WO2023033118A1 - 電池用表面処理金属板 - Google Patents

電池用表面処理金属板 Download PDF

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Publication number
WO2023033118A1
WO2023033118A1 PCT/JP2022/033006 JP2022033006W WO2023033118A1 WO 2023033118 A1 WO2023033118 A1 WO 2023033118A1 JP 2022033006 W JP2022033006 W JP 2022033006W WO 2023033118 A1 WO2023033118 A1 WO 2023033118A1
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Prior art keywords
nickel
layer
tin
metal plate
treated metal
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English (en)
French (fr)
Japanese (ja)
Inventor
道雄 河村
香織 上原
悦郎 堤
慎一郎 堀江
大輔 松重
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Toyo Kohan Co Ltd
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Toyo Kohan Co Ltd
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Priority to KR1020247009261A priority Critical patent/KR20240048537A/ko
Priority to JP2023516592A priority patent/JP7332838B2/ja
Priority to EP22864700.4A priority patent/EP4398349A4/en
Priority to US18/687,992 priority patent/US20240372109A1/en
Publication of WO2023033118A1 publication Critical patent/WO2023033118A1/ja
Priority to JP2023091930A priority patent/JP2023110037A/ja
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • 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
    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H01M4/662—Alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/669—Steels
    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/534—Electrode connections inside a battery casing characterised by the material of the leads or tabs
    • 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
    • H01M10/30—Nickel accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a surface-treated metal plate for batteries that can suppress gas generation and has excellent electrolyte resistance.
  • Nickel-cadmium batteries, nickel-metal hydride batteries, etc. have been put into practical use and are widely known as types of secondary batteries of so-called alkaline batteries, in which the electrolyte is an alkaline aqueous solution.
  • alkaline secondary batteries air batteries and nickel-zinc batteries that use nickel hydroxide or the like for the positive electrode, zinc or the like for the negative electrode active material, and an alkaline aqueous solution for the electrolyte are being actively developed as next-generation batteries. ing.
  • nickel-zinc batteries have high electromotive force and high energy density as water-based batteries, that zinc is inexpensive, that they do not contain rare metals, that both nickel and zinc are recyclable metals, For example, it is safer than lithium-ion batteries because it uses an aqueous electrolyte.
  • Patent Literature 1 an alloy of copper and tin is used as the material for the current collector of the negative electrode to increase the hydrogen overvoltage, thereby solving the problem of hydrogen gas generation as described above.
  • Patent Document 1 is insufficient in corrosion resistance (electrolyte solution resistance) when used in a practical alkaline secondary battery. That is, in order to exhibit sufficient battery performance as an alkaline secondary battery, the concentration of potassium hydroxide in the electrolyte is preferably 20% by weight or more. % by weight.
  • the concentration of potassium hydroxide in the electrolyte is preferably 20% by weight or more. % by weight.
  • the corrosion resistance is improved compared to copper alone, it still dissolves in the above-described high-concentration electrolyte environment. In addition, since the dissolution is further accelerated during the discharge reaction, it cannot be put to practical use.
  • nickel which is generally considered to have excellent alkali resistance
  • dissolution in alkaline electrolyte can be suppressed, but nickel has a small hydrogen overvoltage and hydrogen gas is likely to be generated.
  • zinc is involved in the battery reaction, the potential difference between zinc and zinc in the alkaline electrolyte is large, and hydrogen gas is remarkably likely to be generated.
  • the present inventors have developed a negative electrode current collector material and a battery tab/lead material that can suppress gas generation during charging and discharging of an alkaline secondary battery and can suppress dissolution in an electrolytic solution.
  • a surface-treated metal sheet for batteries that can be used as a battery container (battery exterior material)
  • we conducted extensive research we conducted extensive research.
  • the present inventors have found that it is possible to achieve both of the above-described problems by making the surface-treated metal sheet for batteries have a specific structure, and have completed the present invention.
  • the present inventors have made intensive studies to achieve the above object, and as a result, according to the surface-treated metal plate for batteries comprising a nickel-tin alloy layer on at least one side of an iron- or nickel-based metal plate, the above-mentioned We have found that the object can be achieved, and have completed the present invention.
  • a surface-treated metal plate for a battery wherein the substrate of the surface-treated metal plate for a battery is a metal plate based on iron or nickel, and a nickel-tin alloy layer is formed on at least one surface of the metal plate.
  • a surface-treated metal plate for a battery comprising:
  • GDS high frequency glow discharge luminescence surface analysis
  • the nickel-tin alloy layer contains, as an alloy phase, a nickel-tin alloy that provides diffraction peaks in the diffraction angle 2 ⁇ range of 40 to 42° and the diffraction angle 2 ⁇ range of 46 to 48°.
  • the metal plate is an electrolytic foil made of pure iron, an electrolytic foil made of pure nickel, or an electrolytic foil made of a binary alloy of iron and nickel. for surface-treated metal plates.
  • FIG. 1 is a cross-sectional view of a surface-treated metal plate for batteries according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of a surface-treated metal plate for batteries according to another embodiment of the present invention.
  • FIG. 3A is an X-ray diffraction (XRD) chart showing diffraction peaks of Ni—Sn 40-42 or Ni—Sn 46-48 .
  • FIG. 3B is an X-ray diffraction (XRD) chart showing diffraction peaks of Ni 3 Sn 4 .
  • FIG. 3C is an X-ray diffraction (XRD) chart showing diffraction peaks of Ni 3 Sn 2 .
  • FIG. 3D is an X-ray diffraction (XRD) chart showing the diffraction peaks of Ni—Sn 40-42 before and after the anode reaction test.
  • FIG. 3E is an X-ray diffraction (XRD) chart showing the diffraction peaks of Ni—Sn 46-48 before and after the anode reaction test.
  • FIG. 4 is a diagram for explaining a method of measuring thickness by high-frequency glow discharge luminescence surface spectroscopy (GDS).
  • FIG. 5(A) is a graph obtained by GDS measurement of the surface-treated metal plate for battery of Example 1, and FIGS. It is the graph obtained by GDS measurement about a metal plate.
  • the surface-treated metal plate for a battery of the present invention is a surface-treated metal plate used for battery applications, such as current collector applications for positive electrodes or negative electrodes, battery container applications for housing power generation elements of batteries, and the like.
  • used for The battery is not particularly limited, but examples include aqueous batteries such as nickel-cadmium batteries, nickel-hydrogen batteries, air-zinc batteries, and nickel-zinc batteries, and non-aqueous batteries such as lithium-ion batteries, using an alkaline electrolyte.
  • the surface-treated metal sheet for batteries of the present invention is suitable for use in aqueous batteries, and among aqueous batteries, it is particularly useful as a current collector for constituting an aqueous battery (for example, a nickel-zinc battery) in which zinc is involved in the battery reaction. It is suitably used for applications and battery container applications.
  • the present invention can be applied to either a primary battery or a secondary battery as long as it is an aqueous battery. An embodiment of the present invention will be described below based on the drawings.
  • FIG. 1 is a cross-sectional view of a surface-treated metal plate 10 for batteries according to an embodiment of the present invention.
  • the surface-treated metal sheet for battery 10 according to this embodiment includes nickel-tin alloy layers 40 on both sides of a base material 20 .
  • FIG. 1 illustrates a configuration in which the nickel-tin alloy layer 40 is formed through the nickel layer 30 formed on the base material 20, it is not particularly limited to such an embodiment.
  • a structure in which the nickel-tin alloy layer 40 is directly formed on the base material 20 may be used.
  • the nickel-tin alloy layer 40 is formed on both sides of the base material 20, but in the present embodiment, at least one surface of the base material 20 is formed with a nickel-tin alloy layer 40. Any material may be used as long as the layer 40 is formed thereon, and the material is not particularly limited to one in which the nickel-tin alloy layers 40 are formed on both sides. Further, in the present embodiment, the nickel-tin alloy layer 40 may be formed on the surface where suppression of gas generation is required. When used as a current collector for a negative electrode of a nickel-zinc battery, or as a lead material or tab material, the nickel-tin alloy layer 40 is formed on both sides of the base material 20.
  • a nickel-tin alloy layer 40 is formed on the surface of the base material 20 that serves as the inner surface of the battery.
  • the nickel-tin alloy layer 40 is formed on the inner surface of the battery.
  • the surface to be the outer surface of the battery is not particularly limited. can also be formed.
  • the base material 20 is not particularly limited as long as it is a metal plate based on iron or nickel. 003% by weight or less ultra-low carbon steel, non-aging ultra-low carbon steel obtained by adding Ti or Nb to ultra-low carbon steel, or a nickel plate. Low carbon steel and ultra-low carbon steel can be preferably used.
  • an electrolytic foil made of pure iron an electrolytic foil having an iron content of 99.9% by weight or more
  • an electrolytic foil made of pure nickel an electrolytic foil having a nickel content of 99.9% by weight, % or more
  • an electrolytic foil made of a binary alloy of iron and nickel when the surface-treated metal plate 10 for a battery according to the present embodiment is used as a current collector for a positive electrode or a negative electrode, the substrate 20 may be a perforated plate or perforated foil having through holes. good.
  • the thickness of the base material 20 is not particularly limited. 0.025 to 0.8 mm, particularly preferably 0.025 to 0.3 mm. When used for battery containers, the thickness is preferably 0.1 to 2.0 mm, more preferably 0.15 to 0.8 mm, still more preferably 0.15 to 0.5 mm.
  • a surface-treated metal plate 10 for a battery of this embodiment includes a nickel-tin alloy layer 40 on a base material 20 .
  • FIG. 1 shows an aspect in which the nickel-tin alloy layer 40 is formed on the base material 20 with the nickel layer 30 interposed therebetween. 30 may be omitted.
  • the nickel-tin alloy layer 40 referred to here can be checked for presence or absence of the nickel-tin alloy layer by performing high-frequency glow discharge emission surface analysis (GDS) and X-ray diffraction (XRD) measurement, which will be described later. can.
  • GDS glow discharge emission surface analysis
  • XRD X-ray diffraction
  • the nickel-tin alloy layer 40 may be formed of an alloy of nickel and tin, but from the viewpoint of appropriately exhibiting the effects of the present embodiment, it is preferable that the nickel-tin alloy layer 40 be a binary alloy of nickel and tin. Desirably, it is substantially free of other elements such as iron.
  • the surface-treated metal plate 10 for a battery of the present embodiment may have a ternary alloy layer of iron-nickel-tin, but at least has a layer of a binary alloy of nickel and tin. is desirable.
  • the nickel-tin alloy layer 40 is desirably a binary alloy of nickel and tin, and its crystal structure is not particularly limited .
  • Ni—Sn 40-42 and Ni—Sn 46-48 are binary alloys of nickel and tin
  • high-frequency glow discharge luminescence surface analysis (GDS) and scanning type It can be confirmed using Auger electron spectroscopy (AES) or the like.
  • AES Auger electron spectroscopy
  • Ni intensity, Sn intensity, and Fe intensity can be obtained from the nickel-tin alloy layer 40 formed on the substrate 20 by high-frequency glow discharge emission surface spectroscopy (GDS).
  • GDS high-frequency glow discharge emission surface spectroscopy
  • XRD X-ray diffraction
  • ICDD PDF card 03-065-4553 X-ray diffraction measurement using CuK ⁇ as a radiation source.
  • the diffraction peak of the ( ⁇ 311) plane in the range of diffraction angles 2 ⁇ 32.5 to 33.5° and the (002 ) plane (according to ICDD PDF card 03-065-4553).
  • the nickel-tin alloy layer 40 preferably contains any one of Ni 3 Sn 4 , Ni 3 Sn 2 , Ni--Sn 40-42 and Ni--Sn 46-48 as an alloy phase. More specifically, from the viewpoint of further increasing the electrolyte resistance, it is preferable to contain at least one of Ni 3 Sn 4 and Ni 3 Sn 2 as the alloy phase, and the effect of suppressing gas generation is further increased. From a viewpoint, it is preferable to contain at least one of Ni 3 Sn 4 , Ni—Sn 40-42 and Ni—Sn 46-48 as an alloy phase. In particular, when two of Ni--Sn 40-42 and Ni--Sn 46-48 are contained, the effect of suppressing gas generation is significantly enhanced, which is particularly preferable.
  • Ni 3 Sn 4 as the alloy phase.
  • the nickel-tin alloy layer 40 may contain two or more of Ni 3 Sn 4 , Ni 3 Sn 2 , Ni—Sn 40-42 and Ni—Sn 46-48 as alloy phases.
  • the nickel-tin alloy layer 40 contains alloy phases (for example, Ni 3 Sn) other than alloy phases such as Ni 3 Sn 4 , Ni 3 Sn 2 , Ni--Sn 40-42 , and Ni--Sn 46-48 .
  • the reason why it is desirable to have the above configuration in this embodiment is as follows. That is, as described above, one of the problems in putting alkaline secondary batteries into practical use is the problem of hydrogen gas generation.
  • the reaction conditions for hydrogen gas generation are satisfied under the conditions where a chemical reaction (self-discharge) other than the battery reaction occurs due to the formation of a local battery between dissimilar metals inside the battery. occurs in some cases.
  • a chemical reaction self-discharge
  • Zinc is one of the metals with a low potential among the metals used in aqueous batteries. Therefore, the amount of discharge is large when it becomes a local battery state with other metals used in the battery, and it is easy to satisfy the hydrogen gas generation condition.
  • the self-discharge referred to here includes both side reactions (chemical reactions including hydrogen gas generation processes) during charging and discharging and chemical reactions that occur other than during charging and discharging, that is, in a natural standing state.
  • the current collector material is a member in which hydrogen gas is more likely to be generated and self-discharge is likely to occur because zinc or the like in the electrolyte is deposited on the surface of the current collector material and comes into direct contact.
  • tin in the nickel-tin alloy layer 40 can be said to be a material with a high hydrogen overvoltage.
  • the property of tin is that it has low electrolyte resistance.
  • nickel in the nickel-tin alloy layer 40 has a low hydrogen overvoltage, but is excellent in electrolytic solution resistance. Therefore, the present inventors changed the plating conditions, heat treatment conditions, etc. for forming the nickel-tin alloy layer 40 to obtain alloy layers having different nickel and tin contents, alloy structures, and the like.
  • the inventors of the present invention have made earnest studies and repeated experiments, and have found that the provision of the nickel-tin alloy layer 40 can solve the above-described problems of electrolyte resistance and hydrogen gas generation at the same time.
  • the nickel-tin alloy layer 40 preferably contains at least one of Ni 3 Sn 4 , Ni 3 Sn 2 , Ni--Sn 40-42 , and Ni--Sn 46-48 as an alloy phase.
  • the above alloy phases it has been found that when the alloy phase of Ni 3 Sn 4 is contained, the electrolytic solution resistance and the effect of suppressing gas generation are more excellent.
  • the thickness of the nickel-tin alloy layer 40 is not particularly limited, it is preferably 0.05 to 5.00 ⁇ m, more preferably 0.05 to 3.00 ⁇ m, still more preferably 0.10 to 2.50 ⁇ m. By setting the thickness of the nickel-tin alloy layer 40 within the above range, the effect of suppressing gas generation and the electrolyte resistance can be further enhanced.
  • the thickness of the nickel-tin alloy layer 40 can be obtained by high-frequency glow discharge emission surface analysis (GDS) using a high-frequency glow discharge optical emission spectrometer (GDS measurement device).
  • GDS glow discharge emission surface analysis
  • the high-frequency glow discharge optical emission spectrometer is an analysis method for performing elemental analysis in the depth direction of samples subjected to various surface treatments such as plating and heat treatment, and is destructive analysis by sputtering.
  • a measurement method using a high-frequency glow discharge emission spectrometer is as follows. That is, first, a standard sample in which a pure Ni plating layer with a known thickness was formed on an iron-based metal plate, and a pure Sn plating layer with a known thickness was formed on a stainless steel plate with strike Ni plating. Prepare two of the standard samples formed in . Then, using the above two standard samples, measurement is performed with a high-frequency glow discharge optical emission spectrometer to obtain Ni intensity data, Sn intensity data and Fe intensity data at each depth position.
  • the relationship between the sputtering depth and the sputtering time (etching rate (unit: ⁇ m/sec)) was obtained, and this was used as the etching of the pure Ni plating layer.
  • R Ni be the etching rate of the pure Sn plating layer
  • R Sn be the etching rate.
  • the pure Ni plating layer and the nickel-tin alloy layer have a relationship that their hardness values are close to each other, and in the measurement using a high-frequency glow discharge optical emission spectrometer, there is a correlation between the etching rate and the hardness. Therefore, the etching rate R Ni of the pure Ni plating layer is defined as the etching rate R Ni—Sn of the nickel-tin alloy layer.
  • the strength data of the Ni strength data, Sn strength data, and Fe strength data obtained by the measurement of the two standard samples are corrected so that the respective maximum values become equivalent values.
  • Correction of the intensity data is performed by obtaining correction coefficients that make the respective maximum values equivalent, and correcting the Ni intensity data, the Sn intensity data and the Fe intensity data using the obtained correction coefficients.
  • the correction coefficient for example, in a standard sample in which a pure Ni plating layer is formed on an iron-based metal plate, the maximum value of Ni strength data and Fe strength data is set to 10, and the pure Ni plating layer is set to a value of 10. In a standard sample in which a Sn plating layer is formed on a strike Ni-plated stainless steel plate, the maximum Sn intensity data can be set to a value of 10.
  • the correction coefficient is set so that each of the above maximum values is 10. Then, it is determined that Ni has been detected at the depth positions where the Ni intensity is 1 or more, and it is determined that Sn has been detected at the depth positions where the Sn intensity is 0.2 or more, and the Fe intensity is 1. For the above depth positions, it is determined that Fe has been detected. Therefore, in this measurement, the Ni intensity is 1 or more, the Fe intensity is less than 1, and the Sn intensity is less than 0.2. I judge. Similarly, the depth position at which an intensity indicating a Sn intensity of 0.2 or more, a Ni intensity of less than 1, and an Fe intensity of less than 1 is determined to be a region where a tin layer is formed.
  • the depth position where the intensity indicating the Fe intensity of 1 or more, the Ni intensity of less than 1, and the Sn intensity of less than 0.2 is determined to be a region made of Fe (for example, the base material 20). Furthermore, the Ni intensity is 1 or more, the Sn intensity is 0.2 or more, and the Fe intensity is less than 1.
  • the depth position is determined as a region where the nickel-tin alloy layer 40 is formed, The depth position where the Ni intensity is 1 or more, the Fe intensity is 1 or more, and the Sn intensity is less than 0.2 is determined as a region where an iron-nickel alloy layer is formed.
  • FIG. 4A is a graph obtained by performing GDS measurement on a standard sample in which a pure Ni plating layer is formed on an iron-based metal plate
  • FIG. 3 is a graph obtained by performing GDS measurement on a standard sample in which a pure Sn plating layer is formed on a strike Ni-plated stainless steel plate.
  • the graphs shown in FIGS. 4A and 4B are graphs after correction is performed using the correction coefficients described above.
  • the nickel layer is formed at the depth position where the Ni intensity is 1 or more, the Fe intensity is less than 1, and the Sn intensity is less than 0.2.
  • the battery surface-treated metal plate 10 using a high-frequency glow discharge emission spectrometer, continuously measure changes in Ni intensity, Sn intensity, and Fe intensity in the depth direction from the outermost surface to the base material 20,
  • the etching time (unit: seconds) in the area where it is determined that the nickel-tin alloy layer 40 is formed was measured, and the etching rate R Ni of the pure Ni plating layer and the etching rate R Ni- of the nickel-tin alloy layer were measured.
  • the thickness of the nickel-tin alloy layer 40 can be obtained.
  • FIG. 5A is a graph obtained by GDS measurement of the surface-treated metal plate for batteries of Example 1 described later
  • FIG. 5B is a graph of the surface-treated metal plate for batteries of Example 5 described later.
  • FIG. 5(C) is an enlarged graph of the data at the initial stage of measurement in FIG. 5(B).
  • the nickel-tin alloy layer 40 is at a depth position where an intensity indicating a value of 1 or more for the Ni intensity, 0.2 or more for the Sn intensity, and less than 1 for the Fe intensity is detected.
  • the nickel-tin alloy layer is obtained according to the following formula. 40 thickness can be obtained.
  • Etching time by GDS measurement (unit: seconds) ⁇ etching rate of nickel-tin alloy layer R Ni—Sn (unit: ⁇ m/second) thickness of nickel-tin alloy layer 40 (unit: ⁇ m)
  • the nickel-tin alloy layer 40 is subjected to the above-described X-ray diffraction (XRD) measurement, or high-frequency glow discharge emission surface analysis (GDS) and X-ray diffraction (XRD).
  • XRD X-ray diffraction
  • GDS glow discharge emission surface analysis
  • XRD X-ray diffraction
  • the ratio (atomic %) of Sn in the surface on which the nickel-tin alloy layer 40 is formed is preferably 40 atomic % or more.
  • the ratio (atomic %) of Sn on the surface on which the nickel-tin alloy layer 40 is formed is more preferably 45 atomic % or more, more preferably more than 50 atomic %. is.
  • the nickel-tin alloy layer 40 is formed on the surface or in the lower layer of the tin layer 50, so the Sn content of the surface on which the nickel-tin alloy layer 40 is formed
  • the ratio (atomic %) is not particularly limited and is 100% or less. From the viewpoint of maintaining the ratio of Sn on the surface without changing even after the anode reaction test described later, the Sn content is more preferably 90 atomic % or less, and still more preferably 80 atomic % or less.
  • the nickel layer formed on the outermost surface of the surface-treated metal plate 10 for batteries - it may be a tin alloy layer 40 or a tin layer 50; A two-layer structure in which the tin layer 50 is formed on the nickel-tin alloy layer 40 may also be used.
  • the ratio (atomic %) of Sn on the surface on which the nickel-tin alloy layer 40 is formed can be measured by scanning Auger electron spectroscopy (AES). Specifically, first, the surface of the surface-treated metal plate for battery 10 on which the nickel-tin alloy layer 40 is formed is etched to a depth of 10 nm using a scanning Auger electron spectrometer. , The surface after etching is measured using a scanning Auger electron spectrometer. is the peak intensity of Sn , and the percentage of Ni (atomic %) and the percentage of Sn (atomic %) are calculated from the obtained peak intensity, whereby the ratio of Sn can be obtained.
  • AES scanning Auger electron spectroscopy
  • the ratio of Ni (atomic %) and the ratio of Sn (atomic %) can be calculated. That is, the relative sensitivity coefficient of Ni and the relative sensitivity coefficient of Sn are defined as RSF Ni and RSF Sn , respectively, and can be obtained according to the following equations.
  • Proportion of Ni (atomic %) ( INi / RSFNi )/( INi / RSFNi + ISn / RSFSn ) x 100
  • Sn ratio (atomic %) ( ISn / RSFSn )/( INi / RSFNi + ISn / RSFSn ) x 100
  • the ratio of Ni (atomic %) and the ratio of Sn (atomic %) on the surface referred to here are the ratios when etching is performed at a depth of 10 nm using the above-described scanning Auger electron spectrometer. be.
  • the method for controlling the ratio of Sn on the surface of the surface on which the nickel-tin alloy layer 40 is formed is not particularly limited. A method of forming and performing a normal temperature diffusion treatment or a method of performing a thermal diffusion treatment are preferred.
  • the method of forming the nickel-tin alloy layer 40 is not particularly limited, but a nickel-plated layer and a tin-plated layer are formed in this order on the substrate 20, and the nickel-plated layer and the tin-plated layer are formed at room temperature. Examples include a method of causing diffusion at the interface (normal temperature diffusion treatment), a method of forming a nickel plating layer and a tin plating layer in this order, and performing thermal diffusion treatment by heating. Further, when the substrate 20 is a Ni-based metal plate (including electrolytic foil), a tin-plated layer is formed on the substrate 20, and the nickel-tin alloy layer 40 is formed in the same manner as described above. It is also possible to form
  • a method of plating base material 20 with nickel using a nickel plating bath is suitable.
  • plating baths commonly used for nickel plating such as Watts baths, sulfamic acid baths, fluoride baths, and chloride baths can be used.
  • the nickel plating layer uses a Watt bath with a bath composition of 200 to 350 g/L nickel sulfate, 20 to 60 g/L nickel chloride, and 10 to 50 g/L boric acid, pH 3.0 to 4.8 (preferably pH 3.6 to 4.6), a bath temperature of 50 to 70° C., and a current density of 10 to 40 A/dm 2 (preferably 20 to 30 A/dm 2 ).
  • tin plating is performed on the base material 20 on which the nickel plating layer is formed using a tin plating bath.
  • the tin plating bath is not particularly limited, and methods using known plating baths such as ferrostane bath, MSA bath, halogen bath, and sulfuric acid bath can be used.
  • the treatment temperature in performing the normal temperature diffusion treatment is not particularly limited, but is preferably 0° C. or higher to less than 50° C.
  • the treatment time is not particularly limited, but is preferably 5 hours or longer, more preferably 120 hours or longer, More preferably 360 hours or more, particularly preferably 720 hours or more.
  • the nickel-tin alloy layer 40 can be made to mainly contain either Ni-Sn 40-42 or Ni-Sn 46-48 as an alloy phase. .
  • the temperature is 25° C. or higher, and the treatment time is 720 hours or longer.
  • the heat treatment conditions for heat treatment by box annealing are preferably 50°C or higher and 700°C or lower, more preferably 50°C or higher and 600°C or lower.
  • the soaking time (time after the temperature reaches the target value) when performing heat treatment by box annealing is not particularly limited, but is preferably 0.5 to 8 hours, more preferably 1 to 5 hours. It is preferable that the total time of heating, soaking and cooling is within the range of 3 to 80 hours.
  • the heat treatment conditions may be selected according to the type of alloy phase contained in the nickel-tin alloy layer 40 .
  • the nickel-tin alloy layer 40 mainly contains either Ni--Sn 40-42 or Ni--Sn 46-48 as an alloy phase
  • a box-shaped It is preferable to perform heat treatment by annealing, the heat treatment temperature by box annealing is preferably 50 ° C. or higher and lower than 100 ° C., more preferably 50 ° C. or higher and lower than 80 ° C., and the soaking time is preferably 0.5 to 0.5 ° C. 8 hours, more preferably 1 to 5 hours.
  • the heat treatment temperature is preferably 50° C. or more and less than 100° C., and the heat treatment time is 1 to 8 hours.
  • the heat treatment temperature is 75° C. or more and less than 100° C., and the heat treatment time is 0.5 to 5 hours.
  • the nickel-tin alloy layer 40 mainly contains Ni 3 Sn 4 as an alloy phase, it mainly contains either Ni--Sn 40-42 or Ni--Sn 46-48 . It is preferable to perform heat treatment by box annealing under conditions of a higher temperature than in the case of heat treatment. less than, more preferably 150° C. to less than 250° C., and the soaking time is preferably 1 to 8 hours, more preferably 1 to 5 hours.
  • the temperature is higher than that in the case where Ni 3 Sn 4 is mainly contained as described above.
  • the heat treatment temperature by box annealing is preferably 300 ° C. or higher and 700 ° C. or lower, more preferably 300 ° C. or higher and 600 ° C. or lower, and the soaking time is preferably 1. to 8 hours, more preferably 1 to 5 hours.
  • the method for adding any one of Ni 3 Sn 4 , Ni 3 Sn 2 , Ni—Sn 40-42 , and Ni—Sn 46-48 to the nickel-tin alloy layer 40 is limited to the heat treatment method described above. It may be continuous annealing instead of a single annealing.
  • a tin layer 50 may be provided on the nickel-tin alloy layer 40.
  • the tin layer 50 is formed by partially remaining the tin-plated layer when the nickel-tin alloy layer 40 is formed by the above-described room temperature diffusion treatment method or thermal diffusion treatment method. can do. That is, for example, a nickel plating layer and a tin plating layer are formed in this order on the base material 20, and then a normal temperature diffusion treatment is performed, or a thermal diffusion treatment is performed at a relatively low temperature. can be done.
  • the thickness of the tin layer 50 is not particularly limited, but is preferably 2.0 ⁇ m or less, more preferably less than 1.0 ⁇ m, even more preferably less than 0.5 ⁇ m, even more preferably less than 0.3 ⁇ m, and particularly preferably 0.2 ⁇ m. is less than If the thickness of the tin layer 50 is within the above range, it is believed that there is no adverse effect on battery performance.
  • the lower limit of the thickness of the tin layer 50 is not particularly limited, it is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, and particularly preferably 0.1 ⁇ m or more.
  • the thickness of the tin layer 50 can be adjusted, for example, by controlling the conditions of normal temperature diffusion treatment and thermal diffusion treatment.
  • the thickness of the tin layer 50 was determined by high-frequency glow discharge emission spectroscopic analysis of the battery surface-treated metal plate 10 that was determined to have a tin layer by confirming a Sn diffraction peak by X-ray diffraction (XRD) measurement. It can be obtained using a device. Specifically, in the same manner as the measurement of the thickness of the nickel-tin alloy layer 40 described above, the surface-treated metal plate 10 for battery was measured from the outermost surface to the base material 20 using a high-frequency glow discharge emission spectrometer.
  • the formation region of the tin layer 50 is specified, and the thickness of the tin layer 50 can be obtained from the measured Sn intensity and the etching rate R Sn of the pure Sn plating layer. can.
  • the surface-treated metal plate for battery 10 of the present embodiment further includes a nickel layer 30 as a lower layer of the nickel-tin alloy layer 40 .
  • FIG. 1 illustrates a configuration further including the nickel layer 30 , the configuration is not limited to such a configuration, and a configuration without the nickel layer 30 may be employed.
  • the thickness of the nickel layer 30 is preferably 0.05-5.00 ⁇ m, more preferably 0.15-3.00 ⁇ m, still more preferably 0.25-3.00 ⁇ m. By forming the nickel layer 30 with such a thickness, the surface-treated metal plate for battery 10 can be made to have a higher electrolytic solution resistance.
  • the thickness of the nickel layer 30 was determined by high-frequency glow discharge emission spectroscopic analysis of the battery surface-treated metal plate 10 that was determined to have a nickel layer by confirming a diffraction peak of Ni by X-ray diffraction (XRD) measurement. It can be obtained using a device. Specifically, in the same manner as the measurement of the thickness of the nickel-tin alloy layer 40 described above, the surface-treated metal plate 10 for battery was measured from the outermost surface to the base material 20 using a high-frequency glow discharge emission spectrometer. It is possible to determine the thickness of the nickel layer 30 from the measured Ni strength and the etching rate R Ni of the pure Ni plating layer by specifying the formation region of the nickel layer 30 from the measurement result of the Ni strength measured in the vertical direction. can.
  • the method for forming the nickel layer 30 is not particularly limited. It can be formed by leaving a part of the nickel plating layer formed on. That is, for example, when a nickel plating layer and a tin plating layer are formed in this order on the base material 20, and normal temperature diffusion treatment or thermal diffusion treatment is performed, the thickness of the nickel plating layer to be formed and the treatment conditions are adjusted. By doing so, it is possible to control whether or not the nickel layer 30 is formed and its thickness.
  • the surface-treated metal plate for batteries 10 of the present embodiment may further include an iron-nickel diffusion layer as a lower layer of the nickel layer 30 .
  • the iron-nickel diffusion layer can be formed by using an iron-based metal plate as the base material 20, forming a nickel plating layer on the base material 20, and performing heat treatment.
  • the nickel plating conditions for forming the nickel plating layer are not particularly limited, but, for example, the same conditions as those for the nickel plating layer for forming the nickel-tin alloy layer 40 described above may be used.
  • the heat treatment conditions are not particularly limited, but when heat treatment is performed by box annealing, the heat treatment temperature is preferably over 400 ° C. to 600 ° C. or less, more preferably 450 ° C. to 600 ° C.
  • the soaking time is preferably 0.5 to 8 hours.
  • the heat treatment temperature is preferably 600° C. to 900° C., more preferably 600° C. to 800° C., and the heat treatment time is preferably 3 to 120 seconds. Just do it.
  • the heat treatment conditions for forming the iron-nickel diffusion layer are relatively high temperatures, after forming the iron-nickel diffusion layer in advance (that is, iron- After the heat treatment for forming the nickel diffusion layer), it is desirable to form the nickel-tin alloy layer 40 .
  • the tin adhesion amount (Sn adhesion amount) on the surface on which the nickel-tin alloy layer 40 is formed is preferably 0.05 to 15.0 g/m 2 . More preferably 0.5 to 15.0 g/m 2 , still more preferably 1.0 to 10.0 g/m 2 , particularly preferably 1.0 to 7.0 g/m 2 .
  • the amount of nickel deposited is preferably 2.1 to 65.0 g/m 2 , more preferably 3.0 to 50.0 g/m 2 , still more preferably 3.5 to 25.0 g/m 2 .
  • the amount of attached tin and the amount of attached nickel can each be obtained by performing fluorescent X-ray measurement, ICP emission spectroscopic analysis, or the like on the surface-treated metal plate for battery 10 .
  • the above-described tin deposition amount and nickel deposition amount are the deposition amounts on the surfaces on which the nickel-tin alloy layers 40 are formed. Therefore, as shown in FIG.
  • the above-mentioned range is the amount of adhesion on one side rather than the amount of adhesion on both sides. Further, as shown in FIGS. 1 and 2, the total deposition amount in the case where the surface on which the nickel-tin alloy layer 40 is formed has the nickel layer 30 and the tin layer 50 is the same as the above range.
  • the substrate 20 is a metal plate based on iron or nickel, and the metal plate serving as the substrate 20 has a nickel-tin alloy layer 40 on at least one side thereof. It is possible to suppress gas generation and has excellent electrolytic solution resistance, and in particular, when an alkaline electrolyte is used as the electrolyte, it has a particularly excellent effect of suppressing gas generation. And it exhibits electrolytic solution resistance. Therefore, the surface-treated metal plate 10 for a battery of the present embodiment can be preferably used as a current collector for a positive electrode or a negative electrode or as a battery container by taking advantage of such characteristics. It can be used more preferably as current collectors and battery containers in secondary batteries, and particularly preferably as current collectors and battery containers in nickel-zinc batteries.
  • ⁇ Measurement of thickness of nickel layer and thickness of nickel-tin alloy layer> The thickness of the nickel layer and the thickness of the nickel-tin alloy layer of the surface-treated metal sheets obtained in each example and comparative example were measured by high-frequency glow discharge luminescence surface spectroscopy (GDS). In addition, the GDS measurement was performed under the following conditions.
  • ⁇ GDS measurement device High frequency glow discharge emission spectrometer (GD-Profiler 2, manufactured by Horiba, Ltd.)
  • GD-Profiler 2 manufactured by Horiba, Ltd.
  • Detection function HDD mode
  • ⁇ Anode diameter 4mm
  • Excitation mode normal
  • ⁇ Light source pressure 600 Pa
  • ⁇ Light source output 35W
  • Sn 190 nm
  • Fe 371 nm
  • the specific method for calculating the thickness of each layer was as follows. First, a standard sample in which a pure Ni plating layer with a thickness of 0.79 ⁇ m is formed on a steel plate (cold-rolled plate of low-carbon aluminum-killed steel) and a pure Sn plating layer with a thickness of 1.37 ⁇ m are prepared. Two standard samples were prepared which were formed on a stainless steel plate plated with strike Ni so as to have a thickness of 50 nm or less. Next, using the above two standard samples, the respective intensities of Ni, Sn, and Fe in the thickness direction were measured with a GDS measurement device while performing etching by sputtering. FIG. 4(A) is a graph obtained by performing GDS measurement on the standard sample on which the pure Ni plating layer is formed, and FIG. It is a graph obtained by performing the measurement.
  • the Ni intensity data, Sn intensity data, and Fe intensity data obtained by measuring the standard samples were corrected so that their respective maximum values were approximately the same value. Specifically, using the above two standard samples, a correction coefficient is obtained so that the maximum value of the Ni strength data, Sn strength data, and Fe strength data is 10, and the obtained correction coefficient is used. We corrected the intensity data.
  • the obtained correction data it is assumed that Ni is detected at depth positions where the Ni intensity is 1 or more, and Sn is detected at depth positions where the Sn intensity is 0.2 or more.
  • the boundary points of each layer are determined, the sputtering time in the area where the nickel layer is formed, and the tin The sputtering time in the layered regions was determined. Further, by performing fluorescent X-ray measurement by the above method, the thickness (unit: ⁇ m) converted from the adhesion amount of the nickel layer and the tin layer is divided by the sputtering time for the nickel layer and the tin layer.
  • the etching rate (unit: ⁇ m/sec) of the nickel layer and the tin layer was calculated as follows.
  • the Ni intensity, Sn intensity, and Fe intensity at each depth position were measured by a GDS measuring device while performing etching by sputtering on the surface-treated metal plates obtained in each example and comparative example.
  • the etching rate R Ni of the nickel layer, the etching rate R Sn of the tin layer, and the etching rate R Ni —Sn of the nickel-tin alloy layer obtained above the nickel The thickness of layer 30 and the thickness of nickel-tin alloy layer 40 were determined. Specifically, the thickness of the nickel-tin alloy layer 40 was determined as follows.
  • the Ni intensity is 1 or more, the Sn intensity is less than 0.2, and the Fe intensity is less than 1.
  • the depth position is determined as a region where the nickel layer 30 is formed.
  • X-ray diffraction (XRD) measurement (identification of alloy phase)>
  • the alloy phase contained in the nickel-tin alloy layer 40 was identified by performing X-ray diffraction (XRD) measurement on the surface-treated metal sheets obtained in each example and comparative example.
  • the presence of unalloyed nickel and tin layers was also confirmed by X-ray diffraction (XRD) measurements.
  • XRD X-ray diffraction
  • SmartLab manufactured by Rigaku Corporation was used as an X-ray diffraction measurement device.
  • the specific measurement conditions for the X-ray diffraction (XRD) measurement were as follows.
  • Ni 3 Sn 2 ICDD PDF card 01-072-2561 Fe 2.5 Ni 2.5 Sn: ICDD PDF card 03-065-7279 Further, the presence or absence of the nickel layer and the tin layer was determined based on the presence or absence of the diffraction peak of Ni and the diffraction peak of Sn.
  • Judgment was made based on the peak of the (311) plane appearing between 5 and 93.5° (ICDD PDF card 03-065-2865).
  • AES ⁇ Scanning Auger Electron Spectroscopy
  • the peak of 830 to 860 eV is the peak intensity of Ni
  • the peak of 415 to 445 eV is the peak intensity of Sn . (atomic %) and the proportion of Sn (atomic %) were calculated.
  • the specific measurement conditions for scanning Auger electron spectroscopy (AES) were as follows.
  • the peak intensity I Ni of Ni and the peak intensity I Sn of Sn are divided by the relative sensitivity factor (RSF) corresponding to each element to obtain the ratio of Ni (atomic %) and the ratio of Sn. (atomic %) was calculated. More specifically, the relative sensitivity coefficient of Ni and the relative sensitivity coefficient of Sn are defined as RSFNi and RSFSn , respectively, and obtained according to the following equations.
  • Sn ratio (atomic %) ( ISn / RSFSn )/( INi / RSFNi + ISn / RSFSn ) x 100
  • RSF Ni was 0.469 and RSF Sn was 0.718.
  • the Ni adhesion amount and the Sn adhesion amount contained in the surface-treated metal plate were measured by an anode reaction test using an alkaline solution (30% by weight potassium hydroxide solution). Electrolytic solution resistance was evaluated by measuring before and after the anode reaction test and calculating the dissolution rate of the amount of attached Sn before and after the anode reaction test. Specifically, assuming the anode reaction of the negative electrode current collector plate during discharge where the dissolution reaction tends to proceed, electrochemical measurements were performed to evaluate the dissolution resistance (electrolyte solution resistance) in the alkaline solution during discharge.
  • An anode reaction test was conducted by energizing using the method.
  • the amount of attached Sn before and after the anode reaction test was obtained by the X-ray fluorescence (XRF) measurement described above.
  • Electrolytic solution resistance was evaluated according to the following evaluation criteria 1 or 2. If either one of the following evaluation criteria 1 and 2 is evaluated as “ ⁇ ” or “ ⁇ ”, the attached state of Sn is sufficiently maintained even after the anode reaction test. Therefore, it can be evaluated that it exhibits sufficient electrolyte resistance.
  • the evaluation based on evaluation criteria 1 was performed for each example and comparative example shown in Table 1A, and the evaluation based on evaluation criteria 2 was performed for each example and comparative examples shown in Table 1B.
  • Evaluation criteria 1 the dissolution rate of the amount of deposited Sn was calculated according to the following formula from the amount of deposited Sn before and after the anode reaction test obtained from the above measurement, and evaluated according to the following criteria.
  • Dissolution rate (%) of Sn deposit ⁇ (Sn deposition before anode reaction) - (Sn deposition after anode reaction) / (Sn deposition before anode reaction) ⁇ x 100
  • a case where the dissolution rate of the amount of attached Sn before and after the anode reaction test was 10% or less was indicated as " ⁇ "
  • a case where the rate of change in the amount of attached Sn before and after the anode reaction test was 40% or less was indicated as " ⁇ ".
  • the case where the rate of change in the amount of attached Sn before and after the anode reaction test was more than 40% was evaluated as "x”.
  • Evaluation criteria 2 evaluation was made according to the following criteria from the Sn adhesion amount after the anode reaction test obtained from the above measurement. A case where the amount of attached Sn was 1.0 g/m 2 or more after the anode reaction test was rated as " ⁇ ”, and a case where the amount of attached Sn was less than 1.0 g/m 2 after the anode reaction test was rated as " ⁇ ”.
  • the anode reaction test was conducted under the following conditions.
  • ⁇ Electrochemical measuring instrument HZ5000 manufactured by Hokuto Denko Co., Ltd.
  • ⁇ Test electrode measurement sample (20 mm ⁇ 20 mm)
  • ⁇ Counter electrode Cu plate
  • ⁇ Reference electrode Ag/AgCl (KCl saturated)
  • ⁇ Electrolyte solution 30% by weight potassium hydroxide solution
  • ⁇ Current density 50 mA/cm 2
  • Measurement method Chronopotentiometry ⁇ Amount of electricity: 21 C/cm 2
  • Corrosion current densities of 20 mA/cm 2 or less were evaluated as “ ⁇ ”
  • corrosion current densities of 50 mA/cm 2 or less were evaluated as “ ⁇ ”
  • corrosion current densities exceeding 50 mA/cm 2 were evaluated as “ ⁇ ”.
  • the corrosion current density measurement was performed under the following conditions, and the corrosion current density (unit: mA/cm 2 ) generated between the following test electrode and counter electrode in a 30% by weight potassium hydroxide solution was measured.
  • ⁇ Measuring device HZ5000 manufactured by Hokuto Denko Co., Ltd.
  • ⁇ Test electrode Zn plate (20 ⁇ 20 mm, thickness 0.5 mm)
  • Counter electrode measurement sample (measurement diameter ⁇ 6 mm)
  • Measurement method Chronocoulometry
  • a cold-rolled plate (thickness: 110 ⁇ m) of low-carbon aluminum-killed steel having the chemical composition shown below was prepared as the base material 20.
  • the prepared base material 20 was subjected to electrolytic degreasing and pickling by immersion in sulfuric acid, and then nickel plating was performed under the following conditions to form nickel plating layers on both surfaces of the base material 20 .
  • the nickel plating conditions were as follows. The nickel plating treatment time was set so that the amount of nickel deposited was the amount shown in Tables 1A and 1B. (Bath composition: Watt bath) Nickel sulfate hexahydrate: 250g/L Nickel chloride hexahydrate: 45g/L Boric acid: 30g/L (Plating conditions) Bath temperature: 60°C pH: 4.0-5.0 Agitation: air agitation or jet agitation Current density: 10 A/dm 2
  • the base material 20 on which the nickel plating layer was formed was subjected to tin plating, thereby forming tin plating layers on both surfaces of the base material 20 on which the nickel plating layer was formed.
  • the tin plating conditions were as follows. Further, the tin plating treatment time was set so that the amount of attached tin was as shown in Tables 1A and 1B.
  • the ratio of Ni (atomic %) and the ratio of Sn (atomic %) on the surface on which the nickel-tin alloy layer 40 is formed are measured by scanning Auger electron spectroscopy (AES) according to the method described above. As a result, the proportion of Ni was 18 atomic % and the proportion of Sn was 82 atomic %. Table 2 shows the results. The thickness of the tin layer of the obtained surface-treated metal plate was 0.10 ⁇ m.
  • the nickel-tin alloy layer 40 contains an alloy phase with a diffraction angle 2 ⁇ of 40 to 42° and a diffraction angle 2 ⁇ of 46 to 48°. It is a nickel-tin alloy that gives a diffraction peak in the range of 20°C, and can be judged to contain two of Ni-Sn 40-42 and Ni-Sn 46-48 .
  • the reason is as follows. That is, first, in the graph obtained by performing GDS measurement on the standard sample in which the pure Ni plating layer shown in FIG. Although it can be determined that a nickel layer exists, only peaks of Fe and Ni could be confirmed by XRD measurement, and peaks of iron-nickel alloy could not be confirmed.
  • Example 2 A steel sheet having a nickel plating layer and a tin plating layer was obtained in the same manner as in Example 1, and the obtained steel sheet having a nickel plating layer and a tin plating layer was subjected to a heat treatment (holding temperature) of 50 ° C. and a soaking time ( A surface-treated metal plate having a nickel-tin alloy layer 40 was obtained by performing heat treatment by box annealing under the condition of a holding time of 3 hours and under the condition of a reducing atmosphere. In the heat treatment by box annealing, the temperature was raised for 1 hour and the temperature was lowered for 1 hour.
  • a heat treatment holding temperature
  • a soaking time A surface-treated metal plate having a nickel-tin alloy layer 40 was obtained by performing heat treatment by box annealing under the condition of a holding time of 3 hours and under the condition of a reducing atmosphere. In the heat treatment by box annealing, the temperature was raised for 1 hour and the temperature was lowered for 1 hour.
  • the processing time of nickel plating and tin plating was set so that the nickel adhesion amount and the tin adhesion amount became the amounts shown in Tables 1A and 1B. Then, each of the above-described measurements was performed on the obtained surface-treated metal plate. The results are shown in Tables 1A and 1B. The thickness of the tin layer of the obtained surface-treated metal plate was 0.16 ⁇ m.
  • Examples 3 to 9 Heat treatment by box annealing was performed in the same manner as in Example 2, except that the heat treatment temperature (holding temperature) by box annealing was changed to the temperature shown in Table 1A, so that the surface treatment having the nickel-tin alloy layer 40 I got a metal plate.
  • the temperature was raised for 1 hour and the temperature was lowered for 1 hour.
  • the processing time of nickel plating and tin plating was set so that the nickel adhesion amount and the tin adhesion amount became the amounts shown in Table 1A. Then, each of the above-described measurements was performed on the obtained surface-treated metal plate. Results are shown in Table 1A.
  • Example 5 has a Ni ratio of 44 atomic % and a Sn ratio of 56 atomic %
  • Example 8 has a Ni ratio of 58 atomic % and a Sn ratio of 42 atoms. %Met. Table 2 shows the results.
  • Example 10 to 12 A surface having a nickel-tin alloy layer 40 was prepared in the same manner as in Example 5, except that the nickel plating and tin plating times were changed, thereby changing the nickel coverage and tin coverage as shown in Table 1A. A treated metal plate was obtained. Then, each of the above-described measurements was performed on the obtained surface-treated metal plate. Results are shown in Table 1A.
  • Example 13 A surface-treated metal plate having a nickel-tin alloy layer 40 in the same manner as in Example 5, except that the substrate 20 has through holes with an aperture ratio of 38% and a thickness of 60 ⁇ m. got The nickel plating and tin plating treatment times were set so that the amount of nickel deposited and the amount of tin deposited were the amounts shown in Table 1A. Then, each of the above-described measurements was performed on the obtained surface-treated metal plate. Results are shown in Table 1A.
  • Example 14 As the base material 20, an electrolytic foil made of pure iron with a thickness of 6 ⁇ m (an electrolytic foil with an iron content of 99.9% by weight or more) is used, and the nickel plating and tin plating times are changed, whereby A surface-treated metal plate having a nickel-tin alloy layer 40 was obtained in the same manner as in Example 5, except that the nickel deposition amount and the tin deposition amount were changed as shown in Table 1A. Then, each of the above-described measurements was performed on the obtained surface-treated metal plate. Results are shown in Table 1A.
  • Example 15 As the base material 20, an electrolytic foil made of pure nickel with a thickness of 6 ⁇ m (an electrolytic foil with an iron content of 99.9% by weight or more) is used, nickel plating is not performed, and the tin plating time is set to A surface-treated metal plate having a nickel-tin alloy layer 40 was obtained in the same manner as in Example 5, except that the tin deposition amount was changed as shown in Table 1A. Then, each of the above-described measurements was performed on the obtained surface-treated metal plate. Results are shown in Table 1A.
  • Example 16> The base material was prepared in the same manner as in Example 1, and the treatment times for nickel plating and tin plating were such that the amount of nickel deposited and the amount of tin deposited were as shown in Table 1B.
  • the nickel deposition amount was measured after forming the nickel plating layer on the base material, and then the tin deposition amount was measured after forming the tin plating layer on the nickel plating layer. It was measured. Next, the steel plate having the nickel plating layer and the tin plating layer formed above is left to stand at a temperature of 35 ° C.
  • Example 16 the presence of a nickel layer could be confirmed from the fact that a Ni peak was detected in the X-ray diffraction (XRD) measurement, but the thickness of the nickel layer could not be measured.
  • XRD X-ray diffraction
  • the ratio of Ni (atomic %) and the ratio of Sn (atomic %) on the surface on which the nickel-tin alloy layer 40 is formed are measured by scanning Auger electron spectroscopy (AES) according to the method described above.
  • AES Auger electron spectroscopy
  • Example 2 A surface-treated metal plate was obtained in the same manner as in Example 1, except that only a tin-plated layer was formed on the substrate 20 without forming a nickel-plated layer. Then, each of the above-described measurements was performed on the obtained surface-treated metal plate. Results are shown in Table 1A.
  • Example 3 A surface-treated metal sheet was obtained by performing heat treatment by box annealing in the same manner as in Example 2, except that the heat treatment temperature (holding temperature) by box annealing was changed to 800°C. In the heat treatment by box annealing, the temperature was raised for 1 hour and the temperature was lowered for 1 hour. Then, each of the above-described measurements was performed on the obtained surface-treated metal plate. Results are shown in Table 1A.
  • Example 4 A surface-treated metal plate was obtained in the same manner as in Example 5, except that the nickel plating and tin plating times were changed, thereby changing the nickel adhesion amount and tin adhesion amount as shown in Table 1. Then, each of the above-described measurements was performed on the obtained surface-treated metal plate. Results are shown in Table 1A.
  • Example 5 A steel sheet having a nickel-plated layer and a tin-plated layer was obtained in the same manner as in Example 1, and the obtained steel sheet having a nickel-plated layer and a tin-plated layer was subjected to each of the above measurements without performing normal temperature diffusion treatment or heat treatment. was performed (that is, the above measurements were performed immediately after plating without performing normal temperature diffusion treatment or heat treatment). Results are shown in Table 1B.
  • laminated plating means that nickel plating and tin plating were performed on the substrate in this order.
  • the electrolytic solution resistance is It was excellent, the corrosion current density was reduced, and gas generation was effectively suppressed (Examples 1 to 16).
  • Ni—Sn 40-42 and Ni—Sn 46-48 were used as the alloy phases constituting the nickel-tin alloy layer 40.
  • Examples 3 to 6 and 10 to 15 mainly contain Ni 3 Sn 4 as an alloy phase constituting the nickel-tin alloy layer 40, and Examples 7 to No. 9 mainly contained Ni 3 Sn 2 as an alloy phase constituting the nickel-tin alloy layer 40 .
  • X-ray diffraction (XRD) charts of each alloy phase detected in the examples are shown in FIGS. 3A to 3E. Note that FIG.
  • 3A is an X-ray diffraction (XRD) chart (Example 1) showing two diffraction peaks of Ni—Sn 40-42 and Ni—Sn 46-48
  • FIG . 3C is an X-ray diffraction (XRD) chart showing diffraction peaks (Example 5)
  • FIG. 3C is an X-ray diffraction (XRD) chart showing diffraction peaks of Ni 3 Sn 2 (Example 8).
  • 3D and 3E are X-ray diffraction (XRD) charts respectively showing two diffraction peaks of Ni—Sn 40-42 and Ni—Sn 46-48 before and after the anode reaction test described above (Example 16).
  • Examples 1 and 2 have the tin layer 50 above the nickel-tin alloy layer 40 and the nickel layer 30 below the nickel-tin alloy layer 40.
  • Examples 3 to 15 have the nickel layer 30 below the nickel-tin alloy layer 40, and Example 16 has the tin layer 50 above the nickel-tin alloy layer 40. It was confirmed that there is.
  • Ni—Sn 40-42 and Ni—Sn 46-48 of Examples 1, 2, and 16 are mainly contained. It was confirmed that the effect of suppressing gas generation is more excellent in the case of those with Further, as shown in FIGS. 3D and 3E, as a result of confirming the two diffraction peaks of Ni—Sn 40-42 and Ni—Sn 46-48 before and after the anode reaction test, it was found that even after the anode reaction test, Ni It was confirmed that two peaks of -Sn 40-42 and Ni-Sn 46-48 existed, respectively, and sufficient electrolytic solution resistance was provided.
  • Example 5 the ratio of Ni (atomic %) and the ratio of Sn (atomic %) on the surface on which the nickel-tin alloy layer 40 was formed were measured by scanning Auger electron It was measured by spectroscopic analysis (AES), and it was confirmed that the electrolytic solution resistance and the effect of suppressing gas generation are excellent.
  • the ratios (atomic %) of Ni and Sn on the surface on which the nickel-tin alloy layer 40 was formed were 44 atomic % and 56 atomic %, respectively, and the electrolytic solution resistance and gas generation suppression were achieved. It was confirmed that both effects are much more excellent.
  • Comparative Example 3 As a result of X-ray diffraction (XRD) measurement, Fe 2.5 Ni 2.5 Sn 3 was detected as an alloy phase, and it has a ternary alloy layer of iron-nickel-tin. Also, as a result of measurement by high-frequency glow discharge luminescence surface analysis (GDS), the Fe element contained in the base material 20 is diffused to the surface, and a nickel-tin alloy layer (nickel-tin binary alloy layer ), the corrosion current density was high and gas generation was remarkable.
  • GDS glow discharge luminescence surface analysis
  • FIGS. 5(A) to 5(C) Graphs obtained by GDS measurement for the surface-treated metal plates for batteries of Examples 1 and 5 are shown in FIGS. 5(A) to 5(C), respectively.
  • 5(A) is a graph obtained by GDS measurement of the surface-treated metal plate for batteries of Example 1
  • FIG. 5(B) is a graph obtained by GDS measurement of the surface-treated metal plate for batteries of Example 5.
  • FIG. 5(C) is a graph obtained by enlarging the data in the initial stage of measurement in FIG. 5(B).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Connection Of Batteries Or Terminals (AREA)
PCT/JP2022/033006 2021-09-01 2022-09-01 電池用表面処理金属板 Ceased WO2023033118A1 (ja)

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EP22864700.4A EP4398349A4 (en) 2021-09-01 2022-09-01 SURFACE TREATED METAL SHEET FOR BATTERY
US18/687,992 US20240372109A1 (en) 2021-09-01 2022-09-01 Surface-treated metal sheet for battery
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JP2000048799A (ja) * 1998-07-28 2000-02-18 Matsushita Electric Ind Co Ltd 電 池
JP2006351432A (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

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JPH11297331A (ja) * 1998-04-03 1999-10-29 Sumitomo Special Metals Co Ltd 二次電池並びにその集電体
JP3388408B2 (ja) * 2000-10-24 2003-03-24 鈴鹿工業高等専門学校長 すずーニッケル合金膜の製造方法
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JP4374491B2 (ja) 2003-10-21 2009-12-02 株式会社大和化成研究所 リチウム二次電池用負極
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JP2000048799A (ja) * 1998-07-28 2000-02-18 Matsushita Electric Ind Co Ltd 電 池
JP2006351432A (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

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JP2023110037A (ja) 2023-08-08
EP4398349A4 (en) 2025-08-06
US20240372109A1 (en) 2024-11-07

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