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WO2020045627A1 - Plaque métallique destinée à un récipient de cellule et procédé destiné à la fabrication d'une plaque métallique destinée à un récipient de cellule - Google Patents

Plaque métallique destinée à un récipient de cellule et procédé destiné à la fabrication d'une plaque métallique destinée à un récipient de cellule Download PDF

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Publication number
WO2020045627A1
WO2020045627A1 PCT/JP2019/034121 JP2019034121W WO2020045627A1 WO 2020045627 A1 WO2020045627 A1 WO 2020045627A1 JP 2019034121 W JP2019034121 W JP 2019034121W WO 2020045627 A1 WO2020045627 A1 WO 2020045627A1
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WIPO (PCT)
Prior art keywords
metal plate
battery container
base material
layer
plating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/034121
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English (en)
Japanese (ja)
Inventor
利文 小柳
興 吉岡
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyo Kohan Co Ltd
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Toyo Kohan Co Ltd
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Filing date
Publication date
Application filed by Toyo Kohan Co Ltd filed Critical Toyo Kohan Co Ltd
Priority to JP2020539627A priority Critical patent/JP7413264B2/ja
Priority to CN201980056086.0A priority patent/CN112639171A/zh
Priority to KR1020217002247A priority patent/KR102872693B1/ko
Publication of WO2020045627A1 publication Critical patent/WO2020045627A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • 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
    • 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
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—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
    • H01M50/129—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 organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • H01M50/133—Thickness
    • 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
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • 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 metal plate suitable for a battery container such as a lithium ion secondary battery and a method for producing the metal plate for a battery container.
  • a lithium-ion secondary battery (hereinafter, also referred to as “LiB”) has attracted attention as a high-output, long-life high-performance battery.
  • LiB lithium-ion secondary battery
  • battery containers for accommodating a non-aqueous electrolyte, a positive electrode active material, a negative electrode active material, and the like also take various forms such as a cylindrical shape and a rectangular shape.
  • Patent Literature 1 discloses a technique of accommodating electrodes and the like in a pouch using a laminated metal plate in which a thin metal plate is coated with a resin. According to Patent Document 1, it is mentioned that iron or an alloy of iron is used as a metal foil core material.
  • Patent Documents 2 and 3 a rolled metal plate having a thickness of 200 ⁇ m or less is used, Ni is plated on the rolled metal plate, and then rolling and heat treatment are performed.
  • a technique for forming a diffusion alloy layer containing Ni and Fe is disclosed.
  • a polyolefin-based resin may be formed on a rolled metal plate in order to improve corrosion resistance against an electrolytic solution or the like.
  • the use of the diffusion alloy layer allows the rolled metal plate and the polyolefin-based resin to be formed. It is mentioned that the adhesiveness is improved.
  • the surface treatment layer (plating layer) formed on the base material side is required to have not only properties that can withstand severe processing but also content resistance and adhesion to the film.
  • a metal plate for a battery container has excellent workability (formability), adhesion to a film, and content resistance to a non-aqueous electrolyte such as an organic electrolyte obtained by dissolving a lithium salt in an organic solvent. Improving is very important for gaining competitiveness.
  • An object of the present invention is to solve the above-described problem as an example.For example, even when performing a forming process using a metal plate for battery use, it is possible to suppress cracking of the base material and peeling of the resin, and the coating is performed.
  • the object of the present invention is to provide a metal plate for a battery container, which has excellent adhesion to a resin film, and has excellent content resistance to a nonaqueous electrolytic solution filled in the container, and a method for producing the metal plate for a battery container. I do.
  • a metal plate for a battery container is (1) a metal plate for a battery container used as a battery container, which is made of iron or an alloy of iron and has a thickness of 10 mm.
  • a substrate which is ⁇ 100 [mu] m, at least formed on one surface, 0.5 ⁇ 50.0g / m 2 of Ni plating layer and 0.05 Cr plating ⁇ 10.0 g / m 2 of the substrate And an electroplating layer containing at least one of the layers.
  • the electrochromic plating layer has a higher proportion of metallic Cr than a proportion of hydrated Cr oxide.
  • the electric Ni plating layer is a Ni plating layer composed of only Ni, or a Fe—Ni diffusion layer in which Fe is diffused. , And one selected from Fe-Ni alloy plating layers in which both Fe and Ni are electrodeposited.
  • a surface of the base material which is an inner surface side of the battery container is coated with a polyolefin-based resin. Is preferred.
  • the polyolefin-based resin is a polypropylene resin, and an acid-modified polyolefin layer is interposed between the base material and the polypropylene resin. Is preferred.
  • a surface of the base material which is an outer surface side of the battery container may be a polyester resin, a polyamide resin, or a polyolefin. Preferably, it is coated with one of the resins.
  • the tensile strength of the base material is 260 to 700 MPa, and the elongation of the base material is 5 to 55%. It is preferred that
  • the ratio of the crystal grain size in the plane direction and the thickness direction of the base material is 0.8 to 8. Is preferred.
  • the Ni plating layer and the Ni plating layer An electroplating layer containing at least one of a Cr plating layer is formed, and a surface of the substrate on the outer surface side of the battery container is a Zn plating layer or a Zn alloy of 3 to 30 g / m 2. It is preferable that an electroplating layer containing a plating layer is formed.
  • a method for manufacturing a metal plate for a battery container is a method for manufacturing a metal plate for a battery container including a base material of iron or an alloy of iron, Cold rolling the material to a thickness of 10 to 100 ⁇ m; and forming a Ni plating layer of 0.5 to 50.0 g / m 2 on at least one surface of the base material and a 0.05 to 10. forming an electroplated layer containing at least one of Cr plating layer 0 g / m 2, and having a.
  • ADVANTAGE OF THE INVENTION According to this invention, it can withstand severe shaping
  • a metal plate for a battery container can be realized.
  • the metal plate 10 for a battery container of the present embodiment will be described with reference to FIG.
  • the thickness direction of the battery container metal plate 10 will be referred to as the Z direction
  • the rolling direction of the battery container metal plate 10 will be referred to as the X direction.
  • the definition of these directions does not reduce the scope of the present invention.
  • the metal plate 10 for a battery container according to the present embodiment has a surface treatment layer 2 (electroplating layer 2) on a substrate 1 made of iron or an alloy of iron.
  • the iron alloy include various steel plates applicable as a base material of a battery container.
  • low carbon aluminum killed steel carbon content of 0.01 to 0.15% by weight
  • Ultra-low carbon steel having a carbon content of 0.003% by weight or less or non-aging ultra-low carbon steel obtained by further adding Ti or Nb to ultra-low carbon steel is also included.
  • the thickness of the base material 1 according to the present embodiment is preferably 10 to 100 ⁇ m, more preferably 15 to 60 ⁇ m.
  • the quality tends to be unstable, such as generation of pinholes in the cold rolling step or unstable thickness difference.
  • cracks may occur in the molding process, and the effects intended by the present application may not be obtained.
  • the thickness exceeds 100 ⁇ m, the effect of weight reduction cannot be obtained.
  • the base material 1 is desirably ultra-low carbon steel, and has a thickness of 20 to 80 ⁇ m. And more preferably 30 to 60 ⁇ m.
  • C 0.0001 to 0.1% by weight
  • C is an element that increases the strength of the substrate 1. If the content of C is excessive, the strength is excessively increased and the rollability is reduced. Therefore, the upper limit of the content of C is set to 0.1% by weight.
  • the lower limit of the C content is not particularly limited, but the lower limit of the C content is 0.0001% by weight in consideration of cost.
  • the content of C is more preferably 0.0005 to 0.03% by weight, and still more preferably 0.001 to 0.01% by weight.
  • Si 0.001 to 0.5% by weight
  • Si is an element that increases the strength of the substrate 1. If the Si content is excessive, the strength is excessively increased and the rollability is reduced. Therefore, the upper limit of the Si content is set to 0.5% by weight.
  • the lower limit of the Si content is not particularly limited, but the lower limit of the Si content is 0.001% by weight in consideration of cost. The content of Si is more preferably 0.001 to 0.02% by weight.
  • Mn is an element that increases the strength of the substrate 1. If the content of Mn is excessive, the strength is excessively increased and the rollability decreases, so the upper limit of the content of Mn is set to 1.0% by weight.
  • the lower limit of the Mn content is not particularly limited, but the lower limit of the Mn content is set to 0.01% by weight in consideration of cost.
  • the Mn content is more preferably 0.01 to 0.5% by weight.
  • P is an element that increases the strength of the substrate 1. If the content of P is excessive, the strength is excessively increased and the rollability is reduced. Therefore, the upper limit of the content of P is set to 0.05% by weight.
  • the lower limit of the P content is not particularly limited, but the lower limit of the P content is 0.001% by weight in consideration of cost. The P content is more preferably 0.001 to 0.02% by weight.
  • S is an element that lowers the corrosion resistance of the substrate 1. Therefore, the smaller the S content, the better. In particular, when the content of S exceeds 0.02% by weight, the corrosion resistance is significantly reduced, so the upper limit of the content of S is set to 0.02% by weight.
  • the lower limit of the S content is not particularly limited, but the lower limit of the S content is set to 0.0001% by weight in consideration of cost. The S content is more preferably 0.001 to 0.01% by weight.
  • Al 0.0005 to 0.20% by weight
  • Al is added, for example, as a deoxidizing element for the substrate 1.
  • the Al content is preferably set to 0.0005% by weight or more.
  • the upper limit of the Al content is set to 0.20% by weight.
  • the lower limit of the Al content is not particularly limited, but the lower limit of the Al content is 0.0005% by weight in consideration of cost.
  • the content of Al is more preferably 0.001 to 0.10%.
  • N is an element that lowers the workability of the substrate 1. Therefore, the smaller the content of N, the better. In particular, when the content of N exceeds 0.0040% by weight, the workability is significantly reduced. Therefore, the upper limit of the content of N is set to 0.0040% by weight.
  • the lower limit of the N content is not particularly limited, but the lower limit of the N content is 0.0001% by weight in consideration of cost.
  • the content of N is more preferably 0.001 to 0.0040% by weight.
  • the main element in the remainder of the base material 1 is Fe, and the other elements are impurities which are inevitably mixed during the production.
  • Ti, Nb, B, Cu, Ni, Sn, Cr and the like may be contained as additional components.
  • Ti and Nb have the effect of fixing C and N in the base material 1 as carbides and nitrides and improving the workability of the base material 1, so that Ti: 0.01 to 0.8% by weight, Nb: One or two kinds may be contained in the range of 0.005 to 0.05% by weight.
  • the base material 1 according to the present embodiment is more preferably a steel sheet having less than 10.5% of Cr.
  • the base material 1 according to the present embodiment preferably has at least one of the following characteristics by being annealed after being cold-rolled.
  • the temperature and time required for annealing in the present embodiment are 2 to 9 hours, more preferably 2 to 6 hours when the annealing is performed at 450 ° C. to 650 ° C. (more preferably 500 to 600 ° C.).
  • the required time is 20 to 120 seconds.
  • the tensile strength of the substrate 1 according to the present embodiment is preferably from 260 to 700 MPa. If the tensile strength is less than 260 MPa, there is a problem in that when used as a battery container, it is deformed by an external force, thereby generating cracks and holes, thereby causing leakage of the electrolyte. Further, when the tensile strength exceeds 700 MPa, the workability becomes poor.
  • the tensile strength of the substrate 1 is more preferably 270 to 650 MPa. When more workability is required, it is more preferably 280 to 450 MPa.
  • the tensile strength of the substrate 1 was measured according to the “metallic material tensile test method” described in JIS standard Z2241.
  • the elongation of the substrate 1 according to the present embodiment is preferably 5 to 55%. If the elongation of the base material 1 is less than 5%, workability is poor at corners (corners), and cracks may occur during processing. On the other hand, if the elongation exceeds 55%, a high temperature and a long time are required as annealing conditions for obtaining such characteristics, so that productivity is deteriorated.
  • the elongation of the substrate 1 is more preferably 15 to 55%, and further preferably 20 to 50%.
  • the elongation of the base material 1 was performed according to "Equation (7) of measurement of elongation at break (%) A" of "metallic material tensile test method" described in JIS standard Z2241.
  • the elongation of the base material 1 is preferably 20% or more, and more preferably 30% or more, from the viewpoint of suppressing cracking of the base material 1 during molding and peeling of the resin film from the base material 1. It is still desirable.
  • the ratio of the crystal grain size in the plane direction (rolling direction) and the thickness direction (plane direction / thickness direction) of the substrate 1 according to this embodiment is preferably 0.8 to 8.
  • the “crystal grain size” in the present embodiment is an average value of the crystal grain size existing per unit area (for example, 1 ⁇ m ⁇ 1 ⁇ m).
  • There is no particular limitation on the method of measuring the average crystal grain size For example, a cross-sectional photograph of a metal plate is taken with a scanning electron microscope (SEM) and then, in accordance with JIS G0551 (Annex B or C). Can be measured.
  • the crystal grain size is determined based on each of the test line along the plane direction and the test line along the thickness direction, and the ratio is calculated.
  • the ratio of the crystal grain size described above may be calculated by comparing the longest length value in the rolling direction and the longest length value in the thickness direction in each of the plurality of particles to be measured. It is difficult for the substrate 1 to have a crystal grain ratio of less than 0.8 in a general manufacturing method. On the other hand, when the above-mentioned ratio of crystal grain diameters exceeds 8, cracks are likely to occur during processing.
  • the ratio of the crystal grain diameter of the substrate 1 is more preferably 0.8 to 5. When more workability is required, the ratio of the crystal grain size of the substrate 1 is more preferably 0.8 to 4.
  • a surface treatment layer 2 (also referred to as an electroplating layer) by electroplating is formed on at least a surface on the inner surface side of the battery container on the base material 1 according to the present embodiment.
  • the surface of the substrate 1 on the outer surface side of the battery container is the same as the above-mentioned inner surface or at least one layer from the viewpoint of establishing oxidation prevention and ease of manufacture.
  • the surface treatment layer 2 may be formed.
  • the surface treatment layer 2 is formed by electroplating, for example, to improve adhesion to a resin film when immersed in an electrolytic solution and to ensure corrosion resistance to the electrolytic solution when the resin film has a defect.
  • Examples thereof include a Cr plating layer to be formed, and a Ni alloy plating exemplified by a Ni plating layer and an Fe—Ni alloy plating layer. Further, a plurality of these plating layers may be provided. For example, a Ni plating layer may be formed on the base material 1 and then a Cr plating layer may be formed.
  • the surface treatment layer of this embodiment may be formed, for example, after the base material 1 is annealed after cold rolling, or formed after the base material 1 is cold-rolled and before annealing. It is also possible.
  • the Fe—Ni diffusion layer may be formed by heat treatment. At this time, an Fe—Ni diffusion layer may be formed between the Ni plating layer and the substrate 1, or the iron of the substrate 1 diffuses throughout the Ni plating layer, and An Fe—Ni diffusion layer may be directly formed.
  • the surface treatment layers 2 are formed on both surfaces of the substrate 1 in FIG. 1, the surface treatment layer 2 may be formed on at least the inner surface of the battery container. Alternatively, different types of surface treatment layers 2 (electroplating layers) may be formed on both surfaces of the substrate 1. For example, an electroplating layer (first electroplating layer) containing at least one of a Ni plating layer and a Cr plating layer is formed on a surface of the base material 1 on the inner surface side of the battery container.
  • first electroplating layer first electroplating layer containing at least one of a Ni plating layer and a Cr plating layer is formed on a surface of the base material 1 on the inner surface side of the battery container.
  • a Zn plating layer or a Zn alloy layer (for example, Zn—Ni, Zn—Co, Zn—Co—Mo, Zn—Fe, Zn—Sn) having a different corrosion resistance mechanism (as a sacrificial anticorrosion layer) is formed on the outer surface.
  • a second electroplating layer may be formed.
  • the electroplating layer containing the Zn plating layer or the Zn alloy plating layer as the sacrificial anticorrosion layer preferably has a Zn plating amount of, for example, 3 to 30 g / m 2 , and more preferably 5 to 25 g / m 2 . More preferably, the amount of plating is used.
  • Zn plating dissolves in the electrolytic solution, so it cannot be used as an inner surface that is always in contact.
  • it is effective for sacrificial corrosion prevention when a small amount of the electrolytic solution adheres.
  • Zn is preferentially dissolved at the end face, so that corrosion of the iron as the base material is prevented. This is effective because it can suppress the leakage of the electrolytic solution.
  • the cold-rolled metal plate is electrolytically degreased and pickled by a usual method, and then, for example, the following Ni plating bath is used as an example. be able to.
  • a Ni plating bath a nickel sulfate bath called a Watt bath is mainly used, but a sulfamic acid bath, a borofluoride bath, a chloride bath, or the like may be used.
  • Nickel sulfate 200-350g / l Nickel chloride: 20-60 g / l Boric acid: 10-50 g / l pH: 1.5 to 5.0 Bath temperature: 40-70 ° C Current density: 1 to 40 A / dm 2
  • the Ni plating as the surface treatment layer 2 formed on the substrate 1 is formed using not only pure Ni but also an alloy containing Ni such as a Ni—Co alloy or an Fe—Ni alloy. May be used.
  • the surface treatment layer 2 is made of one of a Ni plating layer composed of only Ni, an Fe—Ni diffusion layer in which Fe is diffused, and an Fe—Ni alloy plating layer in which both Fe and Ni are electrodeposited. May be included.
  • “composed of only Ni” means having only Ni as a metal element, and a substance derived from a plating bath additive or unavoidably mixed in a plating formation process. Impurities such as less than 1% carbon and less than 0.05% sulfur are allowed to be contained.
  • the Ni plating of this embodiment is preferably a Ni plating having a plating amount of 0.5 to 50.0 g / m 2 . If the plating amount of the Ni plating is less than 0.5 g / m 2 , the surface coverage is insufficient, the exposure of the base material is extremely increased, and there arises a problem that the content resistance is insufficient. On the other hand, if the plating amount of the Ni plating exceeds 50.0 g / m 2 , the thickness of the metal layer 10 increases due to an increase in the thickness of the plating layer, which leads to an increase in weight. Further, an increase in the plating processing time or the amount of plating causes a problem that productivity is lowered and manufacturing cost is increased.
  • an Fe—Ni diffusion layer can be formed.
  • the Fe—Ni diffusion layer preferably has a thickness of 0.2 ⁇ m or more and 3.0 ⁇ m or less.
  • the cold-rolled metal plate is electrolytically degreased and pickled by a usual method, and then, for example, the following Cr plating bath is used as an example. be able to.
  • Cr plating bath composition, conditions CrO 3 : 30 to 200 g / l NaF: 1 to 10 g / l pH: 1.0 or less Bath temperature: 35-65 ° C Current density: 5 to 50 A / dm 2
  • the Cr plating as the surface treatment layer 2 is preferably a Cr plating having a plating amount of 0.05 to 10.0 g / m 2 . If the plating amount of the Cr plating is less than 0.05 g / m 2 , the surface coverage is insufficient and the exposure of the base material 1 is extremely increased, resulting in a problem that the content resistance is insufficient. On the other hand, if the plating amount of the Cr plating exceeds 10.0 g / m 2 , similar problems as described above arise, such as an increase in weight, a decrease in productivity, and an increase in manufacturing cost.
  • the Cr plating layer has a higher proportion of metallic Cr than that of Cr hydrated oxide (CrOx).
  • CrOx Cr hydrated oxide
  • At least one surface of the metal plate 10 for a battery container according to the present embodiment may be covered with the thermoplastic resin 3.
  • the surface treatment layer 2 may be coated with a thermoplastic resin as a resin-coated metal plate for a battery container.
  • the battery container metal plate 10 may be configured as a laminate plate in which the surface treatment layer 2 is coated with a thermoplastic resin, or may have a configuration in which only the surface treatment layer 2 is formed. Is also good.
  • the thickness of such a thermoplastic resin 3 is 10 to 100 ⁇ m, and more preferably 10 to 50 ⁇ m.
  • thermoplastic resin 3 of the present embodiment a polyolefin resin, a polyester resin, or a polyamide resin is exemplified.
  • the polyolefin resin, polyester resin or polyamide resin preferably covers both surfaces of the battery container metal plate 10.
  • one surface (the inner surface side of the battery can) of the metal plate 10 for a battery container is preferably covered with a polyolefin-based resin (particularly, a polypropylene resin).
  • various polypropylene resins such as a random propylene resin, a homopropylene resin, and a block propylene resin may be used in a single layer, or they may be used as a multilayer by overlapping them.
  • a known additive may be added to the polypropylene resin.
  • additives include a low-crystalline ethylene butene copolymer, a low-crystalline propylene butene copolymer, a terpolymer composed of a three-component copolymer of ethylene, butene, and propylene, silica, zeolite, Examples thereof include anti-blocking agents such as acrylic resin beads and fatty acid amide-based slip agents.
  • a slip agent for improving the physical stability of the material
  • an antioxidant may be added as the above-mentioned additives.
  • the other surface (outer surface side of the battery can) of the metal plate 10 for a battery container is preferably coated with any of a polyester resin, a polyamide resin, and a polyolefin resin.
  • the polyester resin is preferably coated with polyethylene terephthalate.
  • the polyester resin in addition to polyethylene terephthalate, for example, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, or the like can be used.
  • a modified resin such as a urethane-modified polyester resin, an acryl-modified polyester resin, or an epoxy-modified polyester resin may be used.
  • the thickness of the resin covering one surface (for example, the inner surface side of the battery can) and the thickness of the resin covering the other surface (for example, the outer surface side of the battery can) of the battery container metal plate 10 are required.
  • the thickness may be adjusted appropriately within the above thickness range depending on the corrosion resistance and workability, and the thickness of both surfaces may be the same or different.
  • the polyester resin is preferably non-oriented.
  • the other surface (outer surface side of the battery can) of the battery container metal plate 10 is not limited to the polyester resin (polyethylene terephthalate) described above. Good.
  • both surfaces of the battery container metal plate 10 may be covered with a polyester resin.
  • the thermoplastic resin 3 may be in a form in which the metal plate 10 for a battery container is covered with a known adhesive.
  • a known adhesive for example, an inorganic adhesive such as an acid-modified polyolefin resin, an epoxy resin, an acrylic resin, a urethane resin, a silicone resin, a polyisobutylene-based resin, a fluororesin, or water glass can be used.
  • an acid-modified polyolefin resin layer between the base material 1 and the thermoplastic resin 3 described above. In this case, the surface treatment layer 2, the acid-modified polyolefin layer, and the thermoplastic resin 3 are formed in this order from the substrate 1.
  • Such an acid-modified polyolefin layer is effective for improving the adhesion between the metal plate 10 for a battery container and the polypropylene resin, particularly when the thermoplastic resin 3 is a polypropylene resin.
  • Specific examples of the acid-modified polyolefin layer include, for example, polypropylene graft-modified with an unsaturated carboxylic acid, and a copolymer obtained by copolymerizing propylene with acrylic acid or methacrylic acid.
  • the acid-modified polyolefin layer is preferably an acid-modified polypropylene having a melting point of 145 ° C. to 165 ° C. from the viewpoint of preventing abnormal heat generation and surging and neck-in during melt extrusion.
  • the thermoplastic resin 3 may be laminated on the substrate 1 on which the surface treatment layer 2 is formed, or the thermoplastic resin 3 melted by heating may be extruded by an extrusion width of an extruder.
  • the film may be extruded into a film by the slit and directly laminated on the substrate 1 on which the surface treatment layer 2 is formed by an extrusion lamination method.
  • the presence or absence of stretching of the film is not particularly limited.
  • the film may be a non-stretched film, a uniaxially stretched film, or a biaxially stretched film.
  • the laminating method of the thermoplastic resin 3 may be different between one surface (the inner surface side of the battery can) and the other surface (the outer surface side of the battery can) of the metal plate 10 for a battery container.
  • the other surface (the outer surface side of the battery can) of the base material 1 is further coated on the surface treatment layer 2 with the thermoplastic resin 3 stretched via, for example, a two-component curable polyurethane-based adhesive.
  • a stretched PET film or a stretched polyamide film may be dry-laminated.
  • a method in which polypropylene and acid-modified polypropylene are extruded into a multilayer film and directly laminated on the surface treatment layer 2 a multilayer film of polypropylene and acid-modified polypropylene is prepared in advance, and A method of thermally laminating on the surface treatment layer 2 or the like can also be adopted.
  • a method for manufacturing the metal plate 10 for a battery container of the present embodiment will be described with reference to FIG.
  • a metal plate made of iron or an iron alloy is prepared, and cold rolling is performed by putting the metal plate into a rolling mill that performs press working (step 1).
  • a cold-rolled substrate 1 having a thickness of 10 to 100 ⁇ m is formed. This cold rolling may be performed in multiple stages as necessary, or a heat treatment may be performed in between.
  • an annealing treatment is performed on the obtained base material 1 (step 2).
  • the temperature of the substrate 1 in the annealing treatment is 450 to 650 ° C, more preferably 500 to 600 ° C.
  • the time required for this annealing treatment is 2 to 9 hours, more preferably 2 to 6 hours.
  • the annealing can be performed in 20 to 120 seconds, but is preferably performed in the former temperature range from the viewpoint of improving workability.
  • the substrate 1 is subjected to a surface treatment (plating treatment), and on at least one surface of the substrate 1, a surface treatment layer 2 (at least one of a Ni plating layer and a Cr plating layer) A plating layer is formed (Step 3).
  • the surface treatment layer 2 (electroplating layer) formed in step 3 is, for example, a plating amount of 0.5 to 50.0 g / m 2 for a Ni plating layer, and a plating amount for a Cr plating layer. Is preferably 0.05 to 10.0 g / m 2 .
  • the annealing in Step 2 may be performed after the surface treatment layer 2 is formed.
  • a heat treatment may be further performed, for example, for the purpose of improving workability.
  • the heat treatment at this time can be performed under the same conditions as the annealing conditions described in Step 2. If the rolling process of Step 1 is performed after the plating treatment, cracks may be generated on the surface of the Ni plating film, and the adhesion and corrosion resistance may be reduced, which is not preferable.
  • the substrate 1 after steps 2 and 3 has a tensile strength of 260 to 700 MPa, an elongation of 5 to 55%, and a ratio of the crystal grain size in the plane direction (rolling direction) of the substrate 1 to the thickness direction. It is preferable to have at least one of the characteristics of 0.8 to 8. After the steps 2 and 3 as described above, the metal plate 10 for a battery container can be obtained.
  • step 4 the substrate 1 on which the surface treatment layer 2 is formed is subjected to the above-described process of coating the thermoplastic resin 3 with a thickness of about 10 to 50 ⁇ m (resin coating process).
  • Step 4 is not an essential step in the method for manufacturing the metal plate 10 for a battery container of the present embodiment, and may be omitted as long as it is not configured as a laminate plate (a resin-coated metal plate for a battery container).
  • a polypropylene resin is formed on one surface of the substrate 1 on which the surface treatment layer 2 is formed on the inner surface side of the container, and polyethylene is formed on one surface on the outer surface side of the container. Forming a terephthalate resin or a polypropylene resin can be exemplified.
  • the method of forming the resin is such that, as described above, the side of the substrate 1 on which the surface treatment layer 2 is formed on the container outer surface side employs a dry lamination method via a urethane-based adhesive, The extrusion lamination method via a molten acid-modified polypropylene can be adopted on the side to be formed.
  • the lamination method is not limited to the above, and any side of the substrate 1 on which the surface treatment layer 2 is formed may be a film lamination or an extrusion lamination.
  • the temperature of the substrate 1 on which the surface treatment layer 2 is formed when the thermoplastic resin 3 is coated is adjusted, for example, from room temperature to 280 ° C., and preferably 250 ° C. or lower according to the lamination mode.
  • a resin-coated metal plate for a battery container can be obtained.
  • the dry lamination method it is preferable to perform aging after dry lamination in a temperature environment of, for example, 30 to 100 ° C. for a period of 1 to 7 days.
  • the container shape of the present embodiment has a depth in which corners of a radius of curvature Rc (referred to as Rc because it is a corner in the circumferential direction) are formed at four corners so that a rectangular electrode plate can be accommodated.
  • D has a rectangular concave portion.
  • the side wall of the concave portion and the bottom surface of the concave portion are connected by a radius of curvature Rp (referred to as Rp because it is defined by R of the punch).
  • Rp radius of curvature
  • the corners R of the four corners of the above-mentioned concave portion are equal, but Rc and Rp may be different values.
  • the reason why the metal plate 10 for a battery case of the present embodiment is very effective for the shape of the battery case having the shapes of the curvature radii Rc and Rp and the depth D will be described in detail below.
  • Rc and Rp and depth D for higher capacity
  • Rc at the four corners of the above-described concave portion during molding, Rp between the side wall and the bottom surface of the concave portion, and depth D are important, but the balance between Rp and depth D is particularly important. Establishing such a balance is ideal because it is ideal to increase the size of each battery so that the battery characteristics of multiple batteries can be guaranteed by one battery. This is particularly important as a battery container for use in vehicles. It is important not only for a single-cell battery but also for a case where a plurality of batteries are assembled and used as a module.
  • Rc and Rp described above it is desirable that both have as small a radius of curvature as possible from the viewpoint of further increasing the area in which the electrodes are arranged and reducing the dead space in the battery.
  • the value of such a radius of curvature Rp is preferably less than 2 mm, more preferably 1.5 mm or less.
  • the value of the radius of curvature Rc varies depending on the use and battery size used, but is preferably less than 10 mm, more preferably 8 mm or less, and still more preferably 5 mm or less, and particularly the length of the short side of the container. If it is less than 50 mm, it is preferably 3 mm or less.
  • the depth D is preferably 5 mm or more, more preferably 6 mm or more.
  • the present inventors have conducted intensive studies on the relationship between the desired radius of curvature Rp and the depth D.
  • the metal plate 10 for a battery container is processed under the above-described conditions to increase the capacity. In this case, there were problems in moldability, adhesion to the resin film after molding, and content resistance after molding.
  • the radius of curvature Rp is set to 1.5 mm or less, the degree of difficulty increases dramatically.
  • the depth D the deeper the forming process is performed, the more severe the processing conditions for the material of the battery container metal plate 10 become.
  • the following three problems occur when the condition that the curvature radius Rp is less than 2 mm and the condition that the depth D is 5 mm or more are combined.
  • the first problem is that the base material 1 is easily cracked during the forming process.
  • the thickness has to be increased and stable molding is difficult, so that it has not been put to practical use.
  • the waving and wrinkles of the flange portion when drawing is performed are increased, and the sealing of the container becomes uncertain.
  • the specific gravity is larger than that of aluminum, so that the thickness of the base material 1 is reduced to suppress an increase in battery weight. Need to be thin.
  • the substrate 1 itself may be used.
  • Content resistance is required. That is, when press molding is performed under severe processing conditions as described above, the resin film covering the substrate 1 may be damaged. Further, even when the resin film itself has a defect such as a pinhole in the first place, the defect tends to spread in severe molding processing. In such a case, since the electrolytic solution comes into contact with the surface of the substrate 1, it is necessary to make the surface of the substrate 1 difficult to elute. In the case where aluminum is used as the base material as in the prior art, processing under the above-mentioned strict processing conditions becomes impossible in the first place due to the poor formability of aluminum.
  • the battery case is hermetically sealed after accommodating battery elements such as an electrode plate and an electrolytic solution.
  • the metal plate for a battery case 10 of the present embodiment can also be applied as a lid member of a battery case used for sealing.
  • the lid member which is a constituent member of such a battery container, may have an accommodation space similar to that of the battery container body shown in FIG. 4 or may be used as a flat plate.
  • the battery container it is preferable to heat seal the lid with the lid member at a peripheral flange portion of the battery container main body having the drawn housing portion.
  • the covering resin on the surface facing the battery container body and the lid member be configured so that the same type of resin such as polypropylene resins or polyester resins face each other.
  • the above-described sealing method is an example and is not limited thereto.
  • a known adhesive may be used.
  • the battery case obtained in the present embodiment is formed using the battery case metal plate 10 of the present embodiment, the adhesion between the nickel-plated metal plate or the chromium-plated metal plate and the resin is obtained. Therefore, it can be suitably used as a battery container for various primary batteries or secondary batteries such as alkaline batteries, nickel-metal hydride batteries, nickel-cadmium batteries, and lithium ion batteries.
  • a cold-rolled plate (thickness: 80 ⁇ m) of ultra low carbon steel having the chemical composition shown below was prepared.
  • the prepared metal plate (metal foil) was annealed at 650 ° C. for 3 hours to obtain a substrate 1 having the following characteristics.
  • TS -Tensile strength
  • EL Elongation
  • Ratio of crystal grain size in plane (rolling) direction and thickness direction 1.2
  • FIG. 3 after taking a photograph of a cross section of the metal plate 10 for a battery container with a scanning electron microscope (SEM), in accordance with JIS G0551 (Annex C), The measurement was performed in each of the plane direction and the thickness direction.
  • SEM scanning electron microscope
  • Ni plating layer 2 (Formation of surface treatment layer 2) Then, the base material 1 after the annealing is subjected to electrolytic degreasing and acid pickling by immersion in sulfuric acid, and then electroplating under the following conditions to obtain an electroplating layer having a Ni plating amount of 4.5 g / m 2. 2 (Ni plating layer) was formed.
  • the conditions for forming the Ni plating layer were as follows. (Formation condition of Ni plating layer) Bath composition: nickel sulfate, nickel chloride, boric acid, pit inhibitor pH: 4.3 Bath temperature: 55 ° C Current density: 10 A / dm 2
  • thermoplastic resin 3 a stretched polyamide film having a thickness of 25 ⁇ m was prepared as the thermoplastic resin 3.
  • a urethane-based adhesive was applied to one surface of the stretched polyamide film by a gravure roll. Thereafter, the applied urethane-based adhesive was dried by heating.
  • the substrate 1 on which the surface treatment layer 2 is formed and the stretched polyamide film to which the urethane-based adhesive is applied are rewound so that the surface treatment layer 2 and the urethane-based adhesive are in contact with each other, and are pressed and dried.
  • the thermoplastic resin 3 was formed by a lamination method.
  • the stretched polyamide film was laminated only on one side of the substrate 1 on which the surface treatment layer 2 was formed. Thus, a metal plate 10 for a battery container was obtained.
  • the outer shape was cut into a size of 80 mm x 120 mm, and the depth D of each of the concave portions after molding was 5 mm using a 33 mm x 54 mm mold. And a press molding (molding pressure: 0.9 MPa) so as to be 6 mm. The press molding was performed such that the side of the stretched polyamide film was on the outer surface side of the battery container.
  • Electrode used for evaluation of content resistance 1 mol / l of lithium hexafluorophosphate (LiPF 6 ) was added to an electrolyte in which ethylene carbonate (EC), dimethyl carbonate (DMC), and diethyl carbonate (DEC) were in a weight ratio of 1: 1 to 1; 1000 ppm of water was added to lithium hexafluorophosphate.
  • EC lithium hexafluorophosphate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • the metal plate 10 for a battery container cut into a size of 15 mm in width ⁇ 100 mm in length was immersed in this electrolytic solution, and stored as an immersion plating material for a predetermined number of days (for example, 14 days) in an environment of 85 ° C.
  • a metal plate having a Ni plating layer formed thereon and not covered with the thermoplastic resin 3 was used as the metal plate 10 for battery containers in this evaluation.
  • the evaluation was performed in a state where the press working at the depth D was not performed. Further, sealing was performed on the side of the metal plate 10 for battery containers that was not evaluated.
  • the immersion plated material was returned to room temperature after a predetermined number of days (for example, 1, 7, or 14 days), and then visually observed.
  • Example 2 The same substrate as in Example 1 was used. The process was performed in the same manner as in Example 1 except that the plating amount of Ni as the surface treatment layer 2 (electroplating layer) was 17.8 g / m 2 .
  • Example 3 The same substrate as in Example 1 was used. The process was performed in the same manner as in Example 1 except that the plating amount of Ni as the surface treatment layer 2 (electroplating layer) was 44.5 g / m 2 .
  • Example 4 The same substrate as in Example 1 was used. After Ni plating having a plating amount of 8.9 g / m 2 was formed on the substrate, the surface treatment layer 2 (electroplating layer) was subjected to a heat treatment at 700 ° C. for 1 minute. Other than that, it carried out similarly to Example 1 mentioned above.
  • Example 5 The same substrate as in Example 1 was used.
  • the base material after the annealing was subjected to electrolytic degreasing and pickling by immersion in sulfuric acid, and then electroplating was performed under the following conditions.
  • an Fe—Ni alloy plating was performed on a copper plate, and the amount of Ni and Fe deposited was determined by X-ray fluorescence. Thereafter, Fe—Ni alloy plating was performed on the iron base material under the same conditions. In this example, the total of Fe and Ni was 8.9 g / m 2 .
  • the conditions for the electroplating were as follows.
  • Example 6 The same substrate as in Example 1 was used. Then, the base material was subjected to electrolytic degreasing and pickling by immersion in sulfuric acid, and then electroplating under the following conditions to obtain an electroplating layer 2 (Cr plating) having a Cr plating amount of 0.05 g / m 2. Layer).
  • the conditions for the electroplating were as follows. (Cr plating conditions) CrO 3 : 50 g / l NaF: 1.7 g / l Bath temperature: 45 ° C Current density: 30 A / dm 2
  • the metal sheet 10 for a battery container obtained above was evaluated for moldability and content resistance in the same manner as in Example 1.
  • Example 7 The same substrate as in Example 1 was used. Except that the amount of Cr plating as the surface treatment layer 2 (electroplating layer) was 0.36 g / m 2 , the same procedure was performed as in Example 6 described above.
  • Example 8 The same substrate as in Example 1 was used. Except that the amount of Cr plating as the surface treatment layer 2 (electroplating layer) was 3.6 g / m 2 , the same procedure was performed as in Example 6 described above.
  • Example 9 The same substrate as in Example 1 was used. Except that the amount of Cr plating as the surface treatment layer 2 (electroplating layer) was 7.19 g / m 2 , the same procedure as in Example 6 was performed.
  • Example 1 The same substrate as in Example 1 was used. Except that the amount of Ni plating as the surface treatment layer 2 (electroplating layer) was 0.1 g / m 2 , the procedure was the same as in Example 1 described above.
  • Example 2 The same substrate as in Example 1 was used.
  • the base material is subjected to electrolytic degreasing and pickling by immersion in sulfuric acid, and then electroplating is performed under the following conditions to obtain an electroplating layer 2 (Zn plating) having a Zn plating amount of 3.6 g / m 2. Layer).
  • the conditions for the electroplating were as follows.
  • Example 4 The same substrate as in Example 1 was used. Then, the base material was subjected to electrolytic degreasing and pickling by immersion in sulfuric acid, and then electroplating under the following conditions to obtain an electroplating layer 2 (Sn plating) having a Sn plating amount of 1.4 g / m 2. Layer).
  • the conditions for the electroplating were as follows.
  • Example 7 The same substrate as in Example 1 was used.
  • the metal plate 10 for a battery container was obtained without forming the surface treatment layer 2 (electroplating layer) on the substrate. Then, in the same manner as in Example 1, evaluation of the moldability and the evaluation of the content resistance were performed on the battery container metal plate 10 (surface-treated pear).
  • Example 10 The same substrate as in Example 1 was used. An electroplating layer 2 (Ni plating layer) having a Ni plating amount of 8.9 g / m 2 was formed on this base material in the same manner as in Example 1. Next, a polypropylene film was formed by extrusion lamination on one surface (on the Ni plating layer) on the inner surface side of the container via the molten acid-modified polypropylene with respect to the base material thus obtained. Further, a stretched polyamide film was formed on one surface on the outer surface side of the container via a urethane-based adhesive by a dry laminating method, whereby a metal plate 10 for a battery container was obtained. The lamination temperature (base temperature) at this time was 250 ° C.
  • Example 2 Evaluation of content resistance 2 As the electrolytic solution used for the content resistance, the same electrolytic solution as in Example 1 described above was used.
  • the above-described pressed metal plate 10 for a battery container was immersed in the electrolytic solution, and stored as an immersion laminate material for a predetermined number of days (for example, 14 days) in an environment of 85 ° C. After a predetermined number of days (1 day, 7 days or 14 days) has elapsed, the temperature of the immersion laminate material is returned to room temperature, and the temperature of the immersion laminate material between the TENSILON RTC-1210A substrate 1 made by ORIENTEC and the adhesive (acid-modified polypropylene) was measured for laminate strength.
  • a predetermined number of days for example, 14 days
  • the temperature of the immersion laminate material is returned to room temperature, and the temperature of the immersion laminate material between the TENSILON RTC-1210A substrate 1 made by ORIENTEC and the adhesive (acid-modified polypropylene) was measured for laminate strength.
  • T-peeling was performed under the condition of a tensile speed of 100 mm / min. Then, when the value of the lamination strength at the first day in the case where the base material was aluminum (Comparative Example 12) was set to 100%, the ratio of the lamination strength after the number of days described above was calculated for each sample, and the peel strength was calculated. The residual rate was used.
  • Example 11 The same substrate as in Example 1 was used. As in Example 10 described above, except that a Cr plating layer having a Cr plating amount of 0.1 g / m 2 was used as the surface treatment layer 2 (electroplating layer) using the same Cr plating bath as in Example 6. went.
  • ⁇ Comparative Example 9> A hard base material having the same thickness as that of Comparative Example 8 (50 ⁇ m) and not subjected to annealing was used. Using the Zn plating bath shown in Comparative Example 2 for this substrate, the Zn plating layer having a Zn plating amount of 5.0 g / m 2 was used as the surface treatment layer 2 (electroplating layer) as described above. Performed in the same manner as in Example 10. As shown in FIG. 5, the crystal grain size was determined by taking a cross-sectional photograph of the battery container metal plate 10 with a scanning electron microscope (SEM) and then conforming to JIS G0551 (Annex C). The measurement was performed in each of the plane direction and the thickness direction.
  • SEM scanning electron microscope
  • Example 12 A 40 ⁇ m-thick cold-rolled aluminum plate (O-material) was prepared as a substrate. On this base material, as in Example 10, a polypropylene film was formed by extrusion lamination on one surface on the inner surface side of the container via a molten acid-modified polypropylene, and one surface on the outer surface side of the container. Then, a stretched polyamide film was formed by a dry lamination method via a urethane-based adhesive to obtain a metal plate 10 for a battery container. In addition, the surface treatment layer 2 was not formed. With respect to the metal plate 10 for a battery container obtained above, the evaluation of the moldability and the evaluation of the content resistance were performed in the same manner as in Example 10.
  • Example 12 The same substrate as in Example 1 was used. On one surface of the substrate, a surface treatment layer 2 composed of a Ni—Fe diffusion layer (Ni plating layer) was formed in the same manner as in Example 4 described above. Next, on the other surface of the base material, a Zn plating layer and a surface treatment layer 2 formed by a chromate treatment were formed in the same manner as in Comparative Example 11 described above.
  • a surface treatment layer 2 composed of a Ni—Fe diffusion layer (Ni plating layer) was formed in the same manner as in Example 4 described above.
  • a Zn plating layer and a surface treatment layer 2 formed by a chromate treatment were formed in the same manner as in Comparative Example 11 described above.
  • the substrate obtained by performing the surface treatment in this manner is configured such that the surface composed of the Ni—Fe diffusion layer is on the inner surface side and the surface composed of the Zn plating layer and the chromate treatment is the outer surface side.
  • a polypropylene film was laminated on the inner surface and a stretched polyamide film was laminated on the outer surface, whereby a metal plate 10 for a battery container was obtained.
  • the above-described moldability and content resistance were evaluated. As a result of the evaluation described above, there was no problem in the moldability on both the inner surface and the outer surface, and the content resistance was also “ ⁇ ” until the 14th day.
  • Table 1 shows the material specifications of each sample used in the above Examples 1 to 11 and Comparative Example.
  • Table 2 shows the surface treatment specifications and the plating amounts for the samples used in Examples 1 to 9 and Comparative Examples 1 to 12, and evaluations of the content resistance 1 and the moldability.
  • Table 3 shows the specifications of the surface treatment and the respective plating amounts, and the evaluation of the physical property resistance 2 and the moldability of the samples used in Examples 10 to 11 and Comparative Examples 9 to 12.
  • Comparative Examples 12 and 11 using aluminum were also used. As a result, it was possible to obtain a result having both the content resistance and the moldability that can withstand the use of a battery can. On the other hand, it was found that Comparative Examples 10 and 11 did not have the content resistance enough to withstand use as a battery container.
  • the metal plate for a battery container of the present invention and the method for producing the same can exhibit sufficient moldability and content resistance for use in a battery container such as a lithium ion secondary battery, and can be used in a wide range of industries using batteries. Applicable.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

L'invention a pour but de fournir : une plaque métallique destinée à un récipient de cellule, la fissuration d'un substrat ou le pelage d'une résine pouvant être supprimé même lors de la réalisation d'un processus de formage à l'aide de la plaque métallique destinée à une application dans une cellule, et la plaque métallique destinée à un récipient de cellule présentant une excellent adhésion à un film de résine appliquée sur cette dernière et présentant une excellent résistance de contenu vis-à-vis d'un électrolyte liquide non aqueux avec lequel le récipient est rempli ; et un procédé destiné à la fabrication d'une plaque métallique destinée à un récipient de cellule. À cet effet, la plaque métallique destinée à un récipient de cellule comprend du fer ou un alliage de fer et s'utilise comme récipient de cellule, l'épaisseur de la plaque métallique étant de 10 à 100 µm, et la plaque métallique présentant, sur au moins l'une de ses surfaces, une couche d'électroplacage contenant une couche de placage de Ni de 0,5 à 50,0 g/m2 et/ou une couche de placage de Cr de 0,05 à 10,0 g/m2.
PCT/JP2019/034121 2018-08-31 2019-08-30 Plaque métallique destinée à un récipient de cellule et procédé destiné à la fabrication d'une plaque métallique destinée à un récipient de cellule Ceased WO2020045627A1 (fr)

Priority Applications (3)

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JP2020539627A JP7413264B2 (ja) 2018-08-31 2019-08-30 電池容器用金属板およびこの電池容器用金属板の製造方法
CN201980056086.0A CN112639171A (zh) 2018-08-31 2019-08-30 电池容器用金属板和该电池容器用金属板的制造方法
KR1020217002247A KR102872693B1 (ko) 2018-08-31 2019-08-30 전지 용기용 금속판 및 이 전지 용기용 금속판의 제조 방법

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7070820B1 (ja) * 2021-02-22 2022-05-18 Ｊｆｅスチール株式会社 成形品の製造方法、ブランク、及び角筒深絞り成形品
WO2022176276A1 (fr) * 2021-02-22 2022-08-25 Ｊｆｅスチール株式会社 Procédé de production d'article moulé, ébauche et article moulé par emboutissage profond de tube polygonal
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WO2022176553A1 (fr) * 2021-02-19 2022-08-25 東洋鋼鈑株式会社 Feuille d'acier pour compartiments de batterie et compartiment de batterie à poche produit à partir de celle-ci
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WO2022176276A1 (fr) * 2021-02-22 2022-08-25 Ｊｆｅスチール株式会社 Procédé de production d'article moulé, ébauche et article moulé par emboutissage profond de tube polygonal
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