtain the nickel alloy coating that disperse has graphite, wherein phosphorus content is 2wt%, and content of graphite is 0.3wt%.
On the steel plate of having handled, apply active material, form the core body similar to example 1.Its character and characteristic are shown in the table 1.
[example 10]
With example 1 similarly, be that the steel plate of 60 μ m carries out degreasing, pickling and substrate nickel and electroplates to thickness.After substrate nickel is electroplated, under the condition identical, carry out DIFFUSION TREATMENT with example 1.After carrying out stabilisation calendering processing, carrying out disperse under following condition has the nickel of graphite-the bismuth alloy plating.And in electroplating bath, also carry out air stirring.Anode is identical with the condition that cathode treatment condition and substrate nickel are electroplated.The method of disperse graphite is identical with example 1.
[groove composition]
Nickelous sulfate 240g/L
Bismuth sulfate 1g/L
EDTA-2Na 20g/L
Disperse means 5ml/L
Graphite 20g/L
Remove to cheat agent 2.0ml/L
[plating condition]
Groove temperature: 45 ± 2 ℃
pH： 1.5
Current density: 10A/dm
2
By disperse the alloy plating of graphite is arranged, obtain the nickel alloy coating that disperse has graphite, wherein bi content is 4wt%, and content of graphite is 0.5wt%.
On the steel plate of having handled, apply active material, form the core body similar to example 1.Its character and characteristic are shown in the table 1.
[comparative example 1]
With example 1 similarly, be that the steel plate of 60 μ m carries out degreasing, pickling and substrate nickel and electroplates to thickness.After substrate nickel is electroplated, under the condition identical, carry out heat diffusion treatment with above-mentioned example.After temper rolling, carry out re-plating with nickel.
Steel plate character and battery behavior in above-mentioned example and the comparative example are measured with following method.
(1) content of graphite in the coating
Use is according to the infrared ray absorbing method of JIS-G-1211.By the difference between the carbon content in the steel plate that calculates carbon content and 1g in the 1g electroplate and do not have plating, determine that disperse has the content of graphite (wt%) in the coating of graphite.Graphite granule 50% accumulative total diameter is measured with laser diffraction distribution of particles measuring instrument.
(2) ratio of surperficial protuberance
After carrying out disperse the plating of graphite arranged, use KEYENCE Co., the digital microscope VH-6300 that Ltd makes observes plate surface.Take pictures with 500 multiplying powers.The shared ratio of protuberance in the photograph is represented with percentage.
(3) experimental technique of active material retentivity
In anode, be thirty minutes long on the surface that is coated in core body under 80 ℃ with applicator such as the active material of 4% carboxy methyl cellulose solution (50 parts of weight), nickel hydroxide (100 parts of weight) and acrylonitrile-styrol copolymer (5 parts of weight).After the oven dry core body, the bed thickness of a side surface is about 300 μ m (both sides are totally 600 μ m).
In negative pole, comprise carboxy methyl cellulose (50 parts of weight), particle diameter less than 200 purpose hydrogen adsorbing alloy LmNi
4.0Co
0.4Mn
0.4Al
0.5, nickel powder (by INCO Co., Ltd make 255) active material of (100 parts of weight) and acrylonitrile-styrol copolymer (5 parts of weight), be coated on the core body under 80 ℃ with applicator and be thirty minutes long.After the oven dry core body, the bed thickness of a side surface is about 300 μ m (both sides are totally 600 μ m).
After oven dry, the thickness of anodal and negative pole is compressed to 400 μ m by roll extrusion.
The battery lead plate that is coated with active material is immersed under 60 ℃ in the 6.3mol KOH solution and reaches 10 days.After this, with the naked eye estimate its fixedly character of active material.If removed active material ratio is less than 10%, this evaluation is represented with zero so.If ratio is 10-20%, estimates and just represent with △.If ratio surpasses 20%, estimate just usefulness * expression.Evaluation result is shown in the table 1.
[table 1] plating condition and handled the characteristic of steel plate
| Example or comparative example | Substrate nickel coating (μ m) | Disperse has the plating of graphite | Characteristic | ||||
| The electroplating bath kind | Content of graphite (wt%) | Thickness of coating (μ m) | The area of surface protuberance compares % | The retentivity of active material | |||
| Anodal | Negative pole | ||||||
| Example 1 | 2.0 | Nickel is electroplated | 0.03 | 0.5 | 0.3 | △ | △ |
| Example 2 | 2.1 | Nickel is electroplated | 0.5 | 1.1 | 10 | ○ | ○ |
| Example 3 | 1.1 | Nickel is electroplated | 1.3 | 1.6 | 37 | ○ | ○ |
| Example 4 | 1.0 | Nickel is electroplated | 2.4 | 2.2 | 67 | ○ | ○ |
| Example 5 | 2.5 | Nickel is electroplated | 0.3 | 2.1 | 11 | ○ | ○ |
| Example 6 | 2.5 | Nickel is electroplated | 0.4 | 2.0 | 14 | ○ | ○ |
| Example 7 | 2.9 | Ni-Co-Fe electroplates | 0.7 | 1.5 | 19 | ○ | ○ |
| Example 8 | 2.0 | Ni-Mn electroplates | 10.0 | 1.6 | 29 | ○ | ○ |
| Example 9 | 1.9 | Ni-P electroplates | 0.3 | 1.5 | 8 | ○ | ○ |
| Example 10 | 1.9 | Ni-Bi electroplates | 0.5 | 1.5 | 28 | ○ | ○ |
| Comparative example 1 | 2.0 | Nickel is electroplated (re-plating) | - | 1.2 | 0 | × | × |
Can judge that from The above results the core body that is carried out the making of surface-treated steel plate by the nickel coating that graphite is arranged with disperse has convex-concave surface, so core body has the character of good fixedly active material.
The present invention is different with conventional nickel coating.The present invention comprises the layer that nickel and disperse have graphite, thereby because of forming concavo-convex surface, fixedly the character of active material is very good thereby make it.
Claims (8)
1. core body that is used for alkaline battery, wherein, this battery comprises: active material is sticked to as the positive plate and the negative plate that form on the core body of tabular collector body; And the housing that is used to seal these two battery lead plates, described core body is characterised in that, is formed with the nickel coating that disperse has graphite on sheet metal.
2. core body that is used for alkaline battery, wherein, this battery comprises: active material is sticked to as the positive plate and the negative plate that form on the core body of tabular collector body; And the housing that is used to seal these two battery lead plates, described core body is characterised in that, is formed with the nickel alloy coating that disperse has graphite on sheet metal.
3. the core body that is used for alkaline battery as claimed in claim 2, wherein, described alloy layer is a kind of in nickel-cobalt alloy layer, nickel-cobalt-iron alloy layer, nickel-manganese alloy layer, nickel-phosphor alloy layer or the nickel-bismuth alloy layer.
4. as each described core body that is used for alkaline battery among the claim 1-3, wherein, in the lower floor of described coating, form diffusion layer.
5. as each described core body that is used for alkaline battery among the claim 1-3, wherein, in the lower floor of described coating, form nickel dam.
6. as each described core body that is used for alkaline battery among the claim 1-3, wherein, content of graphite is 0.3-10wt%.
7. battery that uses the core body of alkaline battery, this battery comprises: active material is sticked to as the positive plate and the negative plate that form on the core body of tabular collector body; And the housing that is used to seal these two battery lead plates, described core body is characterised in that, is formed with the nickel coating that disperse has graphite on sheet metal.
8. battery that uses the core body of alkaline battery, this battery comprises: active material is sticked to as the positive plate and the negative plate that form on the core body of tabular collector body; And the housing that is used to seal these two battery lead plates, described core body is characterised in that, is formed with the nickel alloy coating that disperse has graphite on sheet metal.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20499 | 1999-01-04 | ||
| JP204/1999 | 1999-01-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1332890A CN1332890A (en) | 2002-01-23 |
| CN1163993C true CN1163993C (en) | 2004-08-25 |
Family
ID=11467458
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB998154083A Expired - Fee Related CN1163993C (en) | 1999-01-04 | 1999-12-24 | Core of alkali storage battery and battery using the core |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP4386230B2 (en) |
| CN (1) | CN1163993C (en) |
| AU (1) | AU1799600A (en) |
| MY (1) | MY128343A (en) |
| TW (1) | TW521453B (en) |
| WO (1) | WO2000041259A1 (en) |
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|---|---|---|---|---|
| CN117121229A (en) * | 2021-04-20 | 2023-11-24 | 松下知识产权经营株式会社 | Method for manufacturing battery and electrode |
| EP4329007A1 (en) * | 2021-04-20 | 2024-02-28 | Panasonic Intellectual Property Management Co., Ltd. | Battery |
| CN117121230A (en) * | 2021-04-20 | 2023-11-24 | 松下知识产权经营株式会社 | Method for manufacturing battery and electrode |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05182670A (en) * | 1991-12-27 | 1993-07-23 | Sanyo Electric Co Ltd | Electrode for battery |
| JP3395440B2 (en) * | 1995-04-04 | 2003-04-14 | 松下電器産業株式会社 | Air electrode current collecting material for air battery and air battery provided with the same |
-
1999
- 1999-12-24 CN CNB998154083A patent/CN1163993C/en not_active Expired - Fee Related
- 1999-12-24 WO PCT/JP1999/007268 patent/WO2000041259A1/en active Application Filing
- 1999-12-24 AU AU17996/00A patent/AU1799600A/en not_active Abandoned
- 1999-12-24 JP JP2000592897A patent/JP4386230B2/en not_active Expired - Fee Related
- 1999-12-31 MY MYPI99005814A patent/MY128343A/en unknown
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| WO2000041259A1 (en) | 2000-07-13 |
| AU1799600A (en) | 2000-07-24 |
| TW521453B (en) | 2003-02-21 |
| JP4386230B2 (en) | 2009-12-16 |
| MY128343A (en) | 2007-01-31 |
| CN1332890A (en) | 2002-01-23 |
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