WO2013005774A1 - 電池容器用表面処理鋼板およびその製造方法、電池容器および電池 - Google Patents
電池容器用表面処理鋼板およびその製造方法、電池容器および電池 Download PDFInfo
- Publication number
- WO2013005774A1 WO2013005774A1 PCT/JP2012/067094 JP2012067094W WO2013005774A1 WO 2013005774 A1 WO2013005774 A1 WO 2013005774A1 JP 2012067094 W JP2012067094 W JP 2012067094W WO 2013005774 A1 WO2013005774 A1 WO 2013005774A1
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- WIPO (PCT)
- Prior art keywords
- nickel
- cobalt alloy
- battery
- steel sheet
- alloy layer
- Prior art date
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 74
- 239000010959 steel Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title description 11
- 229910000531 Co alloy Inorganic materials 0.000 claims abstract description 110
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 105
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 22
- 238000007747 plating Methods 0.000 claims description 70
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 69
- 229910052759 nickel Inorganic materials 0.000 claims description 34
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 230000005855 radiation Effects 0.000 claims description 9
- 238000009792 diffusion process Methods 0.000 claims description 6
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000000052 comparative effect Effects 0.000 description 19
- 239000000203 mixture Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 238000000137 annealing Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 239000004327 boric acid Substances 0.000 description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 5
- 229940044175 cobalt sulfate Drugs 0.000 description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000012611 container material Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 3
- 229910017709 Ni Co Inorganic materials 0.000 description 3
- 229910003267 Ni-Co Inorganic materials 0.000 description 3
- 229910003262 Ni‐Co Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910016523 CuKa Inorganic materials 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 2
- 229910000655 Killed steel Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000010409 ironing Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- -1 nickel metal hydride Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000010731 rolling oil Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
- B32B15/015—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium the said other metal being copper or nickel or an alloy thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/02—Heating or cooling
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M50/117—Inorganic material
- H01M50/119—Metals
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M50/1245—Primary casings; Jackets or wrappings characterised by the material having a layered structure characterised by the external coating on the casing
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
-
- 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
- H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
- H01M50/133—Thickness
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
- H01M50/134—Hardness
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
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- C22C19/03—Alloys based on nickel or cobalt based on nickel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/02—Electroplating of selected surface areas
- C25D5/028—Electroplating of selected surface areas one side electroplating, e.g. substrate conveyed in a bath with inhibited background plating
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
- C25D5/611—Smooth layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/615—Microstructure of the layers, e.g. mixed structure
- C25D5/617—Crystalline layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a surface-treated steel sheet for battery containers, a battery container using the surface-treated steel sheet for battery containers, and a battery using the battery container.
- alkaline batteries that are primary batteries, nickel-hydrogen batteries that are secondary batteries, lithium ion batteries, and the like are frequently used as operating power sources.
- These batteries are required to have high performance such as high output and long life, and battery containers filled with power generation elements composed of a positive electrode active material, a negative electrode active material, and the like are also important battery components. There is a need for improved performance.
- Patent Document 1 a battery container material formed by forming nickel alloy plating on both surfaces of a steel plate, and the hardness of the plating layer serving as the battery container inner surface is defined as A battery container material that is set to be higher than the hardness of the plating layer is disclosed.
- Patent Document 1 the effect of improving battery characteristics, in particular, the effect of reducing internal resistance, when the conductive film is not formed is not always sufficient, and therefore further improvement has been demanded.
- the present inventors have formed a nickel-cobalt alloy layer on the outermost surface of the battery container, and the crystal orientation of the nickel-cobalt alloy layer is set to a predetermined value.
- the inventors have found that the above-described object can be achieved by controlling to a range, and have completed the present invention.
- a surface-treated steel sheet for a battery container having a nickel-cobalt alloy layer formed on the outermost surface of the battery container, the CuK ⁇ of the nickel-cobalt alloy layer being a radiation source. and by X-ray diffraction measurement of the diffraction angle 2 ⁇ is 41 ° or more, and the intensity I a of the peak present in the range of less than 43 °, the diffraction angle 2 ⁇ is 43 ° or more, the intensity of the peaks present in the range of 45 ° or less surface treated steel sheet for battery container, characterized in that the ratio of the I B intensity ratio I a / I B is in the range of 0.01 to 0.9 is provided.
- the surface-treated steel sheet for battery containers of the present invention preferably has a nickel layer as a lower layer of the nickel-cobalt alloy layer.
- the surface-treated steel sheet for battery containers of the present invention preferably has an iron-nickel diffusion layer between the nickel-cobalt alloy layer and the steel sheet.
- molding one of the said surface-treated steel sheets for battery containers is provided.
- the battery which uses the said battery container is provided.
- a method for producing a surface-treated steel sheet for a battery container wherein a nickel-cobalt alloy layer is formed on the outermost surface of the battery container, the nickel-cobalt alloy layer being And alloy plating using a nickel-cobalt alloy plating bath having a cobalt / nickel molar ratio of 0.01 to 2.4 under conditions of a bath temperature of 60 to 80 ° C. and a current density of 15 to 40 A / dm 2 .
- a method for producing a surface-treated steel sheet for battery containers is provided.
- a conductive film is formed by forming a nickel-cobalt alloy layer on the outermost surface of the battery container and controlling the crystal orientation of the nickel-cobalt alloy layer within a predetermined range. Even when it is not formed, it is possible to provide a surface-treated steel sheet for battery containers capable of improving battery characteristics, and a battery container and a battery obtained using the surface-treated steel sheet for battery containers.
- FIG. 1 is a diagram showing the results of X-ray diffraction measurement using CuK ⁇ of a nickel-cobalt alloy layer as a radiation source in an example of the present invention.
- the surface-treated steel sheet for battery containers according to the present invention is a surface-treated steel sheet for battery containers in which a nickel-cobalt alloy layer is formed on the outermost surface of the battery container, and the nickel-cobalt alloy layer.
- the X-ray diffraction measurement that the a radiation source CuKa, the diffraction angle 2 ⁇ is 41 ° or more, and the intensity I a of the peak present in the range of less than 43 °, the diffraction angle 2 ⁇ is 43 ° or more, in the range of 45 ° or less is the ratio between the intensity I B of a peak present intensity ratio I a / I B is characterized in that in the range of from 0.01 to 0.9.
- any steel sheet may be used as long as it is excellent in drawing workability, drawing ironing workability, workability by drawing and bending back work (DTR).
- DTR drawing and bending back work
- low carbon aluminum killed steel carbon content 0.01 to 0.15 wt%
- ultra low carbon steel having a carbon content of 0.003 wt% or less
- ultra low carbon steel and Ti or Nb It is possible to use a non-aging ultra-low carbon steel made by adding
- these steel hot-rolled plates are pickled to remove the surface scale (oxide film), then cold-rolled, then electrolytically washed with rolling oil, and then annealed and temper-rolled.
- a thing is used as a substrate.
- the annealing may be either continuous annealing or box annealing, and is not particularly limited.
- the surface-treated steel sheet for battery containers of the present invention is formed by forming a nickel-cobalt alloy layer on the outermost surface that is the inner surface of the battery container.
- Nickel - cobalt alloy layer by X-ray diffraction measurement as a radiation source a CuKa, diffraction angle 2 ⁇ is 41 ° or more, and the intensity I A of the peak present in the range of less than 43 °, the diffraction angle 2 ⁇ is 43 ° or more, is the ratio between the intensity I B of a peak present in the range of 45 ° or less intensity ratio I a / I B is in the range 0.01 to 0.9 and preferably in the range of 0.01-0.4 Is.
- nickel - by the intensity ratio I A / I B of CuK ⁇ cobalt alloy layer by X-ray diffraction measurement of a radiation source is controlled in the above range, the battery container for surface treated steel sheet of the present invention, a nickel -When used as a battery container having a cobalt alloy layer as an inner surface, even when a conductive film is not formed, the battery characteristics can be improved, and particularly an increase in internal resistance after time can be effectively suppressed. Can do.
- the intensity ratio I A / I B by controlling the above range, nickel - cobalt alloy layer can be made to have a sufficient hardness.
- the plating condition is set to a bath temperature exceeding 80 ° C. or 40 A / dm 2 . It is necessary to make the current density higher, and these conditions may cause problems such as poor appearance as described later. On the other hand, if it is too large, the effect of improving the hardness of the nickel-cobalt alloy layer is insufficient. As a result, it is difficult to obtain the effect of improving battery characteristics.
- the intensity ratio I A / I B by X-ray diffraction measurement using CuK ⁇ of the nickel-cobalt alloy layer as a radiation source can be measured, for example, by the following method. That is, first, X-ray diffraction measurement of the nickel-cobalt alloy layer is performed under the conditions of X-ray source: Cu-40 kV, 200 mA, divergence slit: 2 °, scattering slit: 1 °, and light-receiving slit: 0.3 mm.
- the method of forming the nickel-cobalt alloy layer is not particularly limited.
- a nickel-cobalt alloy plating bath having a cobalt / nickel ratio in a predetermined range is used to plate the surface of the steel plate with the nickel-cobalt alloy plating.
- the method of forming a layer is mentioned.
- the nickel-cobalt alloy plating bath used for forming the nickel-cobalt alloy layer a plating bath based on a watt bath containing nickel sulfate, nickel chloride, cobalt sulfate and boric acid is preferably used.
- the cobalt / nickel ratio in the plating bath is preferably in the range of 0.01 to 2.4, more preferably in the range of 0.1 to 0.7, as the molar ratio of cobalt / nickel. preferable.
- nickel sulfate 10 to 300 g / L
- nickel chloride 20 to 60 g / L
- boric acid 10 to 40 g / L
- bath temperature and current density of the plating bath when performing nickel-cobalt alloy plating are preferably set as follows.
- Bath temperature preferably 60-80 ° C, more preferably 65-75 ° C
- Current density preferably 15 to 40 A / dm 2 , more preferably 15 to 30 A / dm 2 , still more preferably 20 to 30 A / dm 2
- the bath temperature and current density of the plating bath during the nickel-cobalt alloy plating to the above specific range, X-ray diffraction measurement using CuK ⁇ of the nickel-cobalt alloy layer as a radiation source is performed.
- the intensity ratio I A / I B can be set to the predetermined range described above.
- the bath temperature is less than 60 ° C.
- a sufficient amount of cobalt does not enter the plating film composition in the plating film, and a nickel-cobalt alloy layer having a desired composition cannot be obtained.
- the conductivity of the nickel-cobalt alloy layer to be produced is lowered.
- the bath temperature exceeds 80 ° C., evaporation of the plating bath becomes significant, and the concentration of the plating bath changes due to evaporation, making it difficult to control the plating.
- the resulting nickel-cobalt alloy layer has low hardness.
- the current density exceeds 40 A / dm 2 , the appearance of the resulting nickel-cobalt alloy layer is deteriorated, and furthermore, cobalt is unevenly contained in the obtained nickel-cobalt alloy layer. As a result, the conductivity of the resulting nickel-cobalt alloy layer is lowered.
- 30A / dm 2 of less than ultra-40A / dm 2 for control over the management of the bath temperature is somewhat difficult, 30A / dm 2 or less is more preferable.
- the bath temperature and current density of the plating bath at the time of nickel-cobalt alloy plating may be within the above ranges, but when the bath temperature of the plating bath is 60 ° C. or higher and lower than 65 ° C., the current density is A relatively high value in the range of 15 to 40 A / dm 2 is preferable.
- the pH of the plating bath is preferably 1.5 to 5.0, more preferably 3.0 to 5.0.
- the base nickel plating may be performed to form the base nickel plating layer.
- the underlying nickel plating layer can be formed using a Watt bath that is usually used, and the thickness thereof is preferably 0.05 to 3.0 ⁇ m, more preferably 0.1 to 2.0 ⁇ m.
- the surface-treated steel sheet for battery containers according to the present invention has a nickel layer and a nickel-cobalt alloy layer (Ni—Co / Ni / Fe) on the steel plate in order from the bottom. be able to.
- the thickness of the nickel-cobalt alloy layer is preferably 0.01 to 2.0 ⁇ m, more preferably 0.05, when the base nickel layer is not formed. ⁇ 1.0 ⁇ m.
- the thickness of the nickel-cobalt alloy layer is preferably 0.01 to 1.0 ⁇ m, more preferably 0.05 to 0.4 ⁇ m. If the nickel-cobalt alloy layer is too thin, sufficient battery characteristics may not be obtained. On the other hand, if the nickel-cobalt alloy layer is too thick, the capacity may increase when the battery can be formed or the battery can is formed.
- the heat treatment is performed after the formation of the base nickel plating layer and before the nickel-cobalt alloy plating. What performed the process to make it diffuse may be used.
- the heat treatment may be performed by either a continuous annealing method or a box annealing method, and the heat treatment conditions may be appropriately selected according to the thickness of the underlying nickel plating layer.
- the heat treatment temperature is preferably 600 to 900 ° C. and the heat treatment time is preferably 3 to 120 seconds.
- the heat treatment temperature is 400 to 700 ° C.
- heat treatment atmosphere non-oxidizing atmosphere or reducing protective gas atmosphere
- heat treatment atmosphere non-oxidizing atmosphere or reducing protective gas atmosphere
- a protective gas composed of 75% hydrogen-25% nitrogen generated by an ammonia cracking method called hydrogen enriched annealing with good heat transfer is used as the protective gas. It is preferable to use it.
- the steel plate and the underlying nickel plating layer can be diffused, and an iron-nickel diffusion layer can be formed on the steel plate.
- the base nickel plating layer may be configured to completely diffuse with iron, or a part of the base nickel plating layer may be left without being diffused with iron. It is good also as such a structure.
- the surface-treated steel sheet for battery containers of the present invention is provided with an iron-nickel diffusion layer and a nickel-cobalt alloy layer in order from the bottom on the steel sheet.
- the structure (Ni—Co / Fe—Ni / Fe) can be obtained.
- the surface-treated steel sheet for battery containers according to the present invention has an iron-nickel diffusion layer, a nickel layer, and a nickel-cobalt alloy layer in order from the bottom on the steel sheet. (Ni—Co / Ni / Fe—Ni / Fe).
- the battery container of the present invention is obtained using the above-described surface-treated steel sheet for battery containers of the present invention.
- the battery container of the present invention is formed by drawing, ironing, DI or DTR forming the above-described surface-treated steel sheet for a battery container of the present invention so that the nickel-cobalt alloy layer is on the inner surface side of the container. .
- the battery container of the present invention is formed by using the above-described surface-treated steel sheet for battery containers of the present invention, even when a conductive film is not formed on the inner surface of the battery container, excellent low internal resistance and the like. Since battery characteristics can be realized, it can be suitably used as a battery container such as a battery using an alkaline electrolyte such as an alkaline battery or a nickel metal hydride battery, or a lithium ion battery.
- Example 1 As an original plate, a steel plate obtained by annealing a cold rolled plate (thickness 0.25 mm) of low carbon aluminum killed steel having the chemical composition shown below was prepared. C: 0.045 wt%, Mn: 0.23% wt, Si: 0.02 wt%, P: 0.012 wt%, S: 0.009 wt%, Al: 0.063 wt%, N: 0.0036% by weight, balance: Fe and inevitable impurities
- the prepared steel sheet was subjected to alkaline electrolytic degreasing and pickling with sulfuric acid, and then subjected to nickel-cobalt alloy plating under the following conditions to form a nickel-cobalt alloy layer having a thickness of 2 ⁇ m.
- a steel plate was obtained.
- the conditions for nickel-cobalt alloy plating were as follows. Bath composition: nickel sulfate, nickel chloride, cobalt sulfate, cobalt chloride, and boric acid in a cobalt / nickel molar ratio of 0.22 pH: 3.5-5.0 Bath temperature: 60 ° C Current density: 15 A / dm 2
- the intensity ratio I A / I B (I A is a diffraction angle 2 ⁇ of 41 ° or more and less than 43 ° in accordance with the following method. strength of existing peaks, I B went diffraction angle 2 ⁇ is 43 ° or more, the intensity of the peaks present in the range of 45 ° or less), and the measurement of the surface hardness.
- diffraction angle 2 ⁇ is 41 ° or more, and the intensity I A of the peak present in the range of less than 43 °, the diffraction angle 2 ⁇ is 43 ° or more, of 45 ° or less calculating the intensity I B of a peak present in the range, and calculate these ratios I a / I B.
- Table 1 The results are shown in Table 1.
- Example 2 Example 1 except that the current density of nickel-cobalt alloy plating at the time of forming the nickel-cobalt alloy layer was 20 A / dm 2 (Example 2) and 30 A / dm 2 (Example 3), respectively. Similarly, a surface-treated steel sheet was obtained and evaluated in the same manner. The results are shown in Table 1.
- Examples 4 to 6 In forming the nickel-cobalt alloy layer, the bath temperature of the nickel-cobalt alloy plating bath is set to 70 ° C., and the current density of the nickel-cobalt alloy plating is set to 15 A / dm 2 (Example 4), 20 A / A surface-treated steel sheet was obtained and evaluated in the same manner as in Example 1 except that dm 2 (Example 5) and 30 A / dm 2 (Example 6) were used. The results are shown in Table 1.
- Examples 7 to 9 In forming the nickel-cobalt alloy layer, the bath temperature of the nickel-cobalt alloy plating bath is set to 80 ° C., and the current density of the nickel-cobalt alloy plating is set to 15 A / dm 2 (Example 7), 20 A / A surface-treated steel sheet was obtained and evaluated in the same manner as in Example 1 except that dm 2 (Example 8) and 30 A / dm 2 (Example 9) were used. The results are shown in Table 1.
- Comparative Examples 1 and 2 >> Example 1 except that the current density of the nickel-cobalt alloy plating in the formation of the nickel-cobalt alloy layer was 5 A / dm 2 (Comparative Example 1) and 10 A / dm 2 (Comparative Example 2), respectively. Similarly, a surface-treated steel sheet was obtained and evaluated in the same manner. The results are shown in Table 1.
- Comparative Examples 3 and 4 When forming the nickel-cobalt alloy layer, the bath temperature of the nickel-cobalt alloy plating bath is 70 ° C., and the current density of the nickel-cobalt alloy plating is 5 A / dm 2 (Comparative Example 3), 10 A / A surface-treated steel sheet was obtained and evaluated in the same manner as in Example 1 except that dm 2 (Comparative Example 4) was used. The results are shown in Table 1.
- Comparative Examples 5 and 6 Like the nickel-cobalt alloy layer is formed, the bath temperature of the nickel-cobalt alloy plating bath is 80 ° C., and the current density of the nickel-cobalt alloy plating is 5 A / dm 2 (Comparative Example 5), 10 A / A surface-treated steel sheet was obtained and evaluated in the same manner as in Example 1, except that dm 2 (Comparative Example 6) was used. The results are shown in Table 1.
- Example 10 As the original plate, the same steel plate as in Example 1 was prepared. After the prepared steel plate was subjected to alkaline electrolytic degreasing and sulfuric acid immersion pickling, nickel plating was performed under the following conditions, and a nickel plating having a thickness of 1.0 ⁇ m. Then, nickel-cobalt alloy plating was performed under the following conditions, and a nickel-cobalt alloy layer having a thickness of 0.2 ⁇ m was formed on the nickel plating layer to obtain a surface-treated steel sheet.
- Bath composition nickel sulfate 250 g / L, nickel chloride 45 g / L, boric acid 30 g / L pH: 3.5-5.0 Bath temperature: 60 ° C Current density: 10 A / dm 2 ⁇ Nickel-cobalt alloy plating> Bath composition: nickel sulfate, nickel chloride, cobalt sulfate, cobalt chloride, and boric acid in a cobalt / nickel molar ratio of 0.22 pH: 3.5-5.0 Bath temperature: 60 ° C Current density: 20 A / dm 2
- a battery container was fabricated by molding into an LR6 type battery (AA battery) container.
- an alkaline manganese battery was produced as follows. That is, manganese dioxide and graphite were collected at a ratio of 10: 1, and potassium hydroxide (10 mol) was added and mixed to prepare a positive electrode mixture.
- the positive electrode mixture was pressed in a mold to form a donut-shaped positive electrode mixture pellet with a predetermined size, and was press-inserted into the battery container obtained above.
- the negative electrode plate spot-welded with the negative electrode current collector rod was attached to the battery container.
- a separator made of vinylon woven fabric is inserted along the inner circumference of the positive electrode mixture pellet inserted into the battery container, and a negative electrode gel made of potassium hydroxide saturated with zinc particles and zinc oxide is added to the battery.
- Example 10 a conductive film containing graphite powder as a main component was not formed on the inner surface of the battery container.
- the surface hardness of the nickel-cobalt alloy layer was measured in the same manner as in Example 1 using the surface-treated steel sheet obtained above. The results are shown in Table 2. Further, according to the following method, the surface roughness of the inner surface of the battery container was measured using the battery container obtained above, and the internal resistance IR was measured using the alkaline manganese battery obtained above. went.
- Examples 11 and 12 Except that the bath temperature of the nickel-cobalt alloy plating bath when forming the nickel-cobalt alloy layer in obtaining the surface-treated steel sheet was 70 ° C. (Example 11) and 80 ° C. (Example 12), respectively.
- Example 11 a surface-treated steel sheet, a battery container, and an alkaline manganese battery were produced and evaluated in the same manner as in Example 10. The results are shown in Table 2.
- Comparative Example 7 A surface-treated steel plate and a battery container were prepared in the same manner as in Example 10 except that the nickel-cobalt alloy layer was not formed when obtaining the surface-treated steel plate, and evaluation was performed in the same manner as in Example 10.
- an alkaline manganese battery was produced in the same manner as in Example 10 except that a conductive film mainly composed of graphite powder was formed on the inner surface of the battery container, and evaluation was performed in the same manner as in Example 10. It was. The results are shown in Table 2.
- Examples 10 to 12 in which the bath temperature of the plating bath during nickel-cobalt alloy plating was 60 to 80 ° C. and the current density was 15 to 40 A / dm 2 were As a result, the surface hardness of the surface-treated steel sheet is increased as compared with Comparative Example 7 in which the cobalt alloy layer was not formed. In addition, as a result, the surface roughness Ra of the battery inner surface after forming the battery container was increased. It became. In Examples 10 to 12, even when a conductive film mainly composed of graphite powder is not formed on the inner surface of the battery container, battery characteristics (internal resistance IR) superior to Comparative Example 7 in which the conductive film is formed are realized. It was confirmed that it was possible.
- internal resistance IR internal resistance
- the thickness of the nickel-cobalt alloy layer was thin. Therefore, the intensity ratio I A / I B was not measured by the X-ray diffraction measurement. From the results, it can be determined that in any of Examples 10 to 12, the intensity ratio I A / I B by X-ray diffraction measurement is in the range of 0.01 to 0.9. Similarly, in Comparative Example 8, a nickel - thin thickness of the cobalt alloy layer, therefore, it was not measured intensity ratio I A / I B by X-ray diffraction measurement, the results of Comparative Example 1 described above, It can be determined that the intensity ratio I A / I B by X-ray diffraction measurement exceeds 0.9.
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Abstract
Description
本発明の電池容器用表面処理鋼板において、好ましくは、前記ニッケル-コバルト合金層と鋼板との間に鉄-ニッケル拡散層を有する。
また、本発明によれば、上記電池容器を用いてなる電池が提供される。
本発明の電池容器用表面処理鋼板は、電池容器内面となる面の最表面に、ニッケル-コバルト合金層が形成されてなる電池容器用表面処理鋼板であって、かつ、該ニッケル-コバルト合金層のCuKαを線源とするX線回折測定による、回折角2θが41°以上、43°未満の範囲に存在するピークの強度IAと、回折角2θが43°以上、45°以下の範囲に存在するピークの強度IBとの比率である強度比IA/IBが0.01~0.9の範囲にあることを特徴とする。
本発明の電池容器用表面処理鋼板の基板となる鋼板としては、絞り加工性、絞りしごき加工性、絞り加工と曲げ戻し加工による加工(DTR)の加工性に優れているものであればよく特に限定されないが、たとえば、低炭素アルミキルド鋼(炭素量0.01~0.15重量%)、炭素量が0.003重量%以下の極低炭素鋼、または、極低炭素鋼にさらにTiやNbを添加してなる非時効性極低炭素鋼などからなるものを用いることができる。
本発明の電池容器用表面処理鋼板は、電池容器内面となる面の最表面に、ニッケル-コバルト合金層が形成されてなる。ニッケル-コバルト合金層は、CuKαを線源とするX線回折測定による、回折角2θが41°以上、43°未満の範囲に存在するピークの強度IAと、回折角2θが43°以上、45°以下の範囲に存在するピークの強度IBとの比率である強度比IA/IBが、0.01~0.9の範囲、好ましくは0.01~0.4の範囲にあるものである。
浴温:好ましくは60~80℃、より好ましくは65~75℃
電流密度:好ましくは15~40A/dm2、より好ましくは15~30A/dm2、さらに好ましくは20~30A/dm2
本発明の電池容器は、上述した本発明の電池容器用表面処理鋼板を用いて得られる。具体的には、本発明の電池容器は、上述した本発明の電池容器用表面処理鋼板を、絞り、しごき、DIまたはDTR成形にてニッケル-コバルト合金層が容器内面側となるように成形する。
原板として、下記に示す化学組成を有する低炭素アルミキルド鋼の冷間圧延板(厚さ0.25mm)を焼鈍して得られた鋼板を準備した。
C:0.045重量%、Mn:0.23重量%、Si:0.02重量%、P:0.012重量%、S:0.009重量%、Al:0.063重量%、N:0.0036重量%、残部:Feおよび不可避的不純物
浴組成:硫酸ニッケル、塩化ニッケル、硫酸コバルト、塩化コバルト、およびホウ酸を、コバルト/ニッケルのモル比0.22で含有
pH:3.5~5.0
浴温:60℃
電流密度:15A/dm2
表面処理鋼板のニッケル-コバルト合金層について、X線回折装置(RINT2500/PC、株式会社リガク製)を用いて、X線源:CuKα-40kV、200mA、発散スリット:2°、散乱スリット:1°、受光スリット:0.3mm、測定範囲:35°≦2θ≦50°の条件で、X線回折測定を行なった。そして、X線回折測定の結果得られた回折パターンより、回折角2θが41°以上、43°未満の範囲に存在するピークの強度IAと、回折角2θが43°以上、45°以下の範囲に存在するピークの強度IBとを演算し、これらの比IA/IBを算出した。結果を表1に示す。
ニッケル-コバルト合金層の表面硬度(Hv10g)は、マイクロビッカース硬度計を用い、荷重10gの条件で測定した。結果を表1に示す。
ニッケル-コバルト合金層を形成する際における、ニッケル-コバルト合金めっきの電流密度を、それぞれ20A/dm2(実施例2)、30A/dm2(実施例3)とした以外は、実施例1と同様にして、表面処理鋼板を得て、同様に評価を行った。結果を表1に示す。
ニッケル-コバルト合金層を形成する際における、ニッケル-コバルト合金めっき浴の浴温を70℃とし、かつ、ニッケル-コバルト合金めっきの電流密度を、それぞれ15A/dm2(実施例4)、20A/dm2(実施例5)、30A/dm2(実施例6)とした以外は、実施例1と同様にして、表面処理鋼板を得て、同様に評価を行った。結果を表1に示す。
ニッケル-コバルト合金層を形成する際における、ニッケル-コバルト合金めっき浴の浴温を80℃とし、かつ、ニッケル-コバルト合金めっきの電流密度を、それぞれ15A/dm2(実施例7)、20A/dm2(実施例8)、30A/dm2(実施例9)とした以外は、実施例1と同様にして、表面処理鋼板を得て、同様に評価を行った。結果を表1に示す。
ニッケル-コバルト合金層を形成する際における、ニッケル-コバルト合金めっきの電流密度を、それぞれ5A/dm2(比較例1)、10A/dm2(比較例2)とした以外は、実施例1と同様にして、表面処理鋼板を得て、同様に評価を行った。結果を表1に示す。
ニッケル-コバルト合金層を形成する際における、ニッケル-コバルト合金めっき浴の浴温を70℃とし、かつ、ニッケル-コバルト合金めっきの電流密度を、それぞれ5A/dm2(比較例3)、10A/dm2(比較例4)とした以外は、実施例1と同様にして、表面処理鋼板を得て、同様に評価を行った。結果を表1に示す。
ニッケル-コバルト合金層を形成する際における、ニッケル-コバルト合金めっき浴の浴温を80℃とし、かつ、ニッケル-コバルト合金めっきの電流密度を、それぞれ5A/dm2(比較例5)、10A/dm2(比較例6)とした以外は、実施例1と同様にして、表面処理鋼板を得て、同様に評価を行った。結果を表1に示す。
一方、ニッケル-コバルト合金めっきを行なう際における電流密度を15A/dm2未満とした比較例1~6は、ニッケル-コバルト合金層のX線回折測定による強度比IA/IBが、いずれも、0.9よりも大きな値となり、ニッケル-コバルト合金層を内面とする電池容器として用いた際に、電池特性の向上効果、特に経時後の内部抵抗の増大の抑制効果が期待できないものであった。
原板として、実施例1と同様の鋼板を準備し、準備した鋼板について、アルカリ電解脱脂、硫酸浸漬の酸洗を行った後、下記条件にてニッケルめっきを行い、厚さ1.0μmのニッケルめっき層を形成し、次いで、下記条件にてニッケル-コバルト合金めっきを行い、ニッケルめっき層の上に、厚さ0.2μmのニッケル-コバルト合金層を形成することにより、表面処理鋼板を得た。
<ニッケルめっき>
浴組成:硫酸ニッケル250g/L、塩化ニッケル45g/L、ほう酸30g/L
pH:3.5~5.0
浴温:60℃
電流密度:10A/dm2
<ニッケル-コバルト合金めっき>
浴組成:硫酸ニッケル、塩化ニッケル、硫酸コバルト、塩化コバルト、およびホウ酸を、コバルト/ニッケルのモル比0.22で含有
pH:3.5~5.0
浴温:60℃
電流密度:20A/dm2
上記にて作製した電池容器の内面側のニッケル-コバルト合金層の表面粗度Raを超深度形状測定顕微鏡(KEYENCE製、VK-8550)により測定した。結果を表2に示す。
上記にて得られたアルカリマンガン電池を、初期の内部抵抗については、常温で1日以上放置し安定させた後に、また経時後の内部抵抗については60℃で20日間放置した後、交流インピーダンス法により内部抵抗(mΩ)を測定した。内部抵抗が低いほど電池特性は良好であると判断することができる。結果を表2に示す。
表面処理鋼板を得る際におけるニッケル-コバルト合金層を形成する際のニッケル-コバルト合金めっき浴の浴温を、それぞれ70℃(実施例11)、80℃(実施例12)とした以外は、実施例10と同様にして、表面処理鋼板、電池容器、およびアルカリマンガン電池を作製し、実施例10と同様に評価を行った。結果を表2に示す。
表面処理鋼板を得る際にニッケル-コバルト合金層を形成しなかった以外は、実施例10と同様にして、表面処理鋼板、および電池容器を作製し、実施例10と同様に評価を行った。そして、比較例7では、電池容器内面に黒鉛粉末を主成分とする導電膜を形成した以外は、実施例10と同様にして、アルカリマンガン電池を作製し、実施例10と同様に評価を行った。結果を表2に示す。
表面処理鋼板を得る際におけるニッケル-コバルト合金層を形成する際のニッケル-コバルト合金めっき浴の浴温を60℃とし、かつ、ニッケル-コバルト合金めっきの電流密度を、5A/dm2とした以外は、実施例1と同様にして、表面処理鋼板を得て、同様に評価を行った。結果を表1に示す。
一方、ニッケル-コバルト合金めっきを行なう際における電流密度を15A/dm2未満とした比較例8は、ニッケル-コバルト合金めっきを行なう際におけるめっき浴の浴温を60~80℃とし、かつ、電流密度を15~40A/dm2とした実施例10~12と比較して、表面処理鋼板の表面硬度が低くなる結果となり、また、これに伴い、電池容器形成後における電池内面の表面粗度Raも低くなる結果となった。そして、比較例8においては、実施例10~12と比較して、電池特性(内部抵抗IR)の向上効果が不十分なものであった。
なお、実施例10~12においては、ニッケル-コバルト合金層の厚みが薄く、そのため、X線回折測定による強度比IA/IBの測定を行わなかったが、上述した実施例1~9の結果より、実施例10~12のいずれも、X線回折測定による強度比IA/IBは0.01~0.9の範囲にあるものと判断することができる。同様に、比較例8においても、ニッケル-コバルト合金層の厚みが薄く、そのため、X線回折測定による強度比IA/IBの測定を行わなかったが、上述した比較例1の結果より、X線回折測定による強度比IA/IBが0.9を超えるものであると判断することができる。
Claims (6)
- 電池容器内面となる面の最表面に、ニッケル-コバルト合金層が形成されてなる電池容器用表面処理鋼板であって、前記ニッケル-コバルト合金層のCuKαを線源とするX線回折測定による、回折角2θが41°以上、43°未満の範囲に存在するピークの強度IAと、回折角2θが43°以上、45°以下の範囲に存在するピークの強度IBとの比率である強度比IA/IBが0.01~0.9の範囲にあることを特徴とする電池容器用表面処理鋼板。
- 前記ニッケル-コバルト合金層の下層として、ニッケル層を有することを特徴とする請求項1に記載の電池容器用表面処理鋼板。
- 前記ニッケル-コバルト合金層と鋼板との間に鉄-ニッケル拡散を有することを特徴とする請求項1または2に記載の電池容器用表面処理鋼板。
- 請求項1~3のいずれかに記載の電池容器用表面処理鋼板を成形加工してなる電池容器。
- 請求項4に記載の電池容器を用いてなる電池。
- 電池容器内面となる面の最表面に、ニッケル-コバルト合金層が形成されてなる電池容器用表面処理鋼板を製造する方法であって、
前記ニッケル-コバルト合金層を、コバルト/ニッケルのモル比が0.01~2.4であるニッケル-コバルト合金めっき浴を用いた合金めっきにより、浴温60~80℃、および電流密度15~40A/dm2の条件にて形成することを特徴とする電池容器用表面処理鋼板の製造方法。
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