WO2014007002A1 - Plaque d'acier traitée en surface destinée à un récipient de batterie, récipient de batterie et batterie - Google Patents

Plaque d'acier traitée en surface destinée à un récipient de batterie, récipient de batterie et batterie Download PDF

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WO2014007002A1
WO2014007002A1 PCT/JP2013/064993 JP2013064993W WO2014007002A1 WO 2014007002 A1 WO2014007002 A1 WO 2014007002A1 JP 2013064993 W JP2013064993 W JP 2013064993W WO 2014007002 A1 WO2014007002 A1 WO 2014007002A1
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nickel
cobalt
cobalt alloy
battery
steel sheet
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PCT/JP2013/064993
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English (en)
Japanese (ja)
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友森　龍夫
慎一郎 堀江
興 吉岡
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東洋鋼鈑株式会社
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Priority to JP2014523645A priority Critical patent/JP6033304B2/ja
Publication of WO2014007002A1 publication Critical patent/WO2014007002A1/fr

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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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • 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
    • H01M50/126—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
    • 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.
  • a battery container material a material that is excellent in resistance to dissolution in a strong alkaline electrolyte and that can realize high battery performance is desired.
  • Patent Document 1 proposes a plated steel sheet in which a nickel plating layer and a cobalt plating layer are formed in order from the bottom on the surface of the steel sheet.
  • Patent Document 1 by forming a cobalt plating layer as the outermost layer, the conductivity in the surface of the plated steel sheet is improved, thereby improving the battery characteristics even when the conductive film is not formed. Yes.
  • Patent Document 1 when the present inventors have examined, when the plated steel sheet disclosed in Patent Document 1 is used as a battery container of a battery using a strong alkaline electrolyte such as an alkaline battery or a nickel metal hydride battery, It was recognized that cobalt was eluted over time, and that this elution of cobalt caused gas generation inside the battery, leading to the occurrence of liquid leakage.
  • a strong alkaline electrolyte such as an alkaline battery or a nickel metal hydride battery
  • the object of the present invention is to have excellent conductivity on the inner surface of the battery container, and effectively prevent cobalt from leaching in a strong alkaline electrolyte having a wide concentration range (particularly, a concentration range used as a battery electrolyte). 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 found that the nickel-cobalt alloy layer formed on the outermost surface of the battery container inner surface is immersed in an aqueous potassium hydroxide solution. It has been found that the above-mentioned object can be achieved when the potential difference with respect to the immersion potential has a predetermined relationship with the concentration of the aqueous potassium hydroxide solution, and the present invention has been completed.
  • a surface-treated steel sheet for a battery container in which a nickel-cobalt alloy layer is formed on the outermost surface of the battery container, wherein x [wt%] (where 30 ⁇ x ⁇ 50)
  • x [wt%] where 30 ⁇ x ⁇ 50
  • y [mV] immersion potential of nickel-cobalt alloy layer”.
  • immersion potential of nickel-cobalt alloy layer "immersion potential of nickel-cobalt alloy layer”.
  • 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.
  • a nickel layer as a lower layer of the nickel-cobalt alloy layer.
  • an iron-nickel diffusion layer and / or an iron-nickel-cobalt diffusion layer is provided between the nickel-cobalt alloy layer and the steel plate.
  • 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 nickel-cobalt alloy layer formed on the outermost surface of the battery container is immersed in a potassium hydroxide aqueous solution, the potential difference with respect to the cobalt immersion potential and the potassium hydroxide aqueous solution
  • concentration so as to satisfy the above-described relationship, it is excellent in conductivity on the inner surface of the battery container and is a strong alkaline electrolyte in a wide concentration range (particularly, a concentration range used as a battery electrolyte).
  • FIG. 1 is a graph showing the relationship between the concentration of an aqueous potassium hydroxide solution and the immersion potential difference between a nickel-cobalt alloy layer and cobalt in Examples and Comparative Examples of the present invention.
  • the surface-treated steel sheet for battery containers of 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 inner surface of the battery container, and x [wt%] (
  • y [mV] “nickel-cobalt alloy”.
  • immersion potential of layer ⁇ “immersion potential of cobalt”
  • 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.
  • the nickel-cobalt alloy layer is calculated by the potential difference between the immersion potential of the nickel-cobalt alloy layer and the cobalt immersion potential in the aqueous potassium hydroxide solution ("immersion potential of the nickel-cobalt alloy layer"-"cobalt immersion potential").
  • immersion potential of the nickel-cobalt alloy layer immersion potential of the nickel-cobalt alloy layer
  • KOH concentration of the aqueous potassium hydroxide solution
  • the surface-treated steel sheet for battery containers of the present invention obtained by controlling the potential difference when the nickel-cobalt alloy layer is immersed in KOH within the range of the above formula (1), the nickel-cobalt alloy layer is disposed on the inner surface.
  • the nickel-cobalt alloy layer When used as a battery container, it has excellent conductivity on the inner surface of the battery container due to the action of cobalt having excellent conductivity, and has a strong alkalinity in a wide concentration range (especially, a concentration range used as a battery electrolyte). Cobalt elution can be effectively prevented with respect to the electrolyte solution.
  • the present inventors have determined that the potential difference with respect to the immersion potential of cobalt when the nickel-cobalt alloy layer formed on the outermost surface of the battery container is immersed in an aqueous potassium hydroxide solution (the above-mentioned nickel-cobalt alloy).
  • the potential difference during the KOH immersion of the nickel-cobalt alloy layer changes when the concentration of the potassium hydroxide aqueous solution changes.
  • the knowledge that the potential difference at the time of KOH immersion of the nickel-cobalt alloy layer that can prevent cobalt elution is different depending on the concentration of the aqueous potassium hydroxide solution is obtained.
  • the potential difference when the nickel-cobalt alloy layer is immersed in KOH and the concentration of the aqueous potassium hydroxide solution should satisfy the relationship of the above formula (1). What satisfies the relationship of following formula (2) from the point that it can raise more is more preferable. y ⁇ ⁇ 3.301x + 258.3 (2)
  • the nickel-cobalt alloy layer and cobalt are immersed in a potassium hydroxide aqueous solution whose concentration is adjusted in the range of 30 to 50% by weight, for example. Then, the natural potential 15 minutes after the start of immersion is measured, and this can be set as the immersion potential.
  • the time for immersing the nickel-cobalt alloy layer and cobalt in the aqueous potassium hydroxide solution should be set based on the time required for the natural potential value to stabilize after immersion. In the present invention, for example, it can be set to 15 minutes as described above.
  • the measurement of the immersion potential of cobalt prepares the cobalt plating steel plate which performed the cobalt plating to the steel plate similar to the surface treatment steel plate for battery containers of this invention, and is the cobalt layer of the prepared cobalt plating steel plate.
  • the natural potential can be measured.
  • the potential difference when the nickel-cobalt alloy layer is immersed in KOH is obtained by measuring the natural potential with respect to / AgCl and then obtaining the potential difference obtained by subtracting the cobalt immersion potential from the immersion potential of the nickel-cobalt alloy layer. Can do.
  • the method of setting the potential difference when the nickel-cobalt alloy layer is immersed in KOH within the range of the above formula (1) is not particularly limited, but examples thereof include the following method. That is, as a first method, a method of forming a nickel-cobalt alloy plating layer on the surface of a steel sheet using a nickel-cobalt alloy plating bath having a cobalt / nickel ratio within a predetermined range can be mentioned. Alternatively, as a second method, a nickel-cobalt alloy plating bath is used to form a nickel-cobalt alloy plating layer on the surface of the steel sheet, and then heat diffusion is performed on the nickel-cobalt alloy plating layer.
  • a third method there is a method in which a nickel plating layer and a cobalt plating layer are formed in this order on the surface of the steel sheet, and then thermally diffused by applying heat treatment thereto to form a nickel-cobalt alloy layer.
  • the method of setting the potential difference when the nickel-cobalt alloy layer is immersed in KOH within the range of the above formula (1) is not particularly limited to the above method.
  • a nickel-cobalt alloy plating layer is formed on the surface of a steel sheet using a nickel-cobalt alloy plating bath having a cobalt / nickel ratio within a predetermined range by the first method
  • a plating bath based on a watt bath containing nickel sulfate, nickel chloride, cobalt sulfate and boric acid.
  • the cobalt / nickel ratio in the plating bath is preferably in the range of 0.10 to 0.29, more preferably in the range of 0.10 to 0.24, 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
  • the nickel-cobalt alloy plating bath When the nickel-cobalt alloy plating bath is used to form a nickel-cobalt alloy plating layer on the surface of the steel plate, the nickel-cobalt alloy plating bath has a bath temperature of 40 to 80 ° C. and a pH of 1.5 to Preferably, the conditions are 5.0 and the current density is 1 to 40 A / dm 2.
  • the plating thickness is preferably 0.01 to 3.0 ⁇ m, more preferably 0.05 to 2.0 ⁇ m, still more preferably. 0.1 to 1.0 ⁇ m.
  • the base nickel plating layer may be formed by performing base nickel plating before forming the nickel-cobalt alloy layer.
  • the underlying nickel plating layer can be usually formed using a watt bath, and the thickness is preferably 0.05 to 3.0 ⁇ m, more preferably 0.1 to 2.0 ⁇ m.
  • the surface-treated steel sheet for battery containers of the present invention has a nickel layer and a nickel-cobalt alloy layer in order from the bottom on the steel sheet (Ni—Co / Ni / Fe).
  • 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 700 to 800 ° C.
  • the heat treatment time is preferably 10 to 300 seconds.
  • the heat treatment temperature is 450 to 600 ° C.
  • 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 formed on the steel sheet in the order from the bottom, the iron-nickel diffusion layer and the nickel-cobalt alloy layer.
  • the structure (Ni—Co / Ni—Fe / Fe) can be obtained.
  • the surface-treated steel sheet for battery containers of 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 / Ni—Fe / Fe).
  • the nickel-cobalt alloy plating bath is first made of nickel sulfate, nickel chloride, A nickel-cobalt alloy layer before heat treatment is formed using a plating bath based on a Watt bath containing cobalt sulfate and boric acid.
  • the cobalt / nickel ratio in the plating bath is preferably in the range of 0.10 to 0.29, and more preferably in the range of 0.10 to 0.24, as the molar ratio of cobalt / nickel.
  • the nickel-cobalt alloy plating is preferably performed under conditions of a bath temperature of 40 to 80 ° C., a pH of 1.5 to 5.0, and a current density of 1 to 40 A / dm 2 , and the plating thickness is preferably 0.01 to The thickness is 2.0 ⁇ m, more preferably 0.05 to 1.0 ⁇ m.
  • the base nickel plating layer may be formed by performing base nickel plating before forming the nickel-cobalt alloy 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 steel sheet on which the nickel-cobalt alloy layer before heat treatment is formed as described above is subjected to a heat diffusion treatment by heat treatment.
  • the heat treatment may be performed by either a continuous annealing method or a box-type annealing method, and the heat treatment conditions include the cobalt / nickel ratio of the nickel-cobalt alloy plating bath used and the nickel-cobalt before the heat treatment.
  • the heat treatment temperature 700 to 800 ° C.
  • heat treatment time 10 seconds to 300 seconds.
  • heat treatment temperature 450 to 600 ° 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.
  • an iron-nickel diffusion layer and / or an iron-nickel-cobalt diffusion layer is formed between the steel plate and the nickel-cobalt alloy layer by performing the thermal diffusion treatment described above. Therefore, the surface-treated steel sheet for battery containers of the present invention has an iron-nickel diffusion layer and / or an iron-nickel-cobalt diffusion layer and a nickel-cobalt alloy layer on the steel plate in order from the bottom. (Ni—Co / Fe—Ni and / or Fe—Ni—Co / Fe).
  • the surface-treated steel sheet for battery containers of the present invention is ironed on the steel sheet in order from the bottom.
  • a structure having a nickel diffusion layer and a nickel-cobalt alloy layer (Ni-Co / Fe-Ni / Fe), or an iron-nickel diffusion layer, a nickel layer, and a nickel-cobalt alloy on a steel plate in order from the bottom A structure having a layer (Ni—Co / Ni / Fe—Ni / Fe) can be employed.
  • a nickel plating layer is formed on the surface of a steel sheet using a nickel plating bath.
  • a plating bath usually used in nickel plating, that is, a watt bath, a citric acid bath, a sulfamic acid bath, a borofluoride bath, a chloride bath, or the like can be used.
  • the nickel plating layer uses a bath composition of nickel sulfate 200 to 350 g / L, nickel chloride 20 to 60 g / L, boric acid 10 to 50 g / L as a watt bath, pH 1.5 to 5.0, bath It can be formed at a temperature of 40 to 80 ° C. and a current density of 1 to 40 A / dm 2 .
  • the thickness of the nickel plating layer is preferably 0.05 to 3.0 ⁇ m, more preferably 0.1 to 2.0 ⁇ m.
  • the cobalt plating layer is formed on the nickel plating layer by performing cobalt plating on the steel plate on which the nickel plating layer is formed.
  • the cobalt plating layer is formed by using, for example, a cobalt plating bath having a bath composition of cobalt sulfate: 200 to 300 g / L, cobalt chloride: 50 to 150 g / L, sodium chloride: 10 to 50 g / L, pH: 2 to 5, It can be formed under conditions of bath temperature: 40 to 80 ° C. and current density: 1 to 40 A / dm 2 .
  • the thickness of the cobalt plating layer is preferably 0.01 to 2.0 ⁇ m, more preferably 0.05 to 1.0 ⁇ m.
  • the steel plate on which the nickel plating layer and the cobalt plating layer are formed is subjected to a heat treatment so that the nickel plating layer and the cobalt plating layer are thermally diffused to form a nickel-cobalt alloy layer.
  • the heat treatment may be performed by either a continuous annealing method or a box-type annealing method, and the heat treatment conditions are appropriately determined according to the thickness of the nickel plating layer before the heat treatment or the thickness of the cobalt plating layer.
  • the heat treatment temperature is preferably 700 to 800 ° C. and the heat treatment time is preferably 10 seconds to 300 seconds.
  • Heat treatment temperature 450 to 600 ° C.
  • heat treatment time 1 hour to 10 hours
  • heat treatment atmosphere non-oxidizing atmosphere or reducing protective gas atmosphere
  • an iron-nickel diffusion layer can be formed between the steel plate and the nickel layer by performing the above-described thermal diffusion treatment, and therefore, for the battery container of the present invention.
  • the surface-treated steel sheet can have a structure (Ni—Co / Ni / Fe—Ni / Fe) having an iron-nickel diffusion layer, a nickel layer, and a nickel-cobalt alloy layer in order from the bottom on the steel sheet. .
  • the nickel layer can be completely thermally diffused.
  • the surface-treated steel sheet for battery containers of the present invention is placed on the steel sheet. From the bottom, a structure having an iron-nickel diffusion layer and a nickel-cobalt alloy layer (Ni—Co / Fe—Ni / Fe) can be employed.
  • the potential difference when the nickel-cobalt alloy layer is immersed in KOH is within the range satisfying the above formula (1).
  • a surface-treated steel sheet can be obtained.
  • the surface-treated steel sheet for a battery container according to the present invention is used as a battery container having a nickel-cobalt alloy layer as an inner surface, it has excellent conductivity on the inner surface of the battery container due to the action of cobalt having excellent conductivity.
  • the potassium hydroxide solution as the strong alkaline electrolyte high dissolution resistance can be ensured according to the concentration of potassium hydroxide in the solution.
  • 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, the battery container has an excellent conductivity on the inner surface of the battery container and a potassium hydroxide solution as a strong alkaline electrolyte.
  • a potassium hydroxide solution as a strong alkaline electrolyte.
  • it is suitable as a battery container such as a battery using an alkaline electrolyte such as an alkaline battery or a nickel metal hydride battery. Can be used.
  • 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.
  • a surface-treated steel sheet having a coating amount of 15 g / m 2 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 0.10 pH: 3.5-5.0 Bath temperature: 60 ° C Current density: 10 A / dm 2
  • the immersion potential of cobalt was measured.
  • a steel plate similar to the above-mentioned surface-treated steel plate is subjected to alkaline electrolytic degreasing and sulfuric acid immersion pickling, and then using a cobalt plating bath containing cobalt sulfate, cobalt chloride, and sodium chloride, pH: 2-5, bath temperature: 60 ° C., a current density: 10A / dm by performing the cobalt plating at 2 conditions, to obtain a cobalt-plated steel sheet amount film is 15 g / m 2, the resulting cobalt-plated steel sheet The immersion potential was measured under the above conditions.
  • the difference between the measured immersion potential of the nickel-cobalt alloy layer and the immersion potential of cobalt was determined to obtain a potential difference when the nickel-cobalt alloy layer was immersed in KOH.
  • the concentration of the potassium hydroxide aqueous solution as the electrolytic solution was changed to 35, 38, 42, 45, and 50% by weight, and the nickel-cobalt alloy layer was immersed in the same manner for each potassium hydroxide aqueous solution of each concentration.
  • the potential and the immersion potential of cobalt were measured, and the potential difference when the nickel-cobalt alloy layer was immersed in KOH was determined. The results are shown in Table 1.
  • Example 2 A surface-treated steel sheet was obtained in the same manner as in Example 1 except that the cobalt / nickel ratio of the bath composition was changed to 0.14 when forming the nickel-cobalt alloy plating layer, and the concentrations shown in Table 2 were obtained. The same evaluation was performed in an aqueous potassium hydroxide solution. The results are shown in Table 2.
  • Example 3 A surface-treated steel sheet was obtained in the same manner as in Example 1 except that the cobalt / nickel ratio of the bath composition was changed to 0.19 when forming the nickel-cobalt alloy plating layer, and the concentrations shown in Table 3 were obtained. The same evaluation was performed in an aqueous potassium hydroxide solution. The results are shown in Table 3.
  • Example 4 A surface-treated steel sheet was obtained in the same manner as in Example 1 except that the cobalt / nickel ratio of the bath composition was changed to 0.24 when forming the nickel-cobalt alloy plating layer, and the concentrations shown in Table 4 were obtained. The same evaluation was performed in an aqueous potassium hydroxide solution. The results are shown in Table 4.
  • Example 5 A surface-treated steel sheet was obtained in the same manner as in Example 1 except that the cobalt / nickel ratio of the bath composition was changed to 0.29 when forming the nickel-cobalt alloy plating layer, and the concentrations shown in Table 5 were obtained. The same evaluation was performed in an aqueous potassium hydroxide solution. The results are shown in Table 5.
  • Example 6 After forming the nickel-cobalt alloy plating layer, the surface was treated in the same manner as in Example 1 except that heat treatment was performed under the conditions of heat treatment temperature: 700 ° C. and heat treatment time: 60 seconds, and heat diffusion was performed. A treated steel plate was obtained and evaluated in the same manner in a potassium hydroxide aqueous solution having the concentration shown in Table 6. The results are shown in Table 6.
  • Example 7 A surface-treated steel sheet was obtained in the same manner as in Example 6 except that the cobalt / nickel ratio of the bath composition was changed to 0.14 when forming the nickel-cobalt alloy plating layer, and the concentrations shown in Table 7 were obtained. The same evaluation was performed in an aqueous potassium hydroxide solution. The results are shown in Table 7.
  • Example 8 A surface-treated steel sheet was obtained in the same manner as in Example 6 except that the cobalt / nickel ratio of the bath composition was changed to 0.19 when forming the nickel-cobalt alloy plating layer, and the concentrations shown in Table 8 were obtained. The same evaluation was performed in an aqueous potassium hydroxide solution. The results are shown in Table 8.
  • Example 9 A surface-treated steel sheet was obtained in the same manner as in Example 6 except that the cobalt / nickel ratio of the bath composition was changed to 0.24 when forming the nickel-cobalt alloy plating layer, and the concentrations shown in Table 9 were obtained. The same evaluation was performed in an aqueous potassium hydroxide solution. The results are shown in Table 9.
  • Example 10 A surface-treated steel sheet was obtained in the same manner as in Example 6 except that the cobalt / nickel ratio of the bath composition was changed to 0.29 when forming the nickel-cobalt alloy plating layer, and the concentrations shown in Table 10 were obtained. The same evaluation was performed in an aqueous potassium hydroxide solution. The results are shown in Table 10.
  • Example 2 A surface-treated steel sheet was obtained in the same manner as in Example 1 except that the cobalt / nickel ratio of the bath composition was changed to 0.35 when forming the nickel-cobalt alloy plating layer. Evaluation was similarly performed in a potassium hydroxide aqueous solution having a concentration. The results are shown in Table 12.
  • Example 3 A surface-treated steel sheet was obtained in the same manner as in Example 1 except that the cobalt / nickel ratio of the bath composition was changed to 0.32 when forming the nickel-cobalt alloy plating layer. Evaluation was similarly performed in a potassium hydroxide aqueous solution having a concentration. The results are shown in Table 13.
  • FIG. 1 (A) is a graph in which the results of all examples and comparative examples (Examples 1 to 10 and Comparative Examples 1 to 3) are plotted.
  • FIG. 1B is a graph in which FIG. ) Is a graph obtained by changing the scale of the vertical axis and enlarging the vicinity of the straight line of the above formula (1) and the above formula (2). As shown in FIG.

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  • Organic Chemistry (AREA)
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Abstract

L'invention concerne une plaque d'acier traitée en surface destinée à un récipient de batterie qui présente une couche d'alliage de nickel-cobalt formée sur la surface la plus externe d'une surface qui forme la surface interne d'un récipient de batterie. La plaque d'acier traitée en surface destinée à un récipient de batterie est caractérisée par l'équation (1) qui est satisfaite lorsque la concentration en hydroxyde de potassium dans une solution aqueuse d'hydroxyde de potassium vaut x % en poids (ici, 30 ≤ x ≤ 50) et lorsque y (mV) représente la différence de potentiel du potentiel d'immersion de la couche d'alliage de nickel-cobalt lorsqu'elle est immergée dans la solution aqueuse d'hydroxyde de potassium à une concentration de x % en poids, par rapport au potentiel d'immersion du cobalt. y ≥ -0,984x + 136,7 … （1）
PCT/JP2013/064993 2012-07-03 2013-05-30 Plaque d'acier traitée en surface destinée à un récipient de batterie, récipient de batterie et batterie WO2014007002A1 (fr)

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
CN111699567A (zh) * 2018-02-14 2020-09-22 日本制铁株式会社 电池容器用表面处理钢板和电池容器用表面处理钢板的制造方法
EP3591098A4 (fr) * 2017-03-02 2021-01-27 Nippon Steel Corporation Tôle d'acier traitée en surface
CN112368425A (zh) * 2018-07-06 2021-02-12 日本制铁株式会社 表面处理钢板和表面处理钢板的制造方法
CN113748225A (zh) * 2019-04-27 2021-12-03 东洋钢钣株式会社 表面处理钢板和其制造方法
EP3819405A4 (fr) * 2018-07-06 2021-12-22 Nippon Steel Corporation Tôle d'acier traitée en surface et procédé de production d'une tôle d'acier traitée en surface

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WO1999003161A1 (fr) * 1997-07-08 1999-01-21 Toyo Kohan Co., Ltd. Feuille d'acier traitee en surface pour boitier de batterie, boitier de batterie et batterie fabriquee a l'aide dudit boitier
JP2006257543A (ja) * 2005-02-18 2006-09-28 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
JP2006351434A (ja) * 2005-06-17 2006-12-28 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
JP2006348362A (ja) * 2005-06-17 2006-12-28 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
JP2012048958A (ja) * 2010-08-26 2012-03-08 Fdk Energy Co Ltd アルカリ電池
WO2013005774A1 (fr) * 2011-07-07 2013-01-10 東洋鋼鈑株式会社 Tôle d'acier traitée en surface pour boîtier de batterie, procédé de production de celle-ci, boîtier de batterie et batterie

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Publication number Priority date Publication date Assignee Title
WO1999003161A1 (fr) * 1997-07-08 1999-01-21 Toyo Kohan Co., Ltd. Feuille d'acier traitee en surface pour boitier de batterie, boitier de batterie et batterie fabriquee a l'aide dudit boitier
JP2006257543A (ja) * 2005-02-18 2006-09-28 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
JP2006351434A (ja) * 2005-06-17 2006-12-28 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
JP2006348362A (ja) * 2005-06-17 2006-12-28 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
JP2012048958A (ja) * 2010-08-26 2012-03-08 Fdk Energy Co Ltd アルカリ電池
WO2013005774A1 (fr) * 2011-07-07 2013-01-10 東洋鋼鈑株式会社 Tôle d'acier traitée en surface pour boîtier de batterie, procédé de production de celle-ci, boîtier de batterie et batterie

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3591098A4 (fr) * 2017-03-02 2021-01-27 Nippon Steel Corporation Tôle d'acier traitée en surface
CN111699567A (zh) * 2018-02-14 2020-09-22 日本制铁株式会社 电池容器用表面处理钢板和电池容器用表面处理钢板的制造方法
CN112368425A (zh) * 2018-07-06 2021-02-12 日本制铁株式会社 表面处理钢板和表面处理钢板的制造方法
EP3819406A4 (fr) * 2018-07-06 2021-12-15 Nippon Steel Corporation Tôle d'acier traitée en surface et son procédé de fabrication
EP3819405A4 (fr) * 2018-07-06 2021-12-22 Nippon Steel Corporation Tôle d'acier traitée en surface et procédé de production d'une tôle d'acier traitée en surface
CN112368425B (zh) * 2018-07-06 2024-03-05 日本制铁株式会社 表面处理钢板和表面处理钢板的制造方法
CN113748225A (zh) * 2019-04-27 2021-12-03 东洋钢钣株式会社 表面处理钢板和其制造方法
CN113748225B (zh) * 2019-04-27 2024-04-30 东洋钢钣株式会社 表面处理钢板和其制造方法

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