WO2015015846A1 - 電池容器用表面処理鋼板、電池容器および電池 - Google Patents
電池容器用表面処理鋼板、電池容器および電池 Download PDFInfo
- Publication number
- WO2015015846A1 WO2015015846A1 PCT/JP2014/061020 JP2014061020W WO2015015846A1 WO 2015015846 A1 WO2015015846 A1 WO 2015015846A1 JP 2014061020 W JP2014061020 W JP 2014061020W WO 2015015846 A1 WO2015015846 A1 WO 2015015846A1
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- Prior art keywords
- iron
- battery
- steel sheet
- nickel alloy
- nickel
- Prior art date
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 198
- 239000010959 steel Substances 0.000 title claims abstract description 198
- 238000007747 plating Methods 0.000 claims abstract description 175
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 174
- 238000010438 heat treatment Methods 0.000 claims abstract description 65
- 239000013078 crystal Substances 0.000 claims description 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 113
- 229910052742 iron Inorganic materials 0.000 abstract description 28
- 238000010828 elution Methods 0.000 abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 184
- 229910052759 nickel Inorganic materials 0.000 description 71
- 238000000034 method Methods 0.000 description 32
- 238000005259 measurement Methods 0.000 description 29
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 28
- 239000000203 mixture Substances 0.000 description 20
- 238000009792 diffusion process Methods 0.000 description 19
- 239000007789 gas Substances 0.000 description 19
- 229910052748 manganese Inorganic materials 0.000 description 19
- 239000011572 manganese Substances 0.000 description 19
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 18
- 238000000137 annealing Methods 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 16
- 238000009713 electroplating Methods 0.000 description 15
- 230000003287 optical effect Effects 0.000 description 10
- 230000007704 transition Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 150000002815 nickel Chemical class 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 238000001887 electron backscatter diffraction Methods 0.000 description 6
- 150000002505 iron Chemical class 0.000 description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000358 iron sulfate Inorganic materials 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 238000010409 ironing Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000004381 surface treatment Methods 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
- 229910000655 Killed steel Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- 239000006172 buffering agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- -1 iron ion Chemical class 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
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 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
- 238000012790 confirmation Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000004744 fabric 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
- 239000012212 insulator Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- SQZYOZWYVFYNFV-UHFFFAOYSA-L iron(2+);disulfamate Chemical compound [Fe+2].NS([O-])(=O)=O.NS([O-])(=O)=O SQZYOZWYVFYNFV-UHFFFAOYSA-L 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- CXIHYTLHIDQMGN-UHFFFAOYSA-L methanesulfonate;nickel(2+) Chemical compound [Ni+2].CS([O-])(=O)=O.CS([O-])(=O)=O CXIHYTLHIDQMGN-UHFFFAOYSA-L 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000010731 rolling oil Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- 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
- B32B15/011—Layered products comprising a layer of metal all layers being exclusively metallic all layers being formed of iron alloys or steels
-
- 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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
- H01M50/128—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers with two or more layers of only inorganic material
-
- 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
-
- 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
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- 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.
- Such batteries are required to have longer life and higher performance in accordance with higher performance of the mounted devices, and battery containers filled with power generation elements composed of positive electrode active materials, negative electrode active materials, and the like are also used as batteries.
- power generation elements composed of positive electrode active materials, negative electrode active materials, and the like are also used as batteries.
- Patent Document 1 As such a battery container, for example, in Patent Document 1, after a nickel plating layer is formed on a steel plate, an iron-nickel alloy plating layer is formed and processed so that the iron-nickel alloy layer becomes the inner surface of the battery container.
- a molded battery container is disclosed.
- the surface of the iron-nickel alloy plating layer formed by performing iron-nickel alloy plating is an amorphous portion where iron is easily eluted.
- iron is eluted from the amorphous part in the electrolyte, and this causes damage to the battery container due to the gas generated inside the battery as iron is eluted. As a result, liquid leakage occurs and the battery life is shortened.
- the object of the present invention is to suppress the elution of iron inside the battery when it is used as a battery container, thereby extending the life of the battery and improving battery characteristics such as discharge characteristics. It is providing the surface-treated steel sheet for battery containers made. Another object of the present invention is to provide a battery container and a battery obtained by using such a surface-treated steel sheet for battery containers.
- the present inventors have conducted an iron-nickel plating on the steel sheet, followed by heat treatment, and an average crystal on the outermost surface of the iron-nickel alloy layer formed on the outermost surface.
- the inventors have found that the above object can be achieved by setting the particle size to 1 to 8 ⁇ m, and have completed the present invention.
- a surface-treated steel sheet for a battery container obtained by subjecting a steel sheet to iron-nickel alloy plating and then heat treatment, wherein the outermost layer is an iron-nickel alloy layer,
- the nickel alloy layer is provided with a surface-treated steel sheet for battery containers, wherein an average crystal grain size on the outermost surface is 1 to 8 ⁇ m.
- the content ratio of Fe atoms on the outermost surface of the iron-nickel alloy layer is preferably 12 to 50 atomic%.
- the iron-nickel alloy layer preferably has a Vickers hardness (HV) of 210 to 250.
- molding one of the said surface-treated steel sheets for battery containers is provided.
- the battery which uses the said battery container is provided.
- the present invention when used as a battery container, the elution of iron inside the battery can be suppressed, which can extend the life of the battery and improve battery characteristics such as discharge characteristics. It is possible to provide a surface-treated steel sheet for a battery container, and a battery container and a battery obtained using the surface-treated steel sheet for a battery container.
- FIG. 1 is a configuration diagram of a surface-treated steel sheet for battery containers according to the first embodiment.
- FIG. 2 is a diagram showing the results of measuring the Ni intensity and Fe intensity of the surface-treated steel sheet for battery containers according to the first embodiment using a high-frequency glow discharge emission spectroscopic analyzer.
- FIG. 3 is a configuration diagram of the surface-treated steel sheet for battery containers according to the second embodiment.
- FIG. 4 is a view for explaining a method of manufacturing the surface-treated steel sheet for battery containers according to the second embodiment.
- FIG. 5 is a diagram showing results of measuring Ni intensity and Fe intensity with a high-frequency glow discharge emission spectroscopic analyzer for the surface-treated steel sheet for battery containers according to the second embodiment.
- FIG. 1 is a configuration diagram of a surface-treated steel sheet for battery containers according to the first embodiment.
- FIG. 2 is a diagram showing the results of measuring the Ni intensity and Fe intensity of the surface-treated steel sheet for battery containers according to the first embodiment using a high-frequency glow discharge emission
- FIG. 6 is a configuration diagram illustrating another example of the surface-treated steel sheet for battery containers according to the second embodiment.
- FIG. 7 is a diagram showing results of measuring Ni intensity and Fe intensity by a high-frequency glow discharge emission spectroscopic analyzer for another example of the surface-treated steel sheet for battery containers according to the second embodiment.
- FIG. 8 is a diagram for explaining a method of manufacturing the surface-treated steel sheet for battery containers according to the third embodiment.
- FIG. 9 is a diagram showing the results of measuring the Ni intensity and the Fe intensity with a high-frequency glow discharge emission spectroscopic analyzer for the surface-treated steel sheet for battery containers of Examples.
- FIG. 1 is a diagram showing a configuration of a surface-treated steel sheet 100 for battery containers according to this embodiment.
- the surface-treated steel sheet 100 for a battery container according to the present embodiment is obtained by performing iron-nickel alloy plating on the steel sheet 10 and then performing heat treatment such as continuous annealing or box annealing. It is a surface-treated steel sheet for battery containers formed by forming an alloy layer 20.
- the steel plate 10 that is the substrate of the surface-treated steel plate 100 for the battery container of the present embodiment is excellent in drawing workability, drawing ironing workability, and 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% by weight
- ultra low carbon steel having a carbon content of 0.003% or less or ultra low carbon steel with Ti or Non-aging ultra-low carbon steel obtained by adding Nb or the like can be used.
- these steel hot-rolled plates are pickled to remove surface scale (oxide film), cold-rolled, and then subjected to electrolytic cleaning of rolling oil, or after the electrolytic cleaning What was annealed and temper-rolled is used as a substrate.
- the annealing may be either continuous annealing or box annealing, and is not particularly limited.
- the iron-nickel alloy layer 20 is the outermost layer of the surface-treated steel sheet 100 for battery containers. After the iron-nickel alloy plating is performed on the steel sheet 10, continuous annealing or box-type processing is performed. It is formed by performing a heat treatment such as annealing, and the average crystal grain size at the outermost surface is controlled in the range of 1 to 8 ⁇ m.
- the iron-nickel alloy layer 20 can be appropriately crystallized by performing heat treatment after the iron-nickel alloy plating is performed on the steel plate 10, and the iron-nickel alloy layer 20 By controlling the average crystal grain size on the outermost surface within the above range, the surface-treated steel sheet for battery container 100 to be obtained is used as a battery container while making the hardness of the surface of the iron-nickel alloy layer 20 appropriate. The elution of iron into the electrolyte can be suppressed.
- the battery life can be extended by improving the leakage resistance of the battery container.
- the iron-nickel alloy layer 20 becomes the inner surface of the battery container.
- processing such as drawing, ironing, DI or DTR molding is performed, a fine and shallow crack can be generated on the surface of the iron-nickel alloy layer 20.
- Such fine and shallow cracks can increase the contact area between the iron-nickel alloy layer 20 and the positive electrode mixture used in the battery, thereby reducing the internal resistance of the battery and reducing the discharge. Battery characteristics such as characteristics can be improved.
- a battery container obtained by forming a steel sheet that has not been subjected to heat treatment after iron-nickel alloy plating has a problem that iron is eluted in the electrolyte and the battery life is shortened.
- the reason for the elution of iron in this manner is, for example, that strain remains on the surface of the layer formed by iron-nickel alloy plating in a state where heat treatment is not performed, and this is caused by such strain. This is presumably because there are many amorphous portions where iron is likely to elute.
- the average crystal grain size on the outermost surface of the iron-nickel alloy layer 20 is too small, the hardness of the iron-nickel alloy layer 20 becomes too high, and the iron-nickel alloy layer is formed when being molded as a battery container. 20, deep cracks reaching the steel plate 10 occur, and the steel plate 10 is exposed. In this case, iron is eluted from the exposed portion of the steel plate 10, and the battery container is damaged by the gas generated along with the elution of the iron, so that the leakage resistance of the battery container is lowered.
- the average crystal grain size on the outermost surface of the iron-nickel alloy layer 20 is too large, the hardness of the iron-nickel alloy layer 20 will be too low, and the inner surface of the battery container will be appropriately formed when being molded as a battery container. Therefore, the effect of reducing the internal resistance of the battery and improving the battery characteristics cannot be obtained.
- the average crystal grain size on the outermost surface of the iron-nickel alloy layer 20 can be measured, for example, by the following method. That is, when the iron-nickel alloy layer 20 is irradiated with an electron beam using a scanning electron microscope (SEM), the electrons obtained by projecting the electron beam reflected on the surface of the iron-nickel alloy layer 20 onto the screen are obtained. By analyzing the backscattering pattern (EBSD (Electron Backscatter Diffraction)), it is possible to obtain information on the crystal grain size for each crystal grain constituting the iron-nickel alloy layer 20 and thereby calculate the average crystal grain size. it can.
- SEM scanning electron microscope
- a region where the reflection angle difference between adjacent irradiation points is within a predetermined range is defined as one crystal grain.
- the crystal grain size can be measured for each crystal grain, and this can be averaged to calculate the average crystal grain size.
- the iron-nickel alloy layer 20 has an average crystal grain size on the outermost surface of 1 to 8 ⁇ m, preferably 2 to 8 ⁇ m.
- the measurement value obtained is the average value on the outermost surface of the iron-nickel alloy layer 20. It shows the crystal grain size.
- the inside is properly crystallized. It is considered that not only the outermost surface of 20 but also the vicinity of the outermost surface, the average crystal grain size is in the above range.
- the surface hardness of the iron-nickel alloy layer 20 is Vickers hardness (HV), preferably 210 to 250, more preferably 220 to 240. If the Vickers hardness of the surface of the iron-nickel alloy layer 20 is too high, when the battery container is molded, the iron-nickel alloy layer 20 is deeply cracked, and the steel plate 10 is exposed, thereby the battery container. As a result, iron is eluted from the exposed portion of the steel plate 10 and the leakage resistance is reduced.
- HV Vickers hardness
- the Vickers hardness of the surface of the iron-nickel alloy layer 20 is too low, the inner surface of the battery container cannot be cracked properly when being molded as a battery container, so that the internal resistance of the battery is lowered and the battery characteristics are reduced. The effect of improving the quality cannot be obtained sufficiently.
- the thickness of the iron-nickel alloy layer 20 is not particularly limited, but is preferably 0.5 to 3.0 ⁇ m, more preferably 1.0 to 2.0 ⁇ m. By setting the thickness of the iron-nickel alloy layer 20 in the above range, the leakage resistance and battery characteristics of the battery container are further improved when the obtained surface-treated steel sheet for battery container 100 is used as a battery container.
- the thickness of the iron-nickel alloy layer 20 can be measured, for example, by the following method. That is, with respect to the surface-treated steel sheet 100 for battery containers, the transition of Ni intensity is measured in the depth direction of the iron-nickel alloy layer 20 using a high-frequency glow discharge optical emission spectrometer, and nickel is present from the start of measurement. By detecting the depth until it stops, the thickness of the iron-nickel alloy layer 20 can be obtained.
- the region where the Ni strength is 1/10 or more of the maximum value is defined as nickel based on the maximum value of the Ni strength. Can be an area where there exists. Therefore, in the present embodiment, the Ni strength is measured in the depth direction for the surface-treated steel sheet 100 for battery containers, and the Ni strength is less than 1/10 of the maximum value of the Ni strength starting from the measurement start time. The measurement time up to this point is calculated, and the thickness of the iron-nickel alloy layer 20 can be obtained based on the calculated measurement time.
- FIG. 2 shows the transition of the Ni intensity and the Fe intensity in the depth direction of the iron-nickel alloy layer 20 with respect to the surface-treated steel sheet 100 for battery containers, using a high-frequency glow discharge optical emission spectrometer. It is a graph which shows a result.
- the horizontal axis indicates the measurement time by the high-frequency glow discharge optical emission spectrometer
- the vertical axis indicates the measured Ni intensity or Fe intensity.
- the maximum value of Ni intensity is a value at the time of about 70 sec, and the Ni intensity is less than 1/10 of such maximum value (in FIG. 2).
- the time point indicated by “Ni strength 1/10”) can be calculated as a time point of about 105 seconds from the start of measurement, and based on the calculated measurement time of about 105 seconds, the iron-nickel alloy layer 20 can be calculated. Can be obtained.
- iron-nickel alloy plating can be performed, for example, by a method such as electrolytic plating or electroless plating, but is performed by electrolytic plating because the average crystal grain size of the obtained iron-nickel alloy layer 20 can be easily controlled. It is preferable.
- a plating bath (iron-nickel plating) containing a buffering agent or the like in addition to the iron salt and nickel salt constituting the iron-nickel alloy layer 20 This is performed by plating the steel plate 10 using a bath.
- iron-nickel plating baths include watt baths and sulfamic acid baths, iron salts such as iron sulfate, nickel salts such as nickel sulfate and nickel chloride, and buffering agents such as boric acid and citric acid. A plating bath to which is added.
- the iron salt and nickel salt to be contained in the iron-nickel plating bath are not particularly limited, but the iron salt is preferably iron sulfate, iron chloride, iron sulfamate, or iron citrate, and the nickel salt is Nickel sulfate, nickel chloride, nickel carbonate, nickel acetate, nickel sulfamate and nickel methanesulfonate are preferred.
- the iron salt and the nickel salt are substantially other than iron and nickel. It is preferable to use one that does not contain metal. However, the iron salt and the nickel salt may contain other metals as long as they are impurities.
- the content ratio of Fe atoms and Ni atoms in the layer formed by iron-nickel alloy plating is not particularly limited, but the content ratio of Fe atoms is preferably 15 to 45 atoms. %, More preferably 20 to 40 atomic%.
- the content ratio of Ni atoms is preferably 55 to 85 atomic%, more preferably 60 to 80 atomic%.
- the average crystal grain size at the outermost surface of the iron-nickel alloy layer 20 becomes too small. If the proportion is too small (that is, if the Ni atom content is too large), the average crystal grain size on the outermost surface of the iron-nickel alloy layer 20 becomes too large.
- the pH of the iron-nickel plating bath is preferably 1.0 to 3.0, more preferably 1.5 to 2.9.
- the pH of the iron-nickel plating bath is preferably 1.0 to 3.0, more preferably 1.5 to 2.9.
- the bath temperature of the iron-nickel plating bath is preferably 40 to 80 ° C., more preferably 50 to 70 ° C.
- the current density when performing electrolytic plating with an iron-nickel plating bath is preferably 5 to 40 A / dm 2 , more preferably 5 to 30 A / dm 2 .
- heat treatment is performed on the steel plate 10 on which the iron-nickel alloy plating is performed.
- the iron-nickel alloy layer 20 is formed by thermally diffusing the layer formed by iron-nickel alloy plating on the steel plate 10.
- methods such as continuous annealing and box type annealing, can be used.
- the heat treatment temperature is preferably 700 to 800 ° C. and the heat treatment time is preferably 10 seconds to 300 seconds.
- the heat treatment temperature is 450 to 650 ° C.
- heat treatment time 1 hour to 10 hours
- heat treatment atmosphere non-oxidizing atmosphere or reducing protective gas atmosphere
- the heat treatment atmosphere is a 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 average crystal grain size on the outermost surface of the iron-nickel alloy layer 20 can be controlled by appropriately adjusting the conditions of the heat treatment temperature and the heat treatment time during the heat treatment. Specifically, the higher the heat treatment temperature or the longer the heat treatment time, the larger the average crystal grain size, while the lower the heat treatment temperature or the shorter the heat treatment time. As the value becomes, the average crystal grain size can be reduced.
- the iron-nickel alloy layer 20 can be appropriately crystallized as described above, thereby forming the surface-treated steel sheet for battery container 100 to be processed.
- the obtained battery container can effectively suppress the elution of iron into the electrolytic solution.
- the surface-treated steel sheet to be obtained has an amorphous portion on the outermost surface, and when used as a battery container, the electrolyte solution from the amorphous portion is used. It is easy for iron to elute.
- the content ratio of Fe atoms and Ni atoms in the iron-nickel alloy layer 20 is not particularly limited, but the content ratio of Fe atoms on the outermost surface is preferably 12 to 50 atomic%, More preferably, it is 15 to 45 atomic%, and further preferably 20 to 40 atomic%.
- the average crystal grain size on the outermost surface of the iron-nickel alloy layer 20 can be controlled within the above range.
- a method of setting the content ratio of Fe atoms on the outermost surface of the iron-nickel alloy layer 20 in the above range for example, a method of adjusting the content ratio of iron salt and nickel salt in the iron-nickel plating bath described above Is mentioned.
- Examples of the method for measuring the proportion of Fe atoms contained in the iron-nickel alloy layer 20 include a method of measuring the proportion of Fe atoms on the outermost surface using a scanning Auger electron spectrometer.
- the surface-treated steel sheet 100 for battery containers according to this embodiment is manufactured.
- the iron-nickel alloy layer 20 is appropriately crystallized by performing heat treatment after iron-nickel alloy plating is performed on the steel sheet 10.
- the average crystal grain size at the outermost surface of the iron-nickel alloy layer 20 within the above range, when the obtained surface-treated steel sheet for battery container 100 is used as a battery container, the liquid-proof solution And battery characteristics can be improved.
- the battery container of this embodiment is obtained by processing and forming the above-described surface-treated steel sheet for battery container 100.
- the battery container can be obtained by forming the above-described surface-treated steel sheet for battery container 100 into a battery container shape by drawing, ironing, DI or DTR molding.
- the battery container surface-treated steel sheet 100 is formed such that the iron-nickel alloy layer 20 is on the battery container inner surface side.
- the battery container obtained in this way uses the surface-treated steel sheet for battery container 100 described above, battery characteristics such as liquid leakage resistance and discharge characteristics are improved, and thereby the battery life is long. In addition, it has excellent battery characteristics such as discharge characteristics. Therefore, 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.
- 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.
- the surface-treated steel sheet 100a for battery containers according to the second embodiment has a configuration as shown in FIG. 3, and an iron-nickel diffusion layer 50 is provided between the iron-nickel alloy layer 20a and the steel sheet 10. Except that it is different in that it has the same structure as the surface-treated steel sheet 100 for battery containers according to the first embodiment.
- the surface-treated steel sheet for battery containers according to the second embodiment is manufactured by the following method. That is, first, the nickel-plated layer 40 and the iron-nickel alloy plated layer 30 are formed in this order on the steel plate 10 to obtain the surface-treated steel plate shown in FIG. Next, the surface-treated steel sheet shown in FIG. 4 is subjected to heat treatment, whereby each layer is thermally diffused to form the iron-nickel alloy layer 20a and the iron-nickel diffusion layer 50, thereby producing the surface-treated steel sheet for battery containers 100a. Is done.
- the iron-nickel alloy plating layer 30 formed on the steel plate 10 can be formed by performing plating under the same conditions as the iron-nickel alloy plating in the first embodiment described above.
- the nickel plating layer 40 formed on 10 can be formed by a known method using a watt bath, a sulfamic acid bath, or the like.
- the surface-treated steel sheet shown in FIG. 4 is subjected to heat treatment, whereby each layer is thermally diffused to form the iron-nickel alloy layer 20a and the iron-nickel diffusion layer 50.
- the iron-nickel alloy layer 20a is formed by thermal diffusion of the nickel plating layer 40 and the iron-nickel alloy plating layer 30, and the iron-nickel diffusion layer 50 is thermally diffused by the steel plate 10 and the nickel plating layer 40. Is formed.
- the nickel plating layer 40 is completely diffused by heat treatment, and as shown in FIG. The single nickel plating layer 40 is not left in 100a.
- the heat treatment conditions are not particularly limited and may be the same as the heat treatment conditions in the first embodiment described above. However, the heat treatment temperature and the heat treatment time are adjusted, and the single nickel plating layer 40 remains. The conditions are such that they will disappear.
- the thickness of the nickel plating layer 40 before the heat treatment is preferably 1.5 ⁇ m or less, more preferably 1.0 ⁇ m or less. If the thickness of the nickel plating layer 40 before the heat treatment exceeds 1.5 ⁇ m, a heat treatment temperature at a high temperature may be necessary to completely diffuse the nickel plating layer, or a long-time heat treatment may be required.
- the steel sheet may be altered by heat.
- the thickness of the nickel plating layer 40 before heat treatment to 1.5 ⁇ m or less, it is possible to suppress the deterioration of the steel sheet due to heat, and by setting the thickness to 1.0 ⁇ m or less, the nickel plating layer 40 is formed by heat treatment. Since the heat treatment temperature at the time of complete diffusion can be made lower, or the heat treatment time can be made shorter, the deterioration of the steel sheet 10 due to heat can be prevented.
- the average crystal grain size at the outermost surface of the iron-nickel alloy layer 20a is the same as that of the iron-nickel alloy layer 20 of the surface-treated steel sheet for battery containers 100 according to the first embodiment described above. It is the same.
- the method for controlling the average crystal grain size on the outermost surface of the iron-nickel alloy layer 20a is not particularly limited.
- the iron-nickel alloy plating is performed under the same conditions as in the first embodiment described above. The method and the method of giving heat processing are mentioned.
- the hardness of the iron-nickel alloy layer 20a is the same as that of the iron-nickel alloy layer 20 of the surface-treated steel sheet for battery containers 100 according to the first embodiment described above.
- the thickness of the iron-nickel alloy layer 20a is not particularly limited, but is preferably 0.1 to 1.0 ⁇ m, more preferably 0.1 to 0.5 ⁇ m. By setting the thickness of the iron-nickel alloy layer 20a within the above range, when the surface-treated steel sheet 100a for battery container obtained is used as a battery container, the leakage resistance and battery characteristics are further improved.
- the thickness of the iron-nickel alloy layer 20a in the surface-treated steel sheet for battery containers 100a can be measured, for example, by the following method. That is, with respect to the surface-treated steel sheet 100a for a battery container, when the change in Ni intensity was measured in the depth direction of the iron-nickel alloy layer 20a using a high-frequency glow discharge emission spectroscopic analyzer, The depth until the strength reaches the maximum value can be detected as the thickness of the iron-nickel alloy layer 20a.
- FIG. 5 shows the transition of Ni intensity and Fe intensity in the depth direction of the iron-nickel alloy layer 20a of the surface-treated steel sheet 100a for battery containers, using a high-frequency glow discharge optical emission spectrometer. It is a graph which shows a result.
- the horizontal axis indicates the measurement time by the high-frequency glow discharge optical emission spectrometer
- the vertical axis indicates the measured Ni intensity or Fe intensity.
- the time point at which the Ni intensity reaches the maximum value can be calculated as the time point of about 45 seconds from the start of measurement.
- the thickness of the iron-nickel alloy layer 20a can be obtained based on the calculated measurement time of about 45 seconds.
- the thickness thereof is usually iron. -Thicker than the nickel alloy plating layer 30.
- the thickness of the iron-nickel diffusion layer 50 is not particularly limited, but the thickness of the iron-nickel diffusion layer 50 is the same as that of the iron-nickel alloy layer 20a described above. It can be measured using a discharge emission spectrometer. That is, with respect to the surface-treated steel sheet 100a for a battery container, the transition of Ni intensity is measured in the depth direction using a high-frequency glow discharge emission spectroscopic analyzer, and the Ni intensity becomes The depth up to less than 1/10 of the maximum value can be detected as the thickness of the iron-nickel diffusion layer 50.
- the depth from the start of measurement to the time point of about 45 sec when the Ni intensity reaches the maximum value is defined as the thickness of the iron-nickel alloy layer 20a. From about 45 sec when the Ni intensity reached the maximum value to about 85 sec (when indicated as “Ni intensity 1/10” in FIG. 5) when the Ni intensity was less than 1/10 of the maximum value. Is the thickness of the iron-nickel diffusion layer 50. At this time, the thickness of the iron-nickel diffusion layer 50 can be obtained based on the measurement time of about 40 seconds from the time of about 45 seconds to the time of about 85 seconds.
- the nickel plating layer 40 and the iron-nickel alloy plating layer 30 are formed on the steel plate 10
- thermal diffusion is performed, and the formed iron-nickel alloy layer 20a is formed.
- the surface-treated steel sheet for battery container 100a obtained is used as a battery container by making the average crystal grain size on the outermost surface the same as in the first embodiment, the first embodiment described above is used.
- the liquid leakage resistance and battery characteristics can be improved.
- the thickness of the nickel plating layer 40 before the heat treatment and the conditions for the heat treatment are adjusted as appropriate, so that the iron-nickel alloy layer 20a as in the surface-treated steel sheet for battery containers 100b shown in FIG.
- a single nickel plating layer 40 may be left between the iron-nickel diffusion layer 50.
- the thickness of the iron-nickel alloy layer 20a can be measured, for example, by the following method. That is, with respect to the surface-treated steel sheet 100b for battery containers, the transition of Fe intensity was measured in the depth direction of the iron-nickel alloy layer 20a using a high-frequency glow discharge optical emission spectrometer, and iron was present from the start of measurement. By detecting the depth until it stops, the thickness of the iron-nickel alloy layer 20a can be obtained.
- the region where the Fe strength is 1/10 or more of the maximum value on the basis of the maximum value of the Fe strength when the Fe strength is measured for the surface-treated steel sheet for battery containers 100b is iron.
- the maximum value of the Fe intensity is measured by the high-frequency glow discharge emission spectroscopic analyzer in the depth direction of the surface-treated steel sheet for battery container 100b until reaching the steel sheet 10, and the Fe intensity and Ni intensity are measured. It shows the Fe strength when the fluctuation disappears.
- FIG. 7 shows the transition of Fe intensity and Ni intensity in the depth direction of the iron-nickel alloy layer 20a of the surface-treated steel sheet 100b for battery containers, using a high-frequency glow discharge emission spectroscopic analyzer. It is a graph which shows a result.
- the horizontal axis indicates the measurement time by the high-frequency glow discharge emission spectrometer, and the vertical axis indicates the measured Fe intensity or Ni intensity.
- the time when the Fe intensity becomes less than 1/10 of the maximum value for the first time starting from the measurement start time (the time indicated by “Fe intensity 1/10” in FIG. 7). ) Can be calculated as about 28 seconds, and the thickness of the iron-nickel alloy layer 20a can be obtained based on the calculated measurement time of about 28 seconds.
- the thickness of the nickel plating layer 40 can also be measured using a high-frequency glow discharge emission spectroscopic analyzer. That is, with respect to the surface-treated steel sheet 100b for battery containers, the transition of the Fe intensity is measured in the depth direction using a high-frequency glow discharge optical emission spectrometer, and the Fe intensity is less than 1/10 of the maximum value. The region can be detected as the thickness of the nickel plating layer 40.
- the depth from the start of measurement to the time point of about 28 sec when the Fe intensity becomes less than 1/10 of the maximum value is the thickness of the iron-nickel alloy layer 20a. Further, from about 28 sec when the Fe intensity becomes less than 1/10 of the maximum value, after the Fe intensity decreases, the Fe intensity increases to about 1/10 or more of the maximum value.
- the depth up to the point of time is the thickness of the nickel plating layer 40. In this case, the thickness of the nickel plating layer 40 can be obtained based on the measurement time of about 22 seconds between the time of about 28 seconds and the time of about 50 seconds.
- an iron-nickel diffusion layer 50 is formed in a deeper portion from about 50 seconds when the Fe strength becomes 1/10 or more of the maximum value. Existing.
- the surface-treated steel sheet for battery containers 100b in which the nickel plating layer 40 is left is formed as a battery container
- the inner surface of the battery container is cracked deeply, and the cracks reach the steel sheet 10, and the steel sheet 10, nickel plating layer
- the steel sheet 10 may be easily eluted into the electrolyte. That is, when the nickel plating layer 40 is left, the battery is formed by the steel plate 10 and the nickel plating layer 40 in the electrolytic solution due to the difference in standard electrode potential between the steel plate 10 and the nickel plating layer 40.
- iron is eluted from the steel plate 10 and diffuses into the electrolyte solution, so that the elution of the steel plate 10 may proceed one after another.
- the elution of the steel sheet 10 is made more effective as compared with the structure shown in FIG. Can be prevented. Therefore, in this embodiment, as shown in FIG. 3, it is preferable that the nickel plating layer 40 is not left.
- a method for confirming whether or not the nickel plating layer 40 remains on the surface-treated steel sheet for battery container 100a for example, a method of measuring Fe intensity using a high-frequency glow discharge emission spectroscopic analyzer can be mentioned. . That is, when the transition of the Fe strength in the thickness direction from the outermost iron-nickel alloy layer 20a to the steel plate 10 is measured using a high-frequency glow discharge optical emission spectrometer, the Fe strength is the maximum of the Fe strength. When there is a region where the value is less than 1/10 of the value, it is determined that the nickel plating layer 40 remains, while there is a region where the Fe strength is less than 1/10 of the maximum value. If not, it can be determined that the nickel plating layer 40 does not remain.
- the region where the Fe strength is less than 1/10 of the maximum value (from about 28 sec to about 50 sec in FIG. 7). Therefore, it can be determined that the nickel plating layer 40 remains.
- the surface-treated steel sheet for battery containers 100a there is no region where the Fe strength is less than 1/10 of the maximum value, and the nickel plating layer 40 remains. It can be judged that it is not.
- the surface-treated steel sheet for battery containers according to the third embodiment forms an iron-nickel alloy plating layer 30a and a nickel plating layer 40a in this order on the steel sheet 10, and then heat-treats them. 1 except that it is manufactured by thermally diffusing each layer to form an iron-nickel alloy layer as the outermost layer, by the same method as the surface-treated steel sheet for battery containers according to the first embodiment shown in FIG. Manufactured and has a similar configuration.
- the iron-nickel alloy plating layer 30a formed on the steel plate 10 can be formed by performing plating under the same conditions as the iron-nickel alloy plating in the first embodiment described above.
- the nickel plating layer 40a formed on 10 can be formed by a known method using a watt bath, a sulfamic acid bath, or the like.
- the iron-nickel alloy plating layer 30a and the nickel plating layer 40a are formed on the steel plate 10 and then heat-treated to form the iron-nickel alloy layer.
- the iron-nickel alloy layer is formed.
- the alloy plating layer 30a and the nickel plating layer 40a are sufficiently diffused so that the iron-nickel alloy layer is formed up to the outermost surface.
- the heat treatment conditions are not particularly limited and may be the same as the heat treatment conditions in the first embodiment described above, but the heat treatment temperature and the heat treatment time may be adjusted as appropriate so that the iron-nickel alloy plating layer 30a and The nickel plating layer 40a is completely diffused so that an iron-nickel alloy layer is formed up to the outermost surface.
- the thickness of the nickel plating layer 40a before the heat treatment is preferably 1.0 ⁇ m or less, more preferably 0.5 ⁇ m or less.
- the average crystal grain size at the outermost surface of the iron-nickel alloy layer is the same as that of the iron-nickel alloy layer 20 of the surface-treated steel sheet for battery containers 100 according to the first embodiment described above. It is.
- the method for controlling the average crystal grain size on the outermost surface of the iron-nickel alloy layer is not particularly limited. For example, a method of performing iron-nickel alloy plating under the same conditions as in the first embodiment described above. And a method of performing heat treatment.
- the hardness of the iron-nickel alloy layer is the same as that of the iron-nickel alloy layer 20 of the surface-treated steel sheet for battery containers 100 according to the first embodiment described above.
- the thickness of the iron-nickel alloy layer is not particularly limited.
- the thickness of the iron-nickel alloy plating layer 30a before the heat treatment is not particularly limited, but is preferably 0.5 to 2.0 ⁇ m, more preferably 0.5 to 1.5 ⁇ m.
- the iron-nickel alloy plating layer 30a and the nickel plating layer 40a are formed on the steel plate 10
- thermal diffusion is performed, and the average grain size of the outermost surface of the formed iron-nickel alloy layer is reduced.
- the ratio of Ni atoms contained in the iron-nickel alloy layer is highest near the outermost surface and gradually decreases as the steel sheet 10 is approached.
- elution of iron in the steel sheet 10 can be more effectively suppressed.
- the content of Ni atoms on the outermost surface of the iron-nickel alloy layer is high. Can be suppressed.
- the content of Ni atoms in the iron-nickel alloy layer on the side close to the steel plate 10 is low.
- the difference in the standard electrode potential between the steel plate 10 and the iron-nickel alloy layer in the vicinity of the steel plate 10 can be reduced.
- nickel plating is performed as in the above-described surface-treated steel plate for battery containers 100a shown in FIG. Compared with the configuration in which the layer 40 is left, the elution of iron in the steel plate 10 can be more effectively suppressed.
- the Ni intensity from the iron-nickel alloy layer on the outermost surface toward the steel sheet 10 is measured.
- Electron backscattering obtained by projecting an electron beam reflected on the surface of a surface-treated steel sheet for battery containers onto a screen when the surface-treated steel sheet for battery containers is irradiated with an electron beam using a scanning electron microscope (SEM) By analyzing the pattern (EBSD), treat the region where the reflection angle difference between adjacent irradiation points is within 2 ° as one crystal grain, calculate the crystal grain size for each crystal grain, and average this Thus, an average crystal grain size on the outermost surface of the surface-treated steel sheet for battery containers was obtained.
- SEM scanning electron microscope
- the Vickers hardness (HV) was measured using a diamond indenter with a micro hardness meter (manufactured by Akashi Seisakusho Co., Ltd., model number: MVK-G2) under the conditions of load: 10 gf and holding time: 10 seconds. By measuring, the surface hardness was measured.
- Short-circuit current is 9 A or more
- B Short-circuit current is 8 A or more and less than 9
- C Short-circuit current is 7 A or more and less than 8
- D Short-circuit current is less than 7 A
- the short-circuit current is 9 A or more
- the amount of generated gas is less than 2 cc B: The amount of generated gas is 2 cc or more and less than 2.5 cc C: The amount of generated gas is 2.5 cc or more and less than 3 cc D: The amount of generated gas is 3 cc or more
- the surface-treated steel sheet for a battery container having an amount of generated gas of less than 3 cc (evaluation A and B) has a long battery life when used as a battery container.
- the surface treated steel sheet for battery containers with a generated gas amount of 2.5 cc or more (evaluation C, D) is judged to have a short battery life when used as a battery container. It was.
- Example 1 As a substrate, a steel sheet obtained by annealing a cold rolled sheet (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%, balance: Fe and inevitable impurities
- the prepared steel sheet was subjected to alkaline electrolytic degreasing and pickling with sulfuric acid immersion, and then subjected to electrolytic plating under the following conditions to form a 2 ⁇ m thick iron-nickel alloy plating layer.
- the following bath composition was adjusted so that the composition of the formed iron-nickel alloy plating layer had a content ratio of Fe atoms of 15 atomic% and a content ratio of Ni atoms of 85%.
- Example 1 only the iron-nickel alloy plating layer as the upper plating layer was formed as the plating layer.
- Bath composition nickel sulfate 240 g / L, nickel chloride 45 g / L, iron sulfate 10 g / L, boric acid 30 g / L pH: 3.0 Bath temperature: 60 ° C Current density: 10 A / dm 2
- the steel sheet on which the iron-nickel alloy plating layer is formed is heat-treated by continuous annealing at a temperature of 700 ° C. for 1 minute under the conditions of a reducing atmosphere, whereby the iron-nickel alloy plating layer is thermally diffused to iron-nickel.
- An alloy layer was formed to obtain a surface-treated steel sheet for battery containers having the configuration shown in FIG.
- measurement of the average crystal grain size, measurement of the content of Fe atoms in the outermost layer after heat treatment, and measurement of surface hardness were performed. It was. The results are shown in Table 1.
- the surface-treated steel sheet for the battery container obtained above is punched to a blank diameter of 57 mm, subjected to several times of drawing so that the iron-nickel alloy layer is on the inner surface side of the battery container, and further removed by redrawing.
- a battery container was fabricated by molding into a cylindrical LR6 type battery (AA battery) container having a diameter of 13.8 mm and a height of 49.3 mm.
- an alkaline manganese battery was produced as follows. That is, manganese dioxide and graphite were sampled at a ratio of 10: 1, and potassium hydroxide (10 mol / L) was added and mixed to prepare a positive electrode mixture. Next, 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. Next, a separator made of vinylon woven cloth is inserted along the inner periphery of the positive electrode mixture pellet inserted into the battery container, and a negative electrode gel made of potassium hydroxide and zinc particles saturated with zinc oxide is inserted. The battery container was filled.
- the alkaline manganese battery was produced by carrying out caulking process. And about the alkaline manganese battery obtained in this way, according to the method mentioned above, evaluation of the battery characteristic and evaluation of the amount of gas generation were performed. The results are shown in Table 1.
- Examples 2 to 5 A surface-treated steel sheet for a battery container and a surface-treated steel sheet for battery containers were prepared in the same manner as in Example 1 except that the plating conditions were changed so that the composition of the iron-nickel alloy plating layer (upper plating layer) formed by electrolytic plating was as shown in Table 1. An alkaline manganese battery was produced and evaluated in the same manner. The results are shown in Table 1.
- Comparative Examples 1 and 2 A surface-treated steel sheet for a battery container and a surface-treated steel sheet for battery containers were prepared in the same manner as in Example 1 except that the plating conditions were changed so that the composition of the iron-nickel alloy plating layer (upper plating layer) formed by electrolytic plating was as shown in Table 1. An alkaline manganese battery was produced and evaluated in the same manner. The results are shown in Table 1.
- Example 3 As the upper plating layer, instead of the above-described iron-nickel alloy plating layer, the same as in Example 1 except that a nickel plating layer having a thickness of 2 ⁇ m was formed by electrolytic plating under the following conditions. A surface-treated steel plate and an alkaline manganese battery were produced and evaluated in the same manner. The results are shown in Table 1.
- Bath composition nickel sulfate 250 g / L, nickel chloride 45 g / L, boric acid 30 g / L pH: 4.2
- Current density 10 A / dm 2
- Comparative Examples 4 and 5 The thickness of the nickel plating layer (upper plating layer) formed by electrolytic plating is shown in Table 1, and in addition to the heat treatment by continuous annealing described above, box annealing is performed under the conditions shown in Table 1. Produced a surface-treated steel sheet for battery containers and an alkaline manganese battery in the same manner as in Comparative Example 3, and evaluated in the same manner. The results are shown in Table 1.
- Example 6 A nickel plating layer (lower plating layer) having a thickness of 0.8 ⁇ m is previously formed on a steel plate under the following conditions, and then an iron-nickel alloy plating layer (upper plating layer) is formed on the nickel plating layer by electrolytic plating. Further, by changing the plating conditions so that the composition and thickness of the formed iron-nickel alloy plating layer are as shown in Table 2, a battery container having a structure in which the nickel plating layer does not remain as shown in FIG. A surface-treated steel sheet for a battery container and an alkaline manganese battery were produced and evaluated in the same manner as in Example 1 except that the surface-treated steel sheet was produced. The results are shown in Table 2.
- Example 6 as the plating layer, an iron-nickel alloy plating layer was formed as the upper plating layer, and a nickel plating layer was formed as the lower plating layer.
- Bath composition nickel sulfate 250 g / L, nickel chloride 45 g / L, boric acid 30 g / L pH: 4.2
- Example 7 3 except that the plating conditions were changed so that the composition of the iron-nickel alloy plating layer (upper plating layer) formed by electrolytic plating was as shown in Table 2.
- Surface-treated steel sheets for battery containers and alkaline manganese batteries were produced and evaluated in the same manner. The results are shown in Table 2.
- Example 6 although the remaining nickel plating layer was not confirmed by the above-described high-frequency glow discharge optical emission spectrometer, the thickness of the nickel plating layer formed as the lower plating layer was relatively small.
- the obtained surface-treated steel sheet for battery containers is considered to have a structure in which no nickel plating layer remains as shown in FIG.
- strength with the high frequency glow discharge emission-spectral-analysis apparatus about the processed steel plate is shown.
- the surface-treated steel sheet for battery containers has a nickel plating layer. Can be determined not to remain. Therefore, compared with the surface-treated steel sheet for battery containers in the graph of FIG.
- the nickel plating layer is more easily diffused. It is considered that the surface-treated steel sheet for a battery container has a configuration in which no nickel plating layer remains as shown in FIG.
- Examples 8 and 9 The thickness of the nickel plating layer (lower plating layer) formed on the steel sheet is as shown in Table 2, and the composition of the iron-nickel alloy plating layer (upper plating layer) formed on the nickel plating layer and Example 6 except that a surface-treated steel sheet for a battery container having a structure in which the nickel plating layer remained as shown in FIG. 6 was produced by changing each plating condition so that the thickness was as shown in Table 2. Similarly, a surface-treated steel sheet for battery containers and an alkaline manganese battery were prepared and evaluated in the same manner. The results are shown in Table 2.
- Example 8 and 9 the surface treatment steel sheet for battery containers was actually evaluated for confirmation of remaining nickel plating layer by the following method. That is, using a high-frequency glow discharge optical emission spectrometer (manufactured by Rigaku, model number: GDS-3860), the transition of Ni intensity and Fe intensity in the thickness direction from the outermost iron-nickel alloy layer to the steel sheet was measured. When there is a region where the Fe strength is less than 1/10 of the maximum value of the Fe strength, it is determined that the nickel plating layer remains, whereas the Fe strength is the maximum value. When the area
- the Fe intensity is less than 1/10 of the maximum value in the region indicated by the alternate long and short dash line, and it can be confirmed that nickel is present alone. Thereby, it confirmed that the structure of the surface treatment steel plate for battery containers of Example 8, 9 was a structure with which the nickel plating layer as shown in FIG. 6 remained.
- Example 10 After forming the iron-nickel alloy plating layer on the steel plate so that the composition and thickness of the iron-nickel alloy plating layer (lower plating layer) formed by electrolytic plating are as shown in Table 3, the iron-nickel alloy layer is further formed.
- a nickel plating layer (upper plating layer) having a thickness of 0.1 ⁇ m is formed on the alloy plating layer, and heat treatment is performed to thermally diffuse the iron-nickel alloy plating layer and the nickel plating layer.
- a surface-treated steel sheet for a battery container and an alkaline manganese battery were prepared and evaluated in the same manner as in Example 1 except that the surface-treated steel sheet for a battery container having the structure shown in FIG. 1 was formed. . The results are shown in Table 3.
- As the plating layer a nickel plating layer was formed as an upper plating layer, and an iron-nickel alloy plating layer was formed as a lower plating layer.
- Example 11 Surface-treated steel sheet for battery containers as in Example 10, except that the plating conditions were changed so that the composition of the iron-nickel alloy plating layer (lower plating layer) formed by electrolytic plating was as shown in Table 3
- An alkaline manganese battery was prepared and evaluated in the same manner. The results are shown in Table 3.
- Comparative Example 6 A surface-treated steel sheet for battery containers and an alkaline manganese battery were prepared in the same manner as in Comparative Example 3 except that the thickness of the nickel plating layer (upper plating layer) formed on the outermost layer was as shown in Table 3. And evaluated. The results are shown in Table 3.
- Comparative Example 7 Surface-treated steel sheet for battery containers as in Example 10, except that the plating conditions were changed so that the composition of the iron-nickel alloy plating layer (lower plating layer) formed by electrolytic plating was as shown in Table 3
- An alkaline manganese battery was prepared and evaluated in the same manner. The results are shown in Table 3.
- Comparative Examples 1 and 3 to 7 in which the average crystal grain size on the outermost surface of the iron-nickel alloy layer is less than 1 ⁇ m or more than 8 ⁇ m the evaluation results of battery characteristics are As a result, the battery characteristics such as discharge characteristics were inferior.
- Comparative Examples 2, 4, and 7 in which the average crystal grain size on the outermost surface of the iron-nickel alloy layer is less than 1 ⁇ m or more than 8 ⁇ m the evaluation results of the gas generation amount are both bad and the battery life is short. It became the result.
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Abstract
Description
本発明の電池容器用表面処理鋼板は、前記鉄-ニッケル合金層のビッカース硬度(HV)が210~250であることが好ましい。
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。
図1は、本実施形態の電池容器用表面処理鋼板100の構成を示す図である。図1に示すように、本実施形態の電池容器用表面処理鋼板100は、鋼板10上に鉄-ニッケル合金めっきを施した後、連続焼鈍や箱型焼鈍などの熱処理を施すことで鉄-ニッケル合金層20を形成してなる電池容器用の表面処理鋼板である。
本実施形態の電池容器用表面処理鋼板100の基板となる鋼板10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TiやNbなどを添加してなる非時効性極低炭素鋼を用いることができる。
鉄-ニッケル合金層20は、図1に示すように、電池容器用表面処理鋼板100の最表層となる層であり、鋼板10上に鉄-ニッケル合金めっきを施した後、連続焼鈍や箱型焼鈍などの熱処理を施すことにより形成され、その最表面における平均結晶粒径が、1~8μmの範囲に制御されたものである。
次いで、本実施形態の電池容器用表面処理鋼板100の製造方法について、説明する。
本実施形態の電池容器は、上述した電池容器用表面処理鋼板100を加工成形することにより得られる。具体的には、電池容器は、上述した電池容器用表面処理鋼板100を、絞り、しごき、DIまたはDTR成形にて、電池容器形状に成形することにより得ることができる。なお、この際においては、電池容器用表面処理鋼板100の鉄-ニッケル合金層20が電池容器内面側となるように成形する。
次いで、本発明の第2実施形態について説明する。
第2実施形態に係る電池容器用表面処理鋼板100aは、図3に示すような構成を有しており、鉄-ニッケル合金層20aと鋼板10との間に、鉄-ニッケル拡散層50を設けたという点において異なる以外は、第1実施形態に係る電池容器用表面処理鋼板100と同様の構成を有する。
次いで、本発明の第3実施形態について説明する。
第3実施形態に係る電池容器用表面処理鋼板は、図8に示すように鋼板10上に鉄-ニッケル合金めっき層30aおよびニッケルめっき層40aをこの順で形成した後、熱処理を施し、これにより、各層を熱拡散させて最表層を鉄-ニッケル合金層とすることにより製造されるという点において異なる以外は、図1に示す第1実施形態に係る電池容器用表面処理鋼板と同様の方法により製造され、同様の構成を有する。
なお、各特性の評価方法は、以下のとおりである。
走査型電子顕微鏡(SEM)を用いて電池容器用表面処理鋼板に電子線を照射した際に、電池容器用表面処理鋼板の表面で反射された電子線をスクリーンに投影して得られる電子後方散乱パターン(EBSD)を解析することにより、隣り合う照射点間の反射角度差が2°以内となる領域を一つの結晶粒として扱い、結晶粒毎に結晶粒径を算出し、これを平均することにより、電池容器用表面処理鋼板の最表面における平均結晶粒径を得た。
走査型オージェ電子分光分析装置(日本電子社製、型番:JAMP-9500F)を用いて、電池容器用表面処理鋼板の表面を測定することによりFe原子の含有割合(原子%)を得た。
電池容器用表面処理鋼板について、微小硬度計(株式会社明石製作所製、型番:MVK-G2)により、ダイヤモンド圧子を用いて、荷重:10gf、保持時間:10秒の条件でビッカース硬度(HV)を測定することにより、表面硬度の測定を行った。
電池容器用表面処理鋼板を用いて製造したアルカリマンガン電池を、温度80℃の環境で3日間保管した後、電池に電流計を接続して閉回路を設け、この際に両端子間に流れる電流(短絡電流)を測定し、得られた電流値に基づいて、以下の基準にて電池特性の評価を行った。
A:短絡電流が9A以上
B:短絡電流が8A以上、9A未満
C:短絡電流が7A以上、8A未満
D:短絡電流が7A未満
なお、電池特性の評価結果においては、短絡電流が9A以上(評価A)の電池容器用表面処理鋼板は、電池特性に優れると判断して合格とし、短絡電流が9A未満(評価B~D)の電池容器用表面処理鋼板については、電池容器として用いた場合における電池特性が劣るものであると判断して不合格とした。
まず、電池容器用表面処理鋼板を用いて製造したアルカリマンガン電池に対して、電気抵抗値が3.9Ωである外部負荷を接続し、1日に1時間放電するという操作を数日間繰り返すことによって、アルカリマンガン電池の電圧を0.4Vまで低下させた。その後、該アルカリマンガン電池を温度60℃の環境で20日間保管した後、水中で破壊し、その際に水中で発生したガスの量を測定した。測定結果については、以下の基準にて評価を行った。
A:発生したガスの量が2cc未満
B:発生したガスの量が2cc以上、2.5cc未満
C:発生したガスの量が2.5cc以上、3cc未満
D:発生したガスの量が3cc以上
なお、ガス発生量の評価結果においては、発生したガスの量が3cc未満(評価A、B)の電池容器用表面処理鋼板は、電池容器として用いた際に電池寿命が長いものであると判断して合格とし、発生したガスの量が2.5cc以上(評価C、D)の電池容器用表面処理鋼板については、電池容器として用いた際に電池寿命が短いものであると判断して不合格とした。
基体として、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%、残部:Feおよび不可避的不純物
浴組成:硫酸ニッケル240g/L、塩化ニッケル45g/L、硫酸鉄10g/L、ホウ酸30g/L
pH:3.0
浴温:60℃
電流密度:10A/dm2
そして、このようにして得られた電池容器用表面処理鋼板について、上述した方法にしたがって、平均結晶粒径の測定、熱処理後の最表層のFe原子の含有割合の測定、表面硬度の測定を行った。結果を表1に示す。
そして、このようにして得られたアルカリマンガン電池について、上述した方法にしたがって、電池特性の評価、ガス発生量の評価を行った。結果を表1に示す。
電解めっきにより形成した鉄-ニッケル合金めっき層(上層めっき層)の組成が表1に示すものとなるようにめっき条件を変更した以外は、実施例1と同様にして電池容器用表面処理鋼板およびアルカリマンガン電池を作製し、同様にして評価を行った。結果を表1に示す。
電解めっきにより形成した鉄-ニッケル合金めっき層(上層めっき層)の組成が表1に示すものとなるようにめっき条件を変更した以外は、実施例1と同様にして電池容器用表面処理鋼板およびアルカリマンガン電池を作製し、同様にして評価を行った。結果を表1に示す。
上層めっき層として、上述した鉄-ニッケル合金めっき層に代えて、下記条件にて電解めっきを行うことで厚さ2μmのニッケルめっき層を形成した以外は、実施例1と同様にして電池容器用表面処理鋼板およびアルカリマンガン電池を作製し、同様にして評価を行った。結果を表1に示す。
浴組成:硫酸ニッケル250g/L、塩化ニッケル45g/L、ホウ酸30g/L
pH:4.2
浴温:60℃
電流密度:10A/dm2
電解めっきにより形成したニッケルめっき層(上層めっき層)の厚さを表1に示すものとし、さらに、上述した連続焼鈍による熱処理に代えて、表1に示す条件にて箱型焼鈍を行った以外は、比較例3と同様にして電池容器用表面処理鋼板およびアルカリマンガン電池を作製し、同様にして評価を行った。結果を表1に示す。
予め鋼板上に下記条件にて厚さ0.8μmのニッケルめっき層(下層めっき層)を形成した後、該ニッケルめっき層上に電解めっきにより鉄-ニッケル合金めっき層(上層めっき層)を形成し、さらに、形成される鉄-ニッケル合金めっき層の組成および厚みが表2に示すものとなるようにめっき条件を変更することで、図3に示すようなニッケルめっき層が残存しない構成の電池容器用表面処理鋼板を作製した以外は、実施例1と同様にして、電池容器用表面処理鋼板およびアルカリマンガン電池を作製し、同様にして評価を行った。結果を表2に示す。なお、実施例6では、めっき層としては、上層めっき層として鉄-ニッケル合金めっき層を形成し、下層めっき層としてニッケルめっき層を形成した。
浴組成:硫酸ニッケル250g/L、塩化ニッケル45g/L、ホウ酸30g/L
pH:4.2
浴温:60℃
電流密度:10A/dm2
電解めっきにより形成した鉄-ニッケル合金めっき層(上層めっき層)の組成が表2に示すものとなるようにめっき条件を変更した以外は、実施例6と同様にして、図3に示す構成の電池容器用表面処理鋼板およびアルカリマンガン電池を作製し、同様にして評価を行った。結果を表2に示す。
鋼板上に形成したニッケルめっき層(下層めっき層)の厚みが表2に示すものとなるようにし、かつ、該ニッケルめっき層上に形成した鉄-ニッケル合金めっき層(上層めっき層)の組成および厚みが表2に示すものとなるように各めっき条件を変更することで、図6に示すようなニッケルめっき層が残存した構成の電池容器用表面処理鋼板を作製した以外は、実施例6と同様にして、電池容器用表面処理鋼板およびアルカリマンガン電池を作製し、同様にして評価を行った。結果を表2に示す。
電解めっきにより形成した鉄-ニッケル合金めっき層(下層めっき層)の組成および厚みが表3に示すものとなるように鋼板上に鉄-ニッケル合金めっき層を形成した後、さらに、該鉄-ニッケル合金めっき層上に厚さ0.1μmのニッケルめっき層(上層めっき層)を形成し、熱処理を行なうことで、鉄-ニッケル合金めっき層およびニッケルめっき層を熱拡散させて鉄-ニッケル合金層を形成し、図1に示す構成の電池容器用表面処理鋼板を作製した以外は、実施例1と同様にして、電池容器用表面処理鋼板およびアルカリマンガン電池を作製し、同様にして評価を行った。結果を表3に示す。なお、実施例10では、めっき層としては、上層めっき層としてニッケルめっき層を形成し、下層めっき層として鉄-ニッケル合金めっき層を形成した。
電解めっきにより形成した鉄-ニッケル合金めっき層(下層めっき層)の組成が表3に示すものとなるようにめっき条件を変更した以外は、実施例10と同様にして、電池容器用表面処理鋼板およびアルカリマンガン電池を作製し、同様にして評価を行った。結果を表3に示す。
最表層に形成されるニッケルめっき層(上層めっき層)の厚さを表3に示すものとした以外は、比較例3と同様にして電池容器用表面処理鋼板およびアルカリマンガン電池を作製し、同様にして評価を行った。結果を表3に示す。
電解めっきにより形成した鉄-ニッケル合金めっき層(下層めっき層)の組成が表3に示すものとなるようにめっき条件を変更した以外は、実施例10と同様にして、電池容器用表面処理鋼板およびアルカリマンガン電池を作製し、同様にして評価を行った。結果を表3に示す。
10…鋼板
20、20a…鉄-ニッケル合金層
30、30a…鉄-ニッケル合金めっき層
40、40a…ニッケルめっき層
50…鉄-ニッケル拡散層
Claims (5)
- 鋼板上に鉄-ニッケル合金めっきを施した後、熱処理を施してなる電池容器用表面処理鋼板であって、
最表層が鉄-ニッケル合金層であり、
前記鉄-ニッケル合金層は、最表面における平均結晶粒径が1~8μmであることを特徴とする電池容器用表面処理鋼板。 - 前記鉄-ニッケル合金層の最表面におけるFe原子の含有割合が12~50原子%であ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。
- 前記鉄-ニッケル合金層のビッカース硬度(HV)が210~250であ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。
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KR1020157036497A KR102216706B1 (ko) | 2013-07-31 | 2014-04-18 | 전지 용기용 표면 처리 강판, 전지 용기 및 전지 |
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PCT/JP2014/061020 WO2015015846A1 (ja) | 2013-07-31 | 2014-04-18 | 電池容器用表面処理鋼板、電池容器および電池 |
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US (1) | US9887396B2 (ja) |
JP (1) | JP6292789B2 (ja) |
KR (1) | KR102216706B1 (ja) |
CN (1) | CN105431959B (ja) |
WO (1) | WO2015015846A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018011287A1 (de) | 2016-07-13 | 2018-01-18 | Saint-Gobain Glass France | Beheiztes glas |
WO2020137874A1 (ja) | 2018-12-27 | 2020-07-02 | 日本製鉄株式会社 | 加工後耐食性に優れたNiめっき鋼板、及びNiめっき鋼板の製造方法 |
Families Citing this family (2)
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KR102477435B1 (ko) * | 2020-12-09 | 2022-12-15 | 주식회사 티씨씨스틸 | 가공성이 우수한 니켈 도금 열처리 강판 및 이의 제조방법 |
KR102514058B1 (ko) | 2021-05-20 | 2023-03-28 | 주식회사 티씨씨스틸 | 니켈 도금 스테인레스 강판 및 이의 제조방법 |
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JPH06346284A (ja) * | 1993-06-04 | 1994-12-20 | Katayama Tokushu Kogyo Kk | 電池用缶の形成材料及びその製造方法 |
JPH10212595A (ja) * | 1998-03-06 | 1998-08-11 | Katayama Tokushu Kogyo Kk | 電池用缶の形成材料の製造方法および該形成材料からなる電池缶 |
JP3429319B2 (ja) * | 1996-05-09 | 2003-07-22 | 東洋鋼鈑株式会社 | 電池ケース及び電池ケース用表面処理鋼板 |
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US4200515A (en) * | 1979-01-16 | 1980-04-29 | The International Nickel Company, Inc. | Sintered metal powder-coated electrodes for water electrolysis prepared with polysilicate-based paints |
CN1124656C (zh) * | 1997-07-08 | 2003-10-15 | 东洋钢板株式会社 | 电池容器、电池容器用的表面处理钢板及其制造方法 |
TW445663B (en) * | 1998-07-24 | 2001-07-11 | Toyo Kohan Co Ltd | A method of surface treatment for a battery container, a surface treated steel sheet for a battery container, a battery container and a battery using thereof |
JP4130989B2 (ja) | 1998-08-10 | 2008-08-13 | 東芝電池株式会社 | アルカリ乾電池 |
JP2006190648A (ja) * | 2004-12-10 | 2006-07-20 | Toyo Kohan Co Ltd | 電池容器用めっき鋼板、その電池容器用めっき鋼板を用いた電池容器、およびその電池容器を用いた電池 |
JP4839024B2 (ja) * | 2005-06-22 | 2011-12-14 | パナソニック株式会社 | 電池缶およびその製造方法 |
JP4983095B2 (ja) * | 2006-05-23 | 2012-07-25 | トヨタ自動車株式会社 | アルカリ蓄電池、及びその製造方法 |
-
2013
- 2013-07-31 JP JP2013158573A patent/JP6292789B2/ja active Active
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2014
- 2014-04-18 CN CN201480043048.9A patent/CN105431959B/zh active Active
- 2014-04-18 WO PCT/JP2014/061020 patent/WO2015015846A1/ja active Application Filing
- 2014-04-18 KR KR1020157036497A patent/KR102216706B1/ko active IP Right Grant
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2016
- 2016-01-29 US US15/011,331 patent/US9887396B2/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH06346284A (ja) * | 1993-06-04 | 1994-12-20 | Katayama Tokushu Kogyo Kk | 電池用缶の形成材料及びその製造方法 |
JP3429319B2 (ja) * | 1996-05-09 | 2003-07-22 | 東洋鋼鈑株式会社 | 電池ケース及び電池ケース用表面処理鋼板 |
JPH10212595A (ja) * | 1998-03-06 | 1998-08-11 | Katayama Tokushu Kogyo Kk | 電池用缶の形成材料の製造方法および該形成材料からなる電池缶 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018011287A1 (de) | 2016-07-13 | 2018-01-18 | Saint-Gobain Glass France | Beheiztes glas |
WO2020137874A1 (ja) | 2018-12-27 | 2020-07-02 | 日本製鉄株式会社 | 加工後耐食性に優れたNiめっき鋼板、及びNiめっき鋼板の製造方法 |
KR20210087073A (ko) | 2018-12-27 | 2021-07-09 | 닛폰세이테츠 가부시키가이샤 | 가공 후 내식성이 우수한 Ni 도금 강판, 및 Ni 도금 강판의 제조 방법 |
Also Published As
Publication number | Publication date |
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KR20160037845A (ko) | 2016-04-06 |
CN105431959A (zh) | 2016-03-23 |
JP6292789B2 (ja) | 2018-03-14 |
CN105431959B (zh) | 2018-07-06 |
US9887396B2 (en) | 2018-02-06 |
US20160211489A1 (en) | 2016-07-21 |
JP2015032346A (ja) | 2015-02-16 |
KR102216706B1 (ko) | 2021-02-16 |
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