WO2017221763A1 - Steel sheet for battery outer cylindrical canister, battery outer cylindrical canister, and battery - Google Patents

Steel sheet for battery outer cylindrical canister, battery outer cylindrical canister, and battery Download PDF

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Publication number
WO2017221763A1
WO2017221763A1 PCT/JP2017/021760 JP2017021760W WO2017221763A1 WO 2017221763 A1 WO2017221763 A1 WO 2017221763A1 JP 2017021760 W JP2017021760 W JP 2017021760W WO 2017221763 A1 WO2017221763 A1 WO 2017221763A1
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WO
WIPO (PCT)
Prior art keywords
battery outer
diffusion layer
battery
steel sheet
amount
Prior art date
Application number
PCT/JP2017/021760
Other languages
French (fr)
Japanese (ja)
Inventor
幹人 須藤
威 鈴木
祐介 中川
由紀夫 小幡
Original Assignee
Ｊｆｅスチール株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ｊｆｅスチール株式会社 filed Critical Ｊｆｅスチール株式会社
Priority to JP2017544977A priority Critical patent/JP6260752B1/en
Priority to CN201780027816.5A priority patent/CN109072449B/en
Publication of WO2017221763A1 publication Critical patent/WO2017221763A1/en

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Classifications

    • 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
    • H01M50/107—Primary casings; Jackets or wrappings characterised by their shape or physical structure having curved cross-section, e.g. round or elliptic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
    • B21D22/20—Deep-drawing
    • 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
    • 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
    • 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
    • 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 steel plate for a battery outer can, a battery outer can and a battery.
  • a primary battery such as an alkaline manganese battery
  • a secondary battery such as a lithium ion battery mounted on a notebook personal computer or a hybrid vehicle, etc. are known.
  • Ni plating is applied to the surface of the steel sheet constituting the outer cylinder can (battery outer cylinder can) used in these batteries, and an Ni layer is formed. Due to the difference in the process of applying Ni plating, there are two types of manufacturing methods for battery outer cans. One is a pre-plating method in which a steel plate to which Ni plating is applied is press-formed into a battery outer can, and thereafter no plating treatment is performed. The other is a post-plating method in which Ni plating is applied to the surface of the battery outer can after press molding using a technique such as barrel plating.
  • Patent Document 1 describes that “having a Fe—Ni diffusion layer having a thickness of 0.5 ⁇ m or more and 4 ⁇ m or less on the surface that becomes the inner surface of the container by press molding, further on the thickness 0.25 ⁇ m or more thereof, having the following Ni layer 4 [mu] m, the surface to be the outer surface of the container attachment amount 0.05 g / m 2 or more, has a 1.5 g / m 2 less than Ni, the A Ni-plated steel sheet for containers, characterized in that Ni is diffused inside and the surface layer has a Ni / (Fe + Ni) mass ratio of 0.1 to 0.9 (claim 1). ).
  • such a steel plate for battery outer cylinder cans Ni-plated steel sheet for containers
  • Ni plating is applied to the outer surface using a technique such as barrel plating. To do.
  • ⁇ Cemented carbide is often used as the material of the mold (mold) used for post-plating press forming, but relatively brittle and hardened steel may also be used.
  • the present invention is a steel plate for battery outer cans used in the post-plating method, the occurrence of scratches is suppressed even when press molding is repeatedly performed using a mold made of quenched steel, and
  • An object of the present invention is to provide a steel plate for a battery outer can that is excellent in the corrosion resistance of the obtained battery outer can, and a battery outer can and a battery using the same.
  • the present invention provides the following [1] to [8].
  • [1] Fe-Ni diffusion layers are provided on both surface layers of the steel sheet, and the Fe-Ni diffusion layer has an Ni-concentrated adhesion amount on one side of the steel sheet of 50 mg / m 2 or more and 500 mg / m 2 or less.
  • a steel plate for battery outer cans. [2] The steel plate for battery outer cans according to [1], wherein the Ni ratio on the outermost surface of the Fe—Ni diffusion layer is 1.0% or more and less than 20.0%. However, the Ni ratio is the ratio of the Ni amount to the total of Fe amount and Ni amount on the outermost surface of the Fe—Ni diffusion layer, and the unit of the Fe amount and the Ni amount is atomic%. .
  • the steel plate for battery outer cans according to [1] or [2], wherein the thickness of the Fe—Ni diffusion layer is 0.01 ⁇ m or more and less than 0.5 ⁇ m.
  • the battery outer cylinder-shaped steel plate has Fe—Ni diffusion layers on the inner and outer surface layers, and further has a Ni layer on the Fe—Ni diffusion layer on the outer surface side of the steel plate.
  • a part of the Fe—Ni diffusion layer on the outer surface side of the steel sheet is an Fe—Ni diffusion layer A having an Ni conversion amount per side of the steel sheet of 50 mg / m 2 or more and 500 mg / m 2 or less. Tube can.
  • a steel plate for a battery outer can used in a post-plating method, the occurrence of scratches is suppressed even when press molding is repeatedly performed using a mold made of quenched steel, and It is possible to provide a steel plate for a battery outer can that is excellent in corrosion resistance of the obtained battery outer can, and a battery outer can and a battery using the same.
  • the steel sheet for battery outer cans of the present invention (hereinafter, also simply referred to as “the steel sheet for cans of the present invention”) has Fe—Ni diffusion layers on both surface layers of the steel sheet.
  • the steel plate for cans of the present invention is a steel plate for battery outer cylinder cans used in post-plating methods, and even when press forming is repeatedly performed using a forming die made of quenched steel, the occurrence of scratches is suppressed.
  • the obtained battery outer can has excellent corrosion resistance. The reason is presumed as follows.
  • the steel sheet for a battery outer can used in the post-plating method described in Patent Document 1 has “Fe—Ni diffusion layer having a thickness of 0.5 ⁇ m or more on the surface that becomes the inner surface of the container by press molding”.
  • the Ni adhesion amount of this Fe—Ni diffusion layer is 4500 mg / m 2 or more in terms of conversion.
  • Such a steel sheet for battery outer cans of Patent Document 1 is a process in which a forming die made of a relatively brittle and hardened steel is repeatedly pressed by a Ni-adhering amount of the Fe—Ni diffusion layer is too hard. It is thought that it will gradually hurt. And since the shaping
  • the Fe—Ni diffusion layer of the steel sheet for cans of the present invention has a reasonably small Ni adhesion amount of 500 mg / m 2 or less, and is considered to be soft enough not to damage a forming die made of hardened steel. For this reason, the generation
  • the corrosion resistance when it is made into a battery outer can (hereinafter also simply referred to as “corrosion resistance”). Becomes better. More specifically, the content of the Fe-Ni diffusion layer is electrochemically stable on the inner surface of the battery outer can when compared with the case where the Fe-Ni diffusion layer is absent or too little. Corrosion resistance against is improved.
  • Ni plating is applied to the outer surface by barrel plating or the like after forming to form a Ni layer.
  • the Ni layer has some pinholes, and corrosion proceeds from here.
  • the potential difference between the Ni layer and the underlayer can be reduced compared to the case where there is no Fe—Ni diffusion layer or too little, and the corrosion resistance. Will improve.
  • the kind of steel plate is not particularly limited.
  • a steel plate for example, a low carbon steel plate or an extremely low carbon steel plate
  • the content of Cr in the steel sheet may cause the steel to harden and deteriorate formability, or may form a Cr oxide on the surface of the steel sheet during annealing, making it impossible to obtain a desired surface state.
  • the Cr content of the steel sheet is preferably less than 3% by mass, and more preferably less than 1% by mass.
  • the manufacturing method of the steel plate is not particularly limited. For example, it is manufactured through processes such as hot rolling, pickling, cold rolling, annealing, and temper rolling from a normal steel slab manufacturing process.
  • the formation of the Fe—Ni diffusion layer is essential, it is possible to apply Ni plating to an unannealed steel sheet after cold rolling, and to diffuse the Ni plating inside the steel sheet together with the annealing treatment of the steel sheet. Above, the most efficient. For this reason, it is preferable to use an unannealed steel sheet after cold rolling as the steel sheet.
  • the steel plate for cans of the present invention has Fe—Ni diffusion layers on the surface layers on both sides of the steel plate.
  • Ni conversion amount (Ni adhesion amount) per one side of the steel sheet is 50 mg / m 2 or more and 500 mg / m 2 or less.
  • the steel plate for cans of this invention is excellent in both scratch resistance and corrosion resistance.
  • Ni deposition amount of Fe-Ni diffusion layer is preferably 350 mg / m 2 or less, 300 mg / m 2 or less is more preferable.
  • the amount of Ni deposited on the Fe—Ni diffusion layer can be measured by surface analysis using fluorescent X-ray analysis.
  • a calibration curve related to the Ni adhesion amount is specified in advance using a Ni adhesion sample with a known Ni adhesion amount, and the Ni adhesion amount is relatively specified using the calibration curve.
  • the fluorescent X-ray analysis is performed, for example, under the following conditions.
  • Apparatus X-ray fluorescence analyzer System 3270 manufactured by Rigaku Corporation ⁇ Measurement diameter: 30 mm ⁇ Measurement atmosphere: Vacuum ⁇ Spectrum: Ni-K ⁇ ⁇ Slit: COARSE -Spectral crystal: TAP The peak count number of Ni—K ⁇ in the fluorescent X-ray analysis of the Fe—Ni diffusion layer measured under the above conditions is used. Using a standard sample with a known adhesion amount measured by the gravimetric method, a calibration curve related to the Ni adhesion amount is specified in advance, and the Ni adhesion amount is relatively determined using the calibration curve.
  • the thickness of the Fe—Ni diffusion layer is 0.01 ⁇ m or more because it is easy to maintain the Fe—Ni diffusion layer after forming and the scratch resistance and corrosion resistance are more excellent. 0.4 ⁇ m or less is more preferable, and 0.38 ⁇ m or less is still more preferable because it is preferably less than 0.5 ⁇ m and scratch resistance is further improved.
  • the thickness of the Fe—Ni diffusion layer can be measured by GDS (glow discharge emission analysis). Specifically, first, sputtering is performed from the surface of the Fe—Ni diffusion layer toward the inside of the steel plate, analysis is performed in the depth direction, and a sputtering time at which the Ni intensity becomes 1/10 of the maximum value is obtained. Next, the relationship between the sputtering depth by GDS and the sputtering time is obtained using pure iron. Using this relationship, the sputtering depth is calculated in terms of pure iron from the sputtering time at which the Ni strength obtained previously becomes 1/10 of the maximum value, and the calculated value is taken as the thickness of the Fe—Ni diffusion layer. GDS was carried out under the following conditions.
  • Ni ratio (hereinafter also simply referred to as “Ni ratio”) on the outermost surface of the Fe—Ni diffusion layer is 1.0% or more and 20.20 because it is more excellent in scratch resistance and corrosion resistance. Preferably it is less than 0%.
  • the Ni ratio on the outermost surface of the Fe—Ni diffusion layer is important because Ni on the outermost surface of the Fe—Ni diffusion layer has a direct effect on the corrosion resistance, but Ni diffused in the steel has a small effect on improving the corrosion resistance. . On the other hand, if the Ni ratio is too high, the outermost surface becomes hard and scratch resistance may be insufficient.
  • the suitable range of Ni ratio is 1.0% or more and less than 20.0% mentioned above.
  • the lower limit of the Ni ratio is more preferably 3.0%.
  • the upper limit of the Ni ratio is more preferably 15.0%, still more preferably 13.0%.
  • the Ni ratio (unit:%) on the outermost surface of the Fe—Ni diffusion layer is the ratio of the Ni amount to the sum of the Fe amount and the Ni amount on the outermost surface of the Fe—Ni diffusion layer, that is, the formula “Ni amount / (Fe amount + Ni amount) ⁇ 100 ”.
  • the unit of Fe amount and Ni amount is atomic%.
  • the amount of Fe (unit: atomic%) and the amount of Ni (unit: atomic%) on the outermost surface of the Fe—Ni diffusion layer were determined by ultrasonically cleaning the steel sheet on which the Fe—Ni diffusion layer was formed in acetone for 10 minutes. It can be measured by performing Auger electron spectroscopy without performing sputtering.
  • Auger electron spectroscopic measurement is performed at 10 points in different fields of view in the same sample, and the average value of the results of measurement at 10 points is used for the Fe amount and Ni amount, respectively.
  • Auger electron spectroscopy measurement was performed under the following conditions.
  • ⁇ Device ULVAC-PHI PHI660 Observation and analysis conditions: acceleration voltage 10.0 kV, current value 0.5 ⁇ A Observation magnification 1,000 times, measurement range 540-900eV
  • the method for forming the Fe—Ni diffusion layers on the surface layers on both surfaces of the steel plate is not particularly limited, but the following method is given as an example.
  • pre-treatment eg, degreasing and pickling
  • a Ni plating bath examples include a watt bath, a sulfamic acid bath, a borofluoride bath, and a chloride bath.
  • the Ni adhesion amount of the formed Fe—Ni diffusion layer can be set to 50 mg / m 2 or more and 500 mg / m 2 or less.
  • annealing for the purpose of recrystallizing the steel sheet is performed on the steel sheet to which Ni plating has been applied.
  • the Ni plating diffuses inside the steel sheet and an Fe—Ni diffusion layer is formed.
  • the soaking temperature is preferably 600 ° C. or more and 800 ° C. or less, and the holding time at this soaking temperature is preferably 10 seconds or more and 60 seconds or less. The shorter the holding time at the soaking temperature, the more difficult Ni diffuses in the steel, and the Ni ratio on the outermost surface increases. From the viewpoint of corrosion resistance, the holding time at the soaking temperature is more preferably less than 30 seconds. .
  • the thickness of the formed Fe—Ni diffusion layer is set to 0.01 ⁇ m or more and less than 0.5 ⁇ m, and the Ni ratio on the outermost surface is set to 1.0% or more and less than 20.0%. This is preferable.
  • shape correction and surface roughness adjustment may be performed by temper rolling as necessary.
  • the manufacturing method of the present invention includes, for example, a step of forming the steel plate for cans of the present invention into a battery outer can shape (for example, a cylindrical shape) by press forming using a forming die, and then into a battery outer can shape. And forming a Ni layer on the outer surface of the formed steel plate for a can of the present invention by applying Ni plating.
  • the method of forming (press molding) is not particularly limited, and can be performed by a general method used for forming a battery outer can.
  • the steel plate for cans of the present invention is punched into a circular shape, drawn into a cup shape, formed into a cylindrical shape or the like by a redrawing and DI (Drawing and Ironing) process.
  • cemented carbide is often used as the material of the mold used, but relatively brittle and hardened steel may be used.
  • the Fe—Ni diffusion layer of the steel sheet for cans of the present invention is considered not to damage the mold made of hardened steel, the generation of scratches on the steel sheet for battery outer cylinder can be suppressed.
  • the Ni adhesion amount, thickness, and Ni ratio of the Fe—Ni diffusion layer subjected to press forming can be changed without maintaining the state before press forming.
  • at least a part of the portion that becomes the outer surface side of the battery outer can (for example, the portion that becomes the end surface of the positive protrusion of the battery outer can) is not press-formed. It remains as processed. Therefore, at least a part of the outer surface side of the battery outer can obtained by using the steel plate for cans of the present invention (battery outer can of the present invention) is Fe-Ni diffusion in the steel plate for cans of the present invention before press forming.
  • the Ni adhesion amount, thickness, and Ni ratio of the layer are maintained as they are.
  • Ni plating after forming into battery outer tube can shape The method for applying Ni plating is not particularly limited, and a conventionally known method can be used.
  • the steel plate for cans of the present invention formed into a battery outer can shape is subjected to Ni plating by a barrel plating method by appropriately adjusting conditions such as current density using a Ni plating bath.
  • the Ni plating bath include a watt bath, a sulfamic acid bath, a borofluoride bath, and a chloride bath.
  • Ni plating is performed on the Fe—Ni diffusion layer on at least the outer surface side of the steel plate for a can of the present invention formed into a battery outer cylinder can shape, thereby forming a Ni layer.
  • the steel plate for cans of the present invention is formed into a battery outer cylinder can shape, Ni plating is less likely to enter inside, and the inner surface of the steel plate for cans of the present invention in the shape of a battery outer cylinder can is Ni. Plating is difficult to apply.
  • the Ni layer may be formed on the inner surface of the battery steel plate for cans of the present invention having a battery outer can shape as well as the outer surface.
  • the thickness of the Ni plating (Ni layer) formed on the Fe—Ni diffusion layer is preferably 1 ⁇ m or more and more preferably 2 ⁇ m or more from the viewpoint of corrosion resistance.
  • the upper limit of the thickness of Ni layer is not specifically limited, For example, 7 micrometers or less are preferable from a viewpoint of economical efficiency.
  • the battery outer can of the present invention is a battery outer can obtained using the steel plate for cans of the present invention. More specifically, the battery outer can of the present invention has a Fe—Ni diffusion layer on the inner surface and outer surface of the battery outer can-shaped steel plate, on the Fe—Ni diffusion layer on the outer surface side of the steel plate. Furthermore, it has a Ni layer, and a part of the Fe—Ni diffusion layer on the outer surface side of the steel sheet has a Ni-concentrated adhesion amount on one side of the steel sheet of 50 mg / m 2 or more and 500 mg / m 2 or less. This is a battery outer can that is an Fe—Ni diffusion layer A.
  • a steel plate is formed into a battery outer can shape by press forming, and on both surfaces (inner surface and outer surface) of this steel plate, similarly to the steel plate for cans of the present invention, An Fe—Ni diffusion layer is formed. Then, Ni plating is performed on the Fe—Ni diffusion layer on at least the outer surface side of the steel plate to form a Ni layer.
  • At least a part of the Fe—Ni diffusion layer on the outer surface side of the battery outer can of the present invention is the Fe—Ni diffusion layer (Ni adhesion amount) in the steel sheet for cans of the present invention before press forming. : 50 mg / m 2 or more and 500 mg / m 2 or less) is maintained as it is. That is, in the battery outer can of the present invention, at least a part of the Fe—Ni diffusion layer on the outer surface side of the battery outer can-shaped steel plate has an Fe deposition amount of Ni of 50 mg / m 2 or more and 500 mg / m 2 or less. -Ni diffusion layer A.
  • the preferable range of the Ni adhesion amount, the thickness and the Ni ratio of the Fe—Ni diffusion layer A in the battery outer can of the present invention is the Ni adhesion amount, thickness and Ni of the Fe—Ni diffusion layer in the steel sheet for cans of the present invention. It is the same as the ratio.
  • the thickness of the Ni layer on the Fe—Ni diffusion layer is as described above, preferably 1 ⁇ m or more, and more preferably 2 ⁇ m or more. Although an upper limit is not specifically limited, 7 micrometers or less are preferable.
  • the battery of this invention is a battery provided with the battery outer cylinder can of this invention, and the electrolyte solution, electrode, and separator which are arrange
  • the steel plate subjected to Ni plating was introduced into a continuous annealing line, the steel plate was annealed, and Ni was diffused inside the steel plate to form Fe—Ni diffusion layers on both surface layers of the steel plate.
  • the thickness (unit: ⁇ m) and Ni ratio (unit:%) of the Fe—Ni diffusion layer were changed to the following Table 1 by using the annealing conditions (soaking temperature and holding time) shown in Table 1 below. It was made to become the numerical value of description.
  • temper rolling was performed, and the test material no. 1 to 27 steel plates for battery outer cans were obtained.
  • ⁇ Manufacture of battery outer can> ⁇ Molding> The obtained steel plate for battery outer can was punched into a circular shape, drawn into a cup, redrawed and formed into a cylindrical 18650 type battery outer can by a DI process. The plate thickness of the side wall portion was reduced to 0.15 mm by the DI process. ⁇ Ni plating >> Then, Ni plating was performed by barrel plating on at least the outer surface of the steel sheet for battery outer cylinder cans formed into a battery outer cylinder can shape to form a Ni layer having a thickness of 4 ⁇ m. In this way, a battery outer can was obtained.
  • the test material No. 1 in which the Ni adhesion amount of the Fe—Ni diffusion layer exceeded 500 mg / m 2 was used. 10-11 and 22-23 were inferior in scratch resistance. The test material No. whose Ni adhesion amount of the Fe—Ni diffusion layer is less than 50 mg / m 2 12 and 24 were inferior in corrosion resistance.
  • Test material No. 1 When comparing 1 to 9, 13 to 21, and 25 to 27, the test material No. 1 in which the Ni ratio on the outermost surface of the Fe—Ni diffusion layer is 1.0% or more and less than 20.0% Nos. 1 to 9, 13 to 21, and 26 to 27 are test materials having Ni ratios of 20.0% or more. The scratch resistance was better than 25.

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

Abstract

Provided are: a steel sheet for a battery outer cylindrical canister, the steel sheet being subjected to post-plating, able to suppress damage even if press molding is repeated using a mold made of quenched steel, and providing a battery outer cylindrical canister with good corrosion resistance; a battery outer cylindrical canister; and a battery using the battery outer cylindrical canister. The steel sheet for the battery outer cylindrical canister comprises Fe-Ni diffusion layers on surface layers on both sides of the steel sheet. The amount of deposition of the Fe-Ni diffusion layers in terms of Ni is 50-500 mg/m2 on each surface of the steel sheet.

Description

電池外筒缶用鋼板、電池外筒缶および電池Steel plate for battery outer can, battery outer can and battery
　本発明は、電池外筒缶用鋼板、電池外筒缶および電池に関する。 The present invention relates to a steel plate for a battery outer can, a battery outer can and a battery.
　電池として、例えば、アルカリマンガン電池などの一次電池；ノート型パソコンまたはハイブリッド型自動車などに搭載されているリチウムイオン電池などの二次電池；等が知られている。 As the battery, for example, a primary battery such as an alkaline manganese battery; a secondary battery such as a lithium ion battery mounted on a notebook personal computer or a hybrid vehicle, etc. are known.
　これらの電池に使用される外筒缶（電池外筒缶）を構成する鋼板の表面には、耐食性の観点から、Ｎｉめっきが付与されて、Ｎｉ層が形成されている。
　Ｎｉめっきを付与する工程の違いから、電池外筒缶には、２種類の製造方法がある。
　１つは、Ｎｉめっきが付与された鋼板を電池外筒缶にプレス成形して、その後めっき処理を行なわない先めっき法である。もう１つは、プレス成形後の電池外筒缶の表面に、バレルめっき等の手法を用いて、Ｎｉめっきを付与する後めっき法である。 From the viewpoint of corrosion resistance, Ni plating is applied to the surface of the steel sheet constituting the outer cylinder can (battery outer cylinder can) used in these batteries, and an Ni layer is formed.
Due to the difference in the process of applying Ni plating, there are two types of manufacturing methods for battery outer cans.
One is a pre-plating method in which a steel plate to which Ni plating is applied is press-formed into a battery outer can, and thereafter no plating treatment is performed. The other is a post-plating method in which Ni plating is applied to the surface of the battery outer can after press molding using a technique such as barrel plating.
　後めっき法に用いる電池外筒缶用鋼板として、例えば、特許文献１には、「プレス成型により容器内面となる面に厚さ０．５μｍ以上、４μｍ以下のＦｅ－Ｎｉ拡散層を有し、さらにその上に厚さ０．２５μｍ以上、４μｍ以下のＮｉ層を有し、容器外面となる面に付着量０．０５ｇ／ｍ2以上、１．５ｇ／ｍ2未満のＮｉを有し、そのＮｉが内部に拡散しており、表層のＮｉ／（Ｆｅ＋Ｎｉ）質量比が０．１以上、０．９以下であることを特徴とする容器用Ｎｉめっき鋼板」が開示されている（請求項１）。
　特許文献１においては、このような電池外筒缶用鋼板（容器用Ｎｉめっき鋼板）をプレス成形して電池外筒缶にした後、バレルめっき等の手法を用いて、外面にＮｉめっきを付与する。 As a steel sheet for battery outer cans used in the post-plating method, for example, Patent Document 1 describes that “having a Fe—Ni diffusion layer having a thickness of 0.5 μm or more and 4 μm or less on the surface that becomes the inner surface of the container by press molding, further on the thickness 0.25μm or more thereof, having the following Ni layer 4 [mu] m, the surface to be the outer surface of the container attachment amount 0.05 g / m 2 or more, has a 1.5 g / m 2 less than Ni, the A Ni-plated steel sheet for containers, characterized in that Ni is diffused inside and the surface layer has a Ni / (Fe + Ni) mass ratio of 0.1 to 0.9 (claim 1). ).
In Patent Document 1, such a steel plate for battery outer cylinder cans (Ni-plated steel sheet for containers) is press-molded into a battery outer cylinder can, and then Ni plating is applied to the outer surface using a technique such as barrel plating. To do.
特許第４９９５１４０号公報Japanese Patent No. 4995140
　後めっき法のプレス成形に使用する成形型（金型）の材料としては、超硬合金が用いられることが多いが、比較的もろい焼入れ鋼が使用される場合もある。 超 Cemented carbide is often used as the material of the mold (mold) used for post-plating press forming, but relatively brittle and hardened steel may also be used.
　焼入れ鋼で作られた成形型を使用して、特許文献１の電池外筒缶用鋼板（容器用Ｎｉめっき鋼板）のプレス成形を繰り返し行なうと、次第に成形型に傷が付き、その結果、成形される電池外筒缶用鋼板に傷を与えてしまう場合がある。この場合、得られる電池外筒缶は、傷を有するため、耐食性に劣るおそれがある。 Using a mold made of hardened steel and repeatedly pressing the steel sheet for battery outer cylinder cans (Ni-plated steel sheet for containers) of Patent Document 1, the mold is gradually damaged, and as a result, the mold is formed. In some cases, the steel plate for the battery outer cylinder can be damaged. In this case, since the obtained battery outer cylinder can has a damage | wound, there exists a possibility that it may be inferior to corrosion resistance.
　そこで、本発明は、後めっき法に用いる電池外筒缶用鋼板であって、焼入れ鋼で作られた成形型を使用してプレス成形を繰り返し行なう場合にも傷付きの発生が抑制され、かつ、得られる電池外筒缶の耐食性にも優れる電池外筒缶用鋼板、ならびに、これを用いた電池外筒缶および電池を提供することを目的とする。 Therefore, the present invention is a steel plate for battery outer cans used in the post-plating method, the occurrence of scratches is suppressed even when press molding is repeatedly performed using a mold made of quenched steel, and An object of the present invention is to provide a steel plate for a battery outer can that is excellent in the corrosion resistance of the obtained battery outer can, and a battery outer can and a battery using the same.
　本発明者らが、鋭意検討した結果、鋼板の両面の表層に特定のＦｅ－Ｎｉ拡散層を有する電池外筒缶用鋼板を用いることによって、上記目的が達成されることを見出し、本発明を完成させた。 As a result of intensive studies by the present inventors, it has been found that the above object can be achieved by using a steel sheet for a battery outer can having a specific Fe—Ni diffusion layer on both surface layers of the steel sheet. Completed.
　すなわち、本発明は、以下の［１］～［８］を提供する。
　［１］鋼板の両面の表層にＦｅ－Ｎｉ拡散層を有し、上記Ｆｅ－Ｎｉ拡散層は、上記鋼板の片面あたりのＮｉ換算の付着量が、５０ｍｇ／ｍ2以上５００ｍｇ／ｍ2以下である、電池外筒缶用鋼板。
　［２］上記Ｆｅ－Ｎｉ拡散層の最表面におけるＮｉ比率が、１．０％以上２０．０％未満である、上記［１］に記載の電池外筒缶用鋼板。ただし、上記Ｎｉ比率は、上記Ｆｅ－Ｎｉ拡散層の最表面における、Ｆｅ量とＮｉ量との合計に対する上記Ｎｉ量の割合であり、上記Ｆｅ量および上記Ｎｉ量の単位は、原子％である。
　［３］上記Ｆｅ－Ｎｉ拡散層の厚さが、０．０１μｍ以上０．５μｍ未満である、上記［１］または［２］に記載の電池外筒缶用鋼板。
　［４］電池外筒缶形状の鋼板の内面および外面の表層にＦｅ－Ｎｉ拡散層を有し、上記鋼板の外面側の上記Ｆｅ－Ｎｉ拡散層上に、更に、Ｎｉ層を有し、上記鋼板の外面側の上記Ｆｅ－Ｎｉ拡散層の一部が、上記鋼板の片面あたりのＮｉ換算の付着量が５０ｍｇ／ｍ2以上５００ｍｇ／ｍ2以下のＦｅ－Ｎｉ拡散層Ａである、電池外筒缶。
　［５］上記Ｆｅ－Ｎｉ拡散層Ａの最表面におけるＮｉ比率が、１．０％以上２０．０％未満である、上記［４］に記載の電池外筒缶。ただし、上記Ｎｉ比率は、上記Ｆｅ－Ｎｉ拡散層の最表面における、Ｆｅ量とＮｉ量との合計に対する上記Ｎｉ量の割合であり、上記Ｆｅ量および上記Ｎｉ量の単位は、原子％である。
　［６］上記Ｆｅ－Ｎｉ拡散層Ａの厚さが、０．０１μｍ以上０．５μｍ未満である、上記［４］または［５］に記載の電池外筒缶。
　［７］上記Ｎｉ層の厚さが、１μｍ以上である、上記［４］～［６］のいずれかに記載の電池外筒缶。
　［８］上記［４］～［７］のいずれかに記載の電池外筒缶と、上記電池外筒缶の内部に配置された電解液、電極およびセパレータと、を備える電池。 That is, the present invention provides the following [1] to [8].
[1] Fe-Ni diffusion layers are provided on both surface layers of the steel sheet, and the Fe-Ni diffusion layer has an Ni-concentrated adhesion amount on one side of the steel sheet of 50 mg / m 2 or more and 500 mg / m 2 or less. A steel plate for battery outer cans.
[2] The steel plate for battery outer cans according to [1], wherein the Ni ratio on the outermost surface of the Fe—Ni diffusion layer is 1.0% or more and less than 20.0%. However, the Ni ratio is the ratio of the Ni amount to the total of Fe amount and Ni amount on the outermost surface of the Fe—Ni diffusion layer, and the unit of the Fe amount and the Ni amount is atomic%. .
[3] The steel plate for battery outer cans according to [1] or [2], wherein the thickness of the Fe—Ni diffusion layer is 0.01 μm or more and less than 0.5 μm.
[4] The battery outer cylinder-shaped steel plate has Fe—Ni diffusion layers on the inner and outer surface layers, and further has a Ni layer on the Fe—Ni diffusion layer on the outer surface side of the steel plate. A part of the Fe—Ni diffusion layer on the outer surface side of the steel sheet is an Fe—Ni diffusion layer A having an Ni conversion amount per side of the steel sheet of 50 mg / m 2 or more and 500 mg / m 2 or less. Tube can.
[5] The battery outer can according to [4], wherein the Ni ratio on the outermost surface of the Fe—Ni diffusion layer A is 1.0% or more and less than 20.0%. However, the Ni ratio is the ratio of the Ni amount to the total of Fe amount and Ni amount on the outermost surface of the Fe—Ni diffusion layer, and the unit of the Fe amount and the Ni amount is atomic%. .
[6] The battery outer can according to [4] or [5], wherein the thickness of the Fe—Ni diffusion layer A is 0.01 μm or more and less than 0.5 μm.
[7] The battery outer can according to any one of [4] to [6], wherein the Ni layer has a thickness of 1 μm or more.
[8] A battery comprising the battery outer can according to any one of [4] to [7], and an electrolyte solution, an electrode, and a separator disposed inside the battery outer can.
　本発明によれば、後めっき法に用いる電池外筒缶用鋼板であって、焼入れ鋼で作られた成形型を使用してプレス成形を繰り返し行なう場合にも傷付きの発生が抑制され、かつ、得られる電池外筒缶の耐食性にも優れる電池外筒缶用鋼板、ならびに、これを用いた電池外筒缶および電池を提供することができる。 According to the present invention, a steel plate for a battery outer can used in a post-plating method, the occurrence of scratches is suppressed even when press molding is repeatedly performed using a mold made of quenched steel, and It is possible to provide a steel plate for a battery outer can that is excellent in corrosion resistance of the obtained battery outer can, and a battery outer can and a battery using the same.
［電池外筒缶用鋼板］
　本発明の電池外筒缶用鋼板（以下、単に「本発明の缶用鋼板」ともいう）は、鋼板の両面の表層にＦｅ－Ｎｉ拡散層を有し、上記Ｆｅ－Ｎｉ拡散層は、上記鋼板の片面あたりのＮｉ換算の付着量（以下、「Ｎｉ付着量」ともいう）が、５０ｍｇ／ｍ2以上５００ｍｇ／ｍ2以下である、電池外筒缶用鋼板である。 [Steel plate for battery outer can]
The steel sheet for battery outer cans of the present invention (hereinafter, also simply referred to as “the steel sheet for cans of the present invention”) has Fe—Ni diffusion layers on both surface layers of the steel sheet. This is a steel sheet for battery outer cans, in which the amount of adhesion in terms of Ni per one side of the steel sheet (hereinafter also referred to as “Ni adhesion amount”) is 50 mg / m 2 or more and 500 mg / m 2 or less.
　本発明の缶用鋼板は、後めっき法に用いる電池外筒缶用鋼板であって、焼入れ鋼で作られた成形型を使用してプレス成形を繰り返し行なう場合にも傷付きの発生が抑制され、かつ、得られる電池外筒缶の耐食性にも優れる。
　その理由は、以下のように推測される。 The steel plate for cans of the present invention is a steel plate for battery outer cylinder cans used in post-plating methods, and even when press forming is repeatedly performed using a forming die made of quenched steel, the occurrence of scratches is suppressed. In addition, the obtained battery outer can has excellent corrosion resistance.
The reason is presumed as follows.
　まず、特許文献１に記載された、後めっき法に用いる電池外筒缶用鋼板は、「プレス成型により容器内面となる面に厚さ０．５μｍ以上…のＦｅ－Ｎｉ拡散層」を有する。このＦｅ－Ｎｉ拡散層のＮｉ付着量は、換算すると、４５００ｍｇ／ｍ2以上となる。
　このような特許文献１の電池外筒缶用鋼板は、Ｆｅ－Ｎｉ拡散層のＮｉ付着量が多すぎて硬くなり、比較的もろい焼入れ鋼で作られた成形型を、プレス成形を繰り返し行なう過程で、次第に傷付けてしまうと考えられる。そして、傷の付いた成形型が使用されるので、成形される電池外筒缶用鋼板に傷を与えてしまうと考えられる。 First, the steel sheet for a battery outer can used in the post-plating method described in Patent Document 1 has “Fe—Ni diffusion layer having a thickness of 0.5 μm or more on the surface that becomes the inner surface of the container by press molding”. The Ni adhesion amount of this Fe—Ni diffusion layer is 4500 mg / m 2 or more in terms of conversion.
Such a steel sheet for battery outer cans of Patent Document 1 is a process in which a forming die made of a relatively brittle and hardened steel is repeatedly pressed by a Ni-adhering amount of the Fe—Ni diffusion layer is too hard. It is thought that it will gradually hurt. And since the shaping | molding die with a damage | wound is used, it is thought that it will give a damage | wound to the steel plate for battery outer cylinder cans shape | molded.
　しかしながら、本発明の缶用鋼板のＦｅ－Ｎｉ拡散層は、そのＮｉ付着量が５００ｍｇ／ｍ2以下と適度に少なく、焼入れ鋼で作られた成形型を傷付けない程度に軟らかいと考えられる。このため、成形される電池外筒缶用鋼板の傷発生が抑制される（以下、「耐傷性に優れる」ともいう）。そして、本発明の缶用鋼板は、このように耐傷性に優れるから、得られる電池外筒缶の耐食性も優れる。 However, the Fe—Ni diffusion layer of the steel sheet for cans of the present invention has a reasonably small Ni adhesion amount of 500 mg / m 2 or less, and is considered to be soft enough not to damage a forming die made of hardened steel. For this reason, the generation | occurrence | production of the damage | wound of the steel plate for battery outer cylinder cans is suppressed (henceforth "it is excellent also in scratch resistance"). And since the steel plate for cans of this invention is excellent in scratch resistance in this way, the corrosion resistance of the battery outer cylinder can obtained is also excellent.
　本発明の缶用鋼板のＦｅ－Ｎｉ拡散層のＮｉ付着量が少なすぎる場合、得られる電池外筒缶の耐食性に劣ることが懸念される。しかし、本発明の缶用鋼板は、Ｆｅ－Ｎｉ拡散層のＮｉ付着量が５０ｍｇ／ｍ2以上と適度に多いため、電池外筒缶にしたときの耐食性（以下、単に「耐食性」ともいう）が良好となる。
　より詳細には、電池外筒缶にしたとき、その内面においては、Ｆｅ－Ｎｉ拡散層は電気化学的に安定なため、Ｆｅ－Ｎｉ拡散層が無い場合または少なすぎる場合と比べて、内容物に対する耐食性が向上する。
　一方、外面においては、成形後にバレルめっき等によってＮｉめっきが付与されてＮｉ層が形成されるが、このＮｉ層には、ピンホールが多少なりとも存在し、ここから腐食が進行する。しかし、Ｎｉ層の下地層として適度にＦｅ－Ｎｉ拡散層があることで、Ｎｉ層と下地層との電位差を、Ｆｅ－Ｎｉ拡散層が無い場合または少なすぎる場合と比べて、縮小でき、耐食性が向上する。 When the amount of Ni deposited on the Fe—Ni diffusion layer of the steel sheet for cans of the present invention is too small, there is a concern that the resulting battery outer can can have poor corrosion resistance. However, since the steel sheet for cans of the present invention has a reasonably high Ni adhesion amount of 50 mg / m 2 or more in the Fe—Ni diffusion layer, the corrosion resistance when it is made into a battery outer can (hereinafter also simply referred to as “corrosion resistance”). Becomes better.
More specifically, the content of the Fe-Ni diffusion layer is electrochemically stable on the inner surface of the battery outer can when compared with the case where the Fe-Ni diffusion layer is absent or too little. Corrosion resistance against is improved.
On the other hand, Ni plating is applied to the outer surface by barrel plating or the like after forming to form a Ni layer. The Ni layer has some pinholes, and corrosion proceeds from here. However, since there is an appropriate Fe—Ni diffusion layer as the underlayer for the Ni layer, the potential difference between the Ni layer and the underlayer can be reduced compared to the case where there is no Fe—Ni diffusion layer or too little, and the corrosion resistance. Will improve.
　以下、本発明の缶用鋼板が備える各部について、より詳細に説明する。 Hereafter, each part with which the steel plate for cans of this invention is provided is demonstrated in detail.
 〈鋼板〉
　鋼板の種類は特に限定されない。通常、電池容器材料として使用される鋼板（例えば、低炭素鋼板または極低炭素鋼板）を用いることができる。ただし、鋼板中のＣｒの含有は、鋼を硬化させて成形性を低下させたり、焼鈍時に鋼板の表面にＣｒ酸化物を形成して、所望の表面状態を得られなくさせたりする恐れがある。このため、鋼板のＣｒ含有量は、３質量％未満が好ましく、１質量％未満がより好ましい。
　鋼板の製造方法も特に限定されない。例えば、通常の鋼片製造工程から熱間圧延、酸洗、冷間圧延、焼鈍、調質圧延等の工程を経て製造される。 <steel sheet>
The kind of steel plate is not particularly limited. Usually, a steel plate (for example, a low carbon steel plate or an extremely low carbon steel plate) used as a battery container material can be used. However, the content of Cr in the steel sheet may cause the steel to harden and deteriorate formability, or may form a Cr oxide on the surface of the steel sheet during annealing, making it impossible to obtain a desired surface state. . For this reason, the Cr content of the steel sheet is preferably less than 3% by mass, and more preferably less than 1% by mass.
The manufacturing method of the steel plate is not particularly limited. For example, it is manufactured through processes such as hot rolling, pickling, cold rolling, annealing, and temper rolling from a normal steel slab manufacturing process.
　本発明においては、Ｆｅ－Ｎｉ拡散層の形成が必須となるから、冷間圧延後の未焼鈍の鋼板にＮｉめっきを施し、鋼板の焼鈍処理と共にＮｉめっきを鋼板内部に拡散させることが、生産上、最も効率が良い。このため、鋼板としては、冷間圧延後の未焼鈍の鋼板を用いることが好ましい。 In the present invention, since the formation of the Fe—Ni diffusion layer is essential, it is possible to apply Ni plating to an unannealed steel sheet after cold rolling, and to diffuse the Ni plating inside the steel sheet together with the annealing treatment of the steel sheet. Above, the most efficient. For this reason, it is preferable to use an unannealed steel sheet after cold rolling as the steel sheet.
 〈Ｆｅ－Ｎｉ拡散層〉
　本発明の缶用鋼板は、鋼板の両面の表層に、Ｆｅ－Ｎｉ拡散層を有する。 <Fe-Ni diffusion layer>
The steel plate for cans of the present invention has Fe—Ni diffusion layers on the surface layers on both sides of the steel plate.
　《Ｎｉ付着量》
　Ｆｅ－Ｎｉ拡散層は、鋼板の片面あたりのＮｉ換算の付着量（Ｎｉ付着量）が、５０ｍｇ／ｍ2以上５００ｍｇ／ｍ2以下である。これにより、本発明の缶用鋼板は、上述したように、耐傷性および耐食性が共に優れる。耐傷性がより優れるという理由から、Ｆｅ－Ｎｉ拡散層のＮｉ付着量は、３５０ｍｇ／ｍ2以下が好ましく、３００ｍｇ／ｍ2以下がより好ましい。 《Ni adhesion amount》
In the Fe—Ni diffusion layer, the Ni conversion amount (Ni adhesion amount) per one side of the steel sheet is 50 mg / m 2 or more and 500 mg / m 2 or less. Thereby, as above-mentioned, the steel plate for cans of this invention is excellent in both scratch resistance and corrosion resistance. For the reason that scratch resistance more excellent, Ni deposition amount of Fe-Ni diffusion layer is preferably 350 mg / m 2 or less, 300 mg / m 2 or less is more preferable.
　Ｆｅ－Ｎｉ拡散層のＮｉ付着量は、蛍光Ｘ線分析により表面分析して測定できる。この場合、Ｎｉ付着量既知のＮｉ付着サンプルを用いて、Ｎｉ付着量に関する検量線をあらかじめ特定しておき、同検量線を用いて相対的にＮｉ付着量を特定する。蛍光Ｘ線分析は、例えば、下記条件により実施される。
　・装置：リガク社製蛍光Ｘ線分析装置Ｓｙｓｔｅｍ３２７０
　・測定径：３０ｍｍ
　・測定雰囲気：真空
　・スペクトル：Ｎｉ－Ｋα
　・スリット：ＣＯＡＲＳＥ
　・分光結晶：ＴＡＰ
　上記条件により測定したＦｅ－Ｎｉ拡散層の蛍光Ｘ線分析のＮｉ－Ｋαのピークカウント数を用いる。重量法で付着量を測定した付着量既知の標準サンプルを用いて、Ｎｉ付着量に関する検量線をあらかじめ特定しておき、同検量線を用いて相対的にＮｉ付着量を求める。 The amount of Ni deposited on the Fe—Ni diffusion layer can be measured by surface analysis using fluorescent X-ray analysis. In this case, a calibration curve related to the Ni adhesion amount is specified in advance using a Ni adhesion sample with a known Ni adhesion amount, and the Ni adhesion amount is relatively specified using the calibration curve. The fluorescent X-ray analysis is performed, for example, under the following conditions.
Apparatus: X-ray fluorescence analyzer System 3270 manufactured by Rigaku Corporation
・ Measurement diameter: 30 mm
・ Measurement atmosphere: Vacuum ・ Spectrum: Ni-Kα
・ Slit: COARSE
-Spectral crystal: TAP
The peak count number of Ni—Kα in the fluorescent X-ray analysis of the Fe—Ni diffusion layer measured under the above conditions is used. Using a standard sample with a known adhesion amount measured by the gravimetric method, a calibration curve related to the Ni adhesion amount is specified in advance, and the Ni adhesion amount is relatively determined using the calibration curve.
　《厚さ》
　本発明の缶用鋼板において、Ｆｅ－Ｎｉ拡散層の厚さは、成形後においてもＦｅ－Ｎｉ拡散層を維持しやすく、かつ、耐傷性および耐食性がより優れるという理由から、０．０１μｍ以上０．５μｍ未満が好ましく、耐傷性が更に優れるという理由から、０．４μｍ以下がより好ましく、０．３８μｍ以下が更に好ましい。 "thickness"
In the steel sheet for cans of the present invention, the thickness of the Fe—Ni diffusion layer is 0.01 μm or more because it is easy to maintain the Fe—Ni diffusion layer after forming and the scratch resistance and corrosion resistance are more excellent. 0.4 μm or less is more preferable, and 0.38 μm or less is still more preferable because it is preferably less than 0.5 μm and scratch resistance is further improved.
　Ｆｅ－Ｎｉ拡散層の厚さは、ＧＤＳ（グロー放電発光分析）によって測定できる。具体的には、まず、Ｆｅ－Ｎｉ拡散層の表面から鋼板の内部に向かって、スパッタリングし、深さ方向の分析を行ない、Ｎｉの強度が最大値の１／１０となるスパッタリング時間を求める。次いで、純鉄を用いてＧＤＳによるスパッタリング深さとスパッタリング時間との関係を求める。この関係を用いて、先に求めたＮｉの強度が最大値の１／１０となるスパッタリング時間から純鉄換算でスパッタリング深さを算出し、算出した値をＦｅ－Ｎｉ拡散層の厚さとする。ＧＤＳは、下記に条件において実施したものである。
　・装置：リガク社製ＧＤＡ７５０
　・陽極内径：４ｍｍ
　・分析モード：高周波低電圧モード
　・放電電力：４０Ｗ
　・制御圧力：２．９ｈＰａ
　・検出器：フォトマル
　・検出波長：Ｎｉ＝３４１．４ｎｍ The thickness of the Fe—Ni diffusion layer can be measured by GDS (glow discharge emission analysis). Specifically, first, sputtering is performed from the surface of the Fe—Ni diffusion layer toward the inside of the steel plate, analysis is performed in the depth direction, and a sputtering time at which the Ni intensity becomes 1/10 of the maximum value is obtained. Next, the relationship between the sputtering depth by GDS and the sputtering time is obtained using pure iron. Using this relationship, the sputtering depth is calculated in terms of pure iron from the sputtering time at which the Ni strength obtained previously becomes 1/10 of the maximum value, and the calculated value is taken as the thickness of the Fe—Ni diffusion layer. GDS was carried out under the following conditions.
・ Device: GDA750 manufactured by Rigaku Corporation
・ Anode inner diameter: 4mm
・ Analysis mode: High frequency low voltage mode ・ Discharge power: 40W
・ Control pressure: 2.9 hPa
・ Detector: Photomal ・ Detection wavelength: Ni = 341.4 nm
　《Ｎｉ比率》
　本発明の缶用鋼板において、Ｆｅ－Ｎｉ拡散層の最表面におけるＮｉ比率（以下、単に「Ｎｉ比率」ともいう）は、耐傷性および耐食性がより優れるという理由から、１．０％以上２０．０％未満であることが好ましい。
　Ｆｅ－Ｎｉ拡散層の最表面のＮｉ比率が重要なのは、Ｆｅ－Ｎｉ拡散層の最表面のＮｉは耐食性に直接効果があるが、鋼中に拡散したＮｉは耐食性向上の効果が小さいからである。一方、Ｎｉ比率が高すぎると最表面が硬くなり耐傷性が不十分となる場合がある。このため、Ｎｉ比率の好適範囲は、上述した１．０％以上２０．０％未満である。
　耐傷性が更に優れるという理由から、Ｎｉ比率の下限は、３．０％がより好ましい。同様の理由から、Ｎｉ比率の上限は、１５．０％がより好ましく、１３．０％が更に好ましい。 << Ni ratio >>
In the steel sheet for cans of the present invention, the Ni ratio (hereinafter also simply referred to as “Ni ratio”) on the outermost surface of the Fe—Ni diffusion layer is 1.0% or more and 20.20 because it is more excellent in scratch resistance and corrosion resistance. Preferably it is less than 0%.
The Ni ratio on the outermost surface of the Fe—Ni diffusion layer is important because Ni on the outermost surface of the Fe—Ni diffusion layer has a direct effect on the corrosion resistance, but Ni diffused in the steel has a small effect on improving the corrosion resistance. . On the other hand, if the Ni ratio is too high, the outermost surface becomes hard and scratch resistance may be insufficient. For this reason, the suitable range of Ni ratio is 1.0% or more and less than 20.0% mentioned above.
For the reason that scratch resistance is further excellent, the lower limit of the Ni ratio is more preferably 3.0%. For the same reason, the upper limit of the Ni ratio is more preferably 15.0%, still more preferably 13.0%.
　Ｆｅ－Ｎｉ拡散層の最表面におけるＮｉ比率（単位：％）は、Ｆｅ－Ｎｉ拡散層の最表面における、Ｆｅ量とＮｉ量との合計に対するＮｉ量の割合であり、すなわち式「Ｎｉ量／（Ｆｅ量＋Ｎｉ量）×１００」で算出される。Ｆｅ量およびＮｉ量の単位は、原子％である。
　Ｆｅ－Ｎｉ拡散層の最表面におけるＦｅ量（単位：原子％）およびＮｉ量（単位：原子％）は、Ｆｅ－Ｎｉ拡散層が形成された鋼板を、アセトン中で１０分間超音波洗浄した後、スパッタを行なうことなく、オージェ電子分光測定を行なうことにより測定できる。オージェ電子分光測定は同一試料中の別視野で１０箇所測定を行ない、Ｆｅ量およびＮｉ量はそれぞれ１０箇所測定結果の平均値を用いる。オージェ電子分光測定は下記条件において実施したものである。
　・装置：ＵＬＶＡＣ－ＰＨＩ社製ＰＨＩ６６０
　・観察および分析条件：加速電圧１０．０ｋＶ、電流値０．５μＡ
　　　　　　　　　　　　観察倍率１，０００倍、測定範囲５４０～９００ｅＶ The Ni ratio (unit:%) on the outermost surface of the Fe—Ni diffusion layer is the ratio of the Ni amount to the sum of the Fe amount and the Ni amount on the outermost surface of the Fe—Ni diffusion layer, that is, the formula “Ni amount / (Fe amount + Ni amount) × 100 ”. The unit of Fe amount and Ni amount is atomic%.
The amount of Fe (unit: atomic%) and the amount of Ni (unit: atomic%) on the outermost surface of the Fe—Ni diffusion layer were determined by ultrasonically cleaning the steel sheet on which the Fe—Ni diffusion layer was formed in acetone for 10 minutes. It can be measured by performing Auger electron spectroscopy without performing sputtering. Auger electron spectroscopic measurement is performed at 10 points in different fields of view in the same sample, and the average value of the results of measurement at 10 points is used for the Fe amount and Ni amount, respectively. Auger electron spectroscopy measurement was performed under the following conditions.
・ Device: ULVAC-PHI PHI660
Observation and analysis conditions: acceleration voltage 10.0 kV, current value 0.5 μA
Observation magnification 1,000 times, measurement range 540-900eV
　《Ｆｅ－Ｎｉ拡散層の形成方法》
　鋼板の両面の表層にＦｅ－Ｎｉ拡散層を形成する方法は、特に限定されないが、一例として、次の方法が挙げられる。 << Method for forming Fe-Ni diffusion layer >>
The method for forming the Fe—Ni diffusion layers on the surface layers on both surfaces of the steel plate is not particularly limited, but the following method is given as an example.
　まず、冷間圧延後の未焼鈍の鋼板に対して、必要に応じて前処理（脱脂および酸洗など）を行なった後、Ｎｉめっき浴を用いて、電流密度等の条件を適宜調整して、Ｎｉめっきを施す。Ｎｉめっき浴としては、例えば、ワット浴、スルファミン酸浴、ほうフッ化物浴および塩化物浴などが挙げられる。
　このとき、Ｎｉめっきの付着量は、鋼板の片面あたり、５０ｍｇ／ｍ2以上５００ｍｇ／ｍ2以下とする。これにより、形成されるＦｅ－Ｎｉ拡散層のＮｉ付着量を、５０ｍｇ／ｍ2以上５００ｍｇ／ｍ2以下にすることができる。 First, pre-treatment (eg, degreasing and pickling) is performed on an unannealed steel sheet after cold rolling as necessary, and then conditions such as current density are appropriately adjusted using a Ni plating bath. Ni plating is applied. Examples of the Ni plating bath include a watt bath, a sulfamic acid bath, a borofluoride bath, and a chloride bath.
At this time, deposition of Ni plating, per side of the steel sheet, and 50 mg / m 2 or more 500 mg / m 2 or less. Thereby, the Ni adhesion amount of the formed Fe—Ni diffusion layer can be set to 50 mg / m 2 or more and 500 mg / m 2 or less.
　次に、Ｎｉめっきを施した鋼板に対して、鋼板の再結晶処理を目的とした焼鈍（好ましくは連続焼鈍）を行なう。これにより、鋼板の焼鈍に伴って、Ｎｉめっきが鋼板内部に拡散し、Ｆｅ－Ｎｉ拡散層が形成される。
　焼鈍条件としては、均熱温度は６００℃以上８００℃以下が好ましく、この均熱温度での保持時間は１０秒以上６０秒以下が好ましい。均熱温度での保持時間が短いほど鋼中にＮｉが拡散しにくくなり、最表面のＮｉ比率が大きくなることから、耐食性の観点から、均熱温度での保持時間は３０秒未満がより好ましい。
　この焼鈍条件であれば、形成されるＦｅ－Ｎｉ拡散層について、その厚さを０．０１μｍ以上０．５μｍ未満にし、かつ、最表面におけるＮｉ比率を１．０％以上２０．０％未満にすることができるため、好ましい。 Next, annealing (preferably continuous annealing) for the purpose of recrystallizing the steel sheet is performed on the steel sheet to which Ni plating has been applied. Thereby, with the annealing of the steel sheet, the Ni plating diffuses inside the steel sheet and an Fe—Ni diffusion layer is formed.
As annealing conditions, the soaking temperature is preferably 600 ° C. or more and 800 ° C. or less, and the holding time at this soaking temperature is preferably 10 seconds or more and 60 seconds or less. The shorter the holding time at the soaking temperature, the more difficult Ni diffuses in the steel, and the Ni ratio on the outermost surface increases. From the viewpoint of corrosion resistance, the holding time at the soaking temperature is more preferably less than 30 seconds. .
With this annealing condition, the thickness of the formed Fe—Ni diffusion layer is set to 0.01 μm or more and less than 0.5 μm, and the Ni ratio on the outermost surface is set to 1.0% or more and less than 20.0%. This is preferable.
　Ｆｅ－Ｎｉ拡散層を形成した後、必要に応じて、調質圧延することによって、形状矯正および表面粗度調整などを行なってもよい。 After forming the Fe—Ni diffusion layer, shape correction and surface roughness adjustment may be performed by temper rolling as necessary.
［電池外筒缶の製造方法］
　次に、本発明の缶用鋼板を用いた電池外筒缶の製造方法（以下、便宜的に「本発明の製造方法」ともいう）について説明する。
　本発明の製造方法は、例えば、本発明の缶用鋼板を、成形型を用いたプレス成形によって電池外筒缶形状（例えば、円筒状）に成形する工程と、その後、電池外筒缶形状に成形された本発明の缶用鋼板の外面に、Ｎｉめっきを施すことによってＮｉ層を形成する工程と、を備える方法が挙げられる。 [Method of manufacturing battery outer can]
Next, a method for manufacturing a battery outer can using the steel plate for cans of the present invention (hereinafter also referred to as “the manufacturing method of the present invention” for convenience) will be described.
The manufacturing method of the present invention includes, for example, a step of forming the steel plate for cans of the present invention into a battery outer can shape (for example, a cylindrical shape) by press forming using a forming die, and then into a battery outer can shape. And forming a Ni layer on the outer surface of the formed steel plate for a can of the present invention by applying Ni plating.
 〈成形（プレス成形）〉
　成形（プレス成形）の方法は、特に限定されず、電池外筒缶の成形に用いられている一般的な方法で行なうことができる。例えば、本発明の缶用鋼板を円形に打ち抜くと共に、カップ状に絞り、再絞りおよびＤＩ（Ｄｒａｗｉｎｇ ａｎｄ Ｉｒｏｎｉｎｇ）工程によって、円筒状等の形状に成形する。 <Molding (press molding)>
The method of forming (press forming) is not particularly limited, and can be performed by a general method used for forming a battery outer can. For example, the steel plate for cans of the present invention is punched into a circular shape, drawn into a cup shape, formed into a cylindrical shape or the like by a redrawing and DI (Drawing and Ironing) process.
　このとき、使用される成形型の材料としては、超硬合金が用いられることが多いが、比較的もろい焼入れ鋼が使用されてもよい。上述したように、本発明の缶用鋼板のＦｅ－Ｎｉ拡散層は、焼入れ鋼で作られた成形型を傷付けないと考えられるため、成形される電池外筒缶用鋼板の傷発生が抑制される。 At this time, cemented carbide is often used as the material of the mold used, but relatively brittle and hardened steel may be used. As described above, since the Fe—Ni diffusion layer of the steel sheet for cans of the present invention is considered not to damage the mold made of hardened steel, the generation of scratches on the steel sheet for battery outer cylinder can be suppressed. The
　プレス成形を受けたＦｅ－Ｎｉ拡散層のＮｉ付着量、厚さおよびＮｉ比率は、プレス成形前の状態は維持されず、変更され得る。
　しかしながら、本発明の缶用鋼板において、電池外筒缶の外面側となる部分の少なくとも一部（例えば、電池外筒缶のプラス側の突起の端面となる部分）は、プレス成形されず、無加工のままである。
　したがって、本発明の缶用鋼板を用いて得られる電池外筒缶（本発明の電池外筒缶）の外面側の少なくとも一部は、プレス成形前の本発明の缶用鋼板におけるＦｅ－Ｎｉ拡散層のＮｉ付着量、厚さおよびＮｉ比率が、そのまま維持されている。 The Ni adhesion amount, thickness, and Ni ratio of the Fe—Ni diffusion layer subjected to press forming can be changed without maintaining the state before press forming.
However, in the steel sheet for cans of the present invention, at least a part of the portion that becomes the outer surface side of the battery outer can (for example, the portion that becomes the end surface of the positive protrusion of the battery outer can) is not press-formed. It remains as processed.
Therefore, at least a part of the outer surface side of the battery outer can obtained by using the steel plate for cans of the present invention (battery outer can of the present invention) is Fe-Ni diffusion in the steel plate for cans of the present invention before press forming. The Ni adhesion amount, thickness, and Ni ratio of the layer are maintained as they are.
 〈電池外筒缶形状に成形した後のＮｉめっき〉
　Ｎｉめっきを施す方法は、特に限定されず、従来公知の方法を用いることができる。例えば、電池外筒缶形状に成形された本発明の缶用鋼板に対して、Ｎｉめっき浴を用いて、電流密度等の条件を適宜調整して、バレルめっき法によって、Ｎｉめっきを施す。Ｎｉめっき浴としては、例えば、ワット浴、スルファミン酸浴、ほうフッ化物浴および塩化物浴などが挙げられる。 <Ni plating after forming into battery outer tube can shape>
The method for applying Ni plating is not particularly limited, and a conventionally known method can be used. For example, the steel plate for cans of the present invention formed into a battery outer can shape is subjected to Ni plating by a barrel plating method by appropriately adjusting conditions such as current density using a Ni plating bath. Examples of the Ni plating bath include a watt bath, a sulfamic acid bath, a borofluoride bath, and a chloride bath.
　これにより、電池外筒缶形状に成形された本発明の缶用鋼板の少なくとも外面側のＦｅ－Ｎｉ拡散層上に、Ｎｉめっきが施されて、Ｎｉ層が形成される。 Thereby, Ni plating is performed on the Fe—Ni diffusion layer on at least the outer surface side of the steel plate for a can of the present invention formed into a battery outer cylinder can shape, thereby forming a Ni layer.
　このとき、本発明の缶用鋼板は、電池外筒缶形状に成形されているため、その内部にＮｉめっきが侵入しにくく、電池外筒缶形状の本発明の缶用鋼板の内面にはＮｉめっきは施されにくい。もっとも、電池外筒缶形状の本発明の缶用鋼板の内面にも、外面と同様に、Ｎｉめっきが施されてＮｉ層が形成されてもよい。 At this time, since the steel plate for cans of the present invention is formed into a battery outer cylinder can shape, Ni plating is less likely to enter inside, and the inner surface of the steel plate for cans of the present invention in the shape of a battery outer cylinder can is Ni. Plating is difficult to apply. However, similarly to the outer surface, the Ni layer may be formed on the inner surface of the battery steel plate for cans of the present invention having a battery outer can shape as well as the outer surface.
　Ｆｅ－Ｎｉ拡散層上に形成されるＮｉめっき（Ｎｉ層）の厚さは、耐食性の観点から、１μｍ以上が好ましく、２μｍ以上がより好ましい。Ｎｉ層の厚さの上限は特に限定されないが、例えば、経済性の観点から、７μｍ以下が好ましい。 The thickness of the Ni plating (Ni layer) formed on the Fe—Ni diffusion layer is preferably 1 μm or more and more preferably 2 μm or more from the viewpoint of corrosion resistance. Although the upper limit of the thickness of Ni layer is not specifically limited, For example, 7 micrometers or less are preferable from a viewpoint of economical efficiency.
［電池外筒缶］
　本発明の電池外筒缶は、本発明の缶用鋼板を用いて得られる電池外筒缶である。
　より詳細には、本発明の電池外筒缶は、電池外筒缶形状の鋼板の内面および外面の表層にＦｅ－Ｎｉ拡散層を有し、上記鋼板の外面側の上記Ｆｅ－Ｎｉ拡散層上に、更に、Ｎｉ層を有し、上記鋼板の外面側の上記Ｆｅ－Ｎｉ拡散層の一部が、上記鋼板の片面あたりのＮｉ換算の付着量が５０ｍｇ／ｍ2以上５００ｍｇ／ｍ2以下のＦｅ－Ｎｉ拡散層Ａである、電池外筒缶である。 [Battery outer can]
The battery outer can of the present invention is a battery outer can obtained using the steel plate for cans of the present invention.
More specifically, the battery outer can of the present invention has a Fe—Ni diffusion layer on the inner surface and outer surface of the battery outer can-shaped steel plate, on the Fe—Ni diffusion layer on the outer surface side of the steel plate. Furthermore, it has a Ni layer, and a part of the Fe—Ni diffusion layer on the outer surface side of the steel sheet has a Ni-concentrated adhesion amount on one side of the steel sheet of 50 mg / m 2 or more and 500 mg / m 2 or less. This is a battery outer can that is an Fe—Ni diffusion layer A.
　本発明の電池外筒缶は、まず、プレス成形によって鋼板が電池外筒缶形状に成形されており、この鋼板の両面（内面および外面）の表層に、本発明の缶用鋼板と同様に、Ｆｅ－Ｎｉ拡散層が形成されている。そして、鋼板の少なくとも外面側のＦｅ－Ｎｉ拡散層上に、Ｎｉめっきが施されて、Ｎｉ層が形成されている。 In the battery outer can of the present invention, first, a steel plate is formed into a battery outer can shape by press forming, and on both surfaces (inner surface and outer surface) of this steel plate, similarly to the steel plate for cans of the present invention, An Fe—Ni diffusion layer is formed. Then, Ni plating is performed on the Fe—Ni diffusion layer on at least the outer surface side of the steel plate to form a Ni layer.
　ここで、上述したように、本発明の電池外筒缶の外面側の少なくとも一部のＦｅ－Ｎｉ拡散層は、プレス成形前の本発明の缶用鋼板におけるＦｅ－Ｎｉ拡散層（Ｎｉ付着量：５０ｍｇ／ｍ2以上５００ｍｇ／ｍ2以下）が、そのまま維持されている。
　すなわち、本発明の電池外筒缶においては、電池外筒缶形状の鋼板の外面側のＦｅ－Ｎｉ拡散層の少なくとも一部が、Ｎｉ付着量が５０ｍｇ／ｍ2以上５００ｍｇ／ｍ2以下のＦｅ－Ｎｉ拡散層Ａである。 Here, as described above, at least a part of the Fe—Ni diffusion layer on the outer surface side of the battery outer can of the present invention is the Fe—Ni diffusion layer (Ni adhesion amount) in the steel sheet for cans of the present invention before press forming. : 50 mg / m 2 or more and 500 mg / m 2 or less) is maintained as it is.
That is, in the battery outer can of the present invention, at least a part of the Fe—Ni diffusion layer on the outer surface side of the battery outer can-shaped steel plate has an Fe deposition amount of Ni of 50 mg / m 2 or more and 500 mg / m 2 or less. -Ni diffusion layer A.
　本発明の電池外筒缶におけるＦｅ－Ｎｉ拡散層ＡのＮｉ付着量、厚さおよびＮｉ比率の好適範囲は、本発明の缶用鋼板におけるＦｅ－Ｎｉ拡散層のＮｉ付着量、厚さおよびＮｉ比率と同様である。 The preferable range of the Ni adhesion amount, the thickness and the Ni ratio of the Fe—Ni diffusion layer A in the battery outer can of the present invention is the Ni adhesion amount, thickness and Ni of the Fe—Ni diffusion layer in the steel sheet for cans of the present invention. It is the same as the ratio.
　本発明の電池外筒缶において、Ｆｅ－Ｎｉ拡散層上のＮｉ層の厚さは、上述したとおりであり、１μｍ以上が好ましく、２μｍ以上がより好ましい。上限は特に限定されないが、７μｍ以下が好ましい。 In the battery outer can of the present invention, the thickness of the Ni layer on the Fe—Ni diffusion layer is as described above, preferably 1 μm or more, and more preferably 2 μm or more. Although an upper limit is not specifically limited, 7 micrometers or less are preferable.
［電池］
　本発明の電池は、本発明の電池外筒缶と、本発明の電池外筒缶の内部に配置された電解液、電極およびセパレータと、を備える電池である。
　すなわち、本発明の電池は、本発明の電池外筒缶の内部に、電池として必要な構成である電解液、電極およびセパレータが少なくとも充填されており、更に、必要に応じて、その他の構成が充填されていてもよい。
　本発明の電池は、本発明の電池外筒缶を使用しているため、耐食性に優れる。 [battery]
The battery of this invention is a battery provided with the battery outer cylinder can of this invention, and the electrolyte solution, electrode, and separator which are arrange | positioned inside the battery outer cylinder can of this invention.
That is, the battery of the present invention is filled with at least the electrolyte solution, the electrode, and the separator, which are necessary components for the battery, inside the battery outer can of the present invention. It may be filled.
Since the battery of the present invention uses the battery outer can of the present invention, it has excellent corrosion resistance.
　以下に、実施例を挙げて本発明を具体的に説明する。ただし、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
 〈電池外筒缶用鋼板の製造〉
　鋼板として、板厚０．２５ｍｍの冷間圧延後の未焼鈍状態のＮｂ添加極低炭素鋼（鋼成分は、質量％で、Ｃ：０．００２％，Ｓｉ：０．０２％，Ｍｎ：０．１５％，Ｐ：０．０１％，Ｓ：０．００８％，Ｎｉ：０．０２％，Ｎｂ：０．０１％）を用いた。この鋼板に、脱脂および酸洗を含む前処理を行なった。
　前処理後の鋼板に対して、ワット浴を用いて、Ｎｉめっきを施した。このとき、下記表１に記載のＮｉ付着量（単位：ｍｇ／ｍ2）となるように、電流密度などの条件を適宜調整した。
　次いで、Ｎｉめっきを施した鋼板を、連続焼鈍ラインに導入して、鋼板を焼鈍すると共に、鋼板内部にＮｉを拡散させて、鋼板の両面の表層にＦｅ－Ｎｉ拡散層を形成した。このとき、下記表１に記載の焼鈍条件（均熱温度および保持時間）にすることによって、Ｆｅ－Ｎｉ拡散層の厚さ（単位：μｍ）およびＮｉ比率（単位：％）が、下記表１に記載の数値になるようにした。
　Ｆｅ－Ｎｉ拡散層を形成した後、調質圧延を施して、試験材Ｎｏ．１～２７の電池外筒缶用鋼板を得た。 <Manufacture of steel sheet for battery outer can>
As a steel plate, an unannealed Nb-added ultra-low carbon steel having a thickness of 0.25 mm after cold rolling (the steel components are mass%, C: 0.002%, Si: 0.02%, Mn: 0 15%, P: 0.01%, S: 0.008%, Ni: 0.02%, Nb: 0.01%). This steel plate was pretreated including degreasing and pickling.
Ni plating was applied to the steel sheet after the pretreatment using a Watt bath. At this time, conditions such as current density were appropriately adjusted so that the Ni adhesion amount (unit: mg / m 2 ) described in Table 1 below was obtained.
Next, the steel plate subjected to Ni plating was introduced into a continuous annealing line, the steel plate was annealed, and Ni was diffused inside the steel plate to form Fe—Ni diffusion layers on both surface layers of the steel plate. At this time, the thickness (unit: μm) and Ni ratio (unit:%) of the Fe—Ni diffusion layer were changed to the following Table 1 by using the annealing conditions (soaking temperature and holding time) shown in Table 1 below. It was made to become the numerical value of description.
After forming the Fe—Ni diffusion layer, temper rolling was performed, and the test material no. 1 to 27 steel plates for battery outer cans were obtained.
 〈電池外筒缶の製造〉
　《成形》
　得られた電池外筒缶用鋼板を、円形に打ち抜くと共に、カップ状に絞り、再絞りおよびＤＩ工程によって、円筒状である１８６５０型の電池外筒缶形状に成形した。側壁部分の板厚は、ＤＩ工程により薄肉化を行ない、０．１５ｍｍとした。
　《Ｎｉめっき》
　その後、電池外筒缶形状に成形された電池外筒缶用鋼板の少なくとも外面に、バレルめっき法によって、Ｎｉめっきを施し、厚さ４μｍのＮｉ層を形成した。こうして、電池外筒缶を得た。 <Manufacture of battery outer can>
<Molding>
The obtained steel plate for battery outer can was punched into a circular shape, drawn into a cup, redrawed and formed into a cylindrical 18650 type battery outer can by a DI process. The plate thickness of the side wall portion was reduced to 0.15 mm by the DI process.
<< Ni plating >>
Then, Ni plating was performed by barrel plating on at least the outer surface of the steel sheet for battery outer cylinder cans formed into a battery outer cylinder can shape to form a Ni layer having a thickness of 4 μm. In this way, a battery outer can was obtained.
 〈評価〉
　《耐食性》
　塩化ナトリウム５ｇおよび３０％過酸化水素水１．５ｃｃを純水１００ｇに混合して得られた水溶液を準備した。この水溶液に、得られた電池外筒缶を、室温下で１６時間浸漬した。浸漬後、電池外筒缶を引き上げて、穴あきの有無を目視で確認し、穴あきが確認された場合には「Ｂ」を、穴あきが確認されなかった場合には「Ａ」を、下記表１に記載した。「Ａ」であれば耐食性に優れる。 <Evaluation>
《Corrosion resistance》
An aqueous solution obtained by mixing 5 g of sodium chloride and 1.5 cc of 30% hydrogen peroxide water with 100 g of pure water was prepared. The obtained battery outer cylinder can was immersed in this aqueous solution at room temperature for 16 hours. After soaking, the battery outer can is pulled up and visually checked for the presence or absence of perforations. If perforations are confirmed, “B” is indicated. If no perforations are confirmed, “A” is indicated below. It described in Table 1. If it is "A", it is excellent in corrosion resistance.
　《耐傷性》
　焼入れ鋼で作られた成形型を用いて、上述した成形を繰り返し行ない、電池外筒缶形状に成形された電池外筒缶用鋼板の表面に目視で傷が確認されるまでの回数（製缶数）をカウントした。
　傷が確認されるまでの製缶数が５０，０００缶以下であった場合には「Ｄ」を、５０，０００缶超７０，０００缶以下であった場合には「Ｃ」を、７０，０００缶超１００，０００缶以下であった場合には「Ｂ」を、製缶数が１００，０００缶を超えても傷が確認されなかった場合は「Ａ」を、下記表１に記載した。
　「Ａ」、「Ｂ」または「Ｃ」であれば耐傷性に優れる。実用上、「Ａ」または「Ｂ」が好ましく、「Ａ」がより好ましい。 《Scratch resistance》
Using a mold made of hardened steel, the above-described molding is repeated, and the number of times until the surface of the battery outer can steel plate formed into a battery outer can shape is visually checked for scratches (can manufacturing Count).
When the number of cans until the scratch is confirmed is 50,000 cans or less, “D” is indicated. When the number of cans exceeds 50,000 cans and 70,000 cans or less, “C” is indicated as 70,70. Table 1 below shows “B” when the number of cans exceeds 100,000 cans, and “A” when the number of cans exceeds 100,000 cans. .
“A”, “B” or “C” is excellent in scratch resistance. Practically, “A” or “B” is preferable, and “A” is more preferable.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　上記表１に示すように、Ｆｅ－Ｎｉ拡散層のＮｉ付着量が５００ｍｇ／ｍ2を超える試験材Ｎｏ．１０～１１および２２～２３は、耐傷性が劣っていた。Ｆｅ－Ｎｉ拡散層のＮｉ付着量が５０ｍｇ／ｍ2未満である試験材Ｎｏ．１２および２４は、耐食性が劣っていた。 As shown in Table 1 above, the test material No. 1 in which the Ni adhesion amount of the Fe—Ni diffusion layer exceeded 500 mg / m 2 was used. 10-11 and 22-23 were inferior in scratch resistance. The test material No. whose Ni adhesion amount of the Fe—Ni diffusion layer is less than 50 mg / m 2 12 and 24 were inferior in corrosion resistance.
　これに対して、Ｆｅ－Ｎｉ拡散層のＮｉ付着量が５０ｍｇ／ｍ2以上５００ｍｇ／ｍ2以下である試験材Ｎｏ．１～９、１３～２１および２５～２７は、耐傷性および耐傷性が共に良好であった。 On the other hand, the test material No. in which the Ni adhesion amount of the Fe—Ni diffusion layer is 50 mg / m 2 or more and 500 mg / m 2 or less. Nos. 1-9, 13-21 and 25-27 both had good scratch resistance and scratch resistance.
　試験材Ｎｏ．１～９、１３～２１および２５～２７を対比すると、Ｆｅ－Ｎｉ拡散層の最表面におけるＮｉ比率が１．０％以上２０．０％未満である試験材Ｎｏ．１～９、１３～２１および２６～２７は、Ｎｉ比率が２０．０％以上である試験材Ｎｏ．２５よりも、耐傷性がより良好であった。 Test material No. When comparing 1 to 9, 13 to 21, and 25 to 27, the test material No. 1 in which the Ni ratio on the outermost surface of the Fe—Ni diffusion layer is 1.0% or more and less than 20.0% Nos. 1 to 9, 13 to 21, and 26 to 27 are test materials having Ni ratios of 20.0% or more. The scratch resistance was better than 25.
　試験材Ｎｏ．１～９を対比すると、試験材Ｎｏ．５～７よりも、Ｎｉ比率がより低い試験材Ｎｏ．１～４および８～９の方が、耐傷性が更に良好であった。
　同様に、試験材Ｎｏ．１３～２１を対比すると、試験材Ｎｏ．１７～１９よりも、Ｎｉ比率がより低い試験材Ｎｏ．１３～１６および２０～２１の方が、耐傷性が更に良好であった。 Test material No. When comparing 1 to 9, the test material No. Test material No. 5 with a lower Ni ratio than 5-7. 1 to 4 and 8 to 9 had better scratch resistance.
Similarly, the test material No. When comparing 13 to 21, test material No. Test material No. 17 with a lower Ni ratio than 17-19. 13-16 and 20-21 had better scratch resistance.

Claims (8)

  1. 　鋼板の両面の表層にＦｅ－Ｎｉ拡散層を有し、
    　前記Ｆｅ－Ｎｉ拡散層は、前記鋼板の片面あたりのＮｉ換算の付着量が、５０ｍｇ／ｍ2以上５００ｍｇ／ｍ2以下である、電池外筒缶用鋼板。     It has Fe-Ni diffusion layers on the surface layers on both sides of the steel plate,
    The Fe—Ni diffusion layer is a steel sheet for battery outer cans, wherein the amount of Ni converted per one side of the steel sheet is 50 mg / m 2 or more and 500 mg / m 2 or less.
  2. 　前記Ｆｅ－Ｎｉ拡散層の最表面におけるＮｉ比率が、１．０％以上２０．０％未満である、請求項１に記載の電池外筒缶用鋼板。
    　ただし、前記Ｎｉ比率は、前記Ｆｅ－Ｎｉ拡散層の最表面における、Ｆｅ量とＮｉ量との合計に対する前記Ｎｉ量の割合であり、前記Ｆｅ量および前記Ｎｉ量の単位は、原子％である。     The steel plate for a battery outer can according to claim 1, wherein the Ni ratio on the outermost surface of the Fe-Ni diffusion layer is 1.0% or more and less than 20.0%.
    However, the Ni ratio is the ratio of the Ni amount to the total of the Fe amount and the Ni amount at the outermost surface of the Fe—Ni diffusion layer, and the unit of the Fe amount and the Ni amount is atomic%. .
  3. 　前記Ｆｅ－Ｎｉ拡散層の厚さが、０．０１μｍ以上０．５μｍ未満である、請求項１または２に記載の電池外筒缶用鋼板。 The steel plate for battery outer cans according to claim 1 or 2, wherein the thickness of the Fe-Ni diffusion layer is 0.01 µm or more and less than 0.5 µm.
  4. 　電池外筒缶形状の鋼板の内面および外面の表層にＦｅ－Ｎｉ拡散層を有し、
    　前記鋼板の外面側の前記Ｆｅ－Ｎｉ拡散層上に、更に、Ｎｉ層を有し、
    　前記鋼板の外面側の前記Ｆｅ－Ｎｉ拡散層の一部が、前記鋼板の片面あたりのＮｉ換算の付着量が５０ｍｇ／ｍ2以上５００ｍｇ／ｍ2以下のＦｅ－Ｎｉ拡散層Ａである、電池外筒缶。     Fe-Ni diffusion layers on the inner and outer surface layers of the battery outer can-shaped steel plate,
    On the Fe-Ni diffusion layer on the outer surface side of the steel plate, further, there is a Ni layer,
    A part of the Fe—Ni diffusion layer on the outer surface side of the steel sheet is a Fe—Ni diffusion layer A having an Ni conversion amount per side of the steel sheet of 50 mg / m 2 or more and 500 mg / m 2 or less. Outer cylinder can.
  5. 　前記Ｆｅ－Ｎｉ拡散層Ａの最表面におけるＮｉ比率が、１．０％以上２０．０％未満である、請求項４に記載の電池外筒缶。
    　ただし、前記Ｎｉ比率は、前記Ｆｅ－Ｎｉ拡散層の最表面における、Ｆｅ量とＮｉ量との合計に対する前記Ｎｉ量の割合であり、前記Ｆｅ量および前記Ｎｉ量の単位は、原子％である。     The battery outer can according to claim 4, wherein the Ni ratio on the outermost surface of the Fe-Ni diffusion layer A is 1.0% or more and less than 20.0%.
    However, the Ni ratio is the ratio of the Ni amount to the total of the Fe amount and the Ni amount at the outermost surface of the Fe—Ni diffusion layer, and the unit of the Fe amount and the Ni amount is atomic%. .
  6. 　前記Ｆｅ－Ｎｉ拡散層Ａの厚さが、０．０１μｍ以上０．５μｍ未満である、請求項４または５に記載の電池外筒缶。 The battery outer can according to claim 4 or 5, wherein a thickness of the Fe-Ni diffusion layer A is 0.01 µm or more and less than 0.5 µm.
  7. 　前記Ｎｉ層の厚さが、１μｍ以上である、請求項４～６のいずれか１項に記載の電池外筒缶。 The battery outer can according to any one of claims 4 to 6, wherein the Ni layer has a thickness of 1 µm or more.
  8. 　請求項４～７のいずれか１項に記載の電池外筒缶と、
    　前記電池外筒缶の内部に配置された電解液、電極およびセパレータと、を備える電池。     A battery outer can according to any one of claims 4 to 7,
    A battery comprising an electrolyte solution, an electrode, and a separator disposed inside the battery outer can.
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