WO2005078823A1

WO2005078823A1 - Plated steel sheet for battery container, battery container using such plated steel sheet, and battery using such battery container

Info

Publication number: WO2005078823A1
Application number: PCT/JP2005/001925
Authority: WO
Inventors: Hitoshi Ohmura; Tatsuo Tomomori; Yoshitaka Honda; Eiji Yamane; Eiji Okamatsu
Original assignee: Toyo Kohan Co., Ltd.
Priority date: 2004-02-13
Filing date: 2005-02-09
Publication date: 2005-08-25
Also published as: JP2005256154A; JP4798955B2

Abstract

Disclosed is a plated steel sheet for battery containers which enables to obtain a battery having excellent discharge characteristics without forming a conductive layer mainly composed of graphite or the like over the inner surface of a battery container. Also disclosed are a battery container using such a plated steel sheet and a battery employing such a battery container. Such a plated steel sheet for battery containers is obtained by forming a nickel layer and/or a nickel alloy layer on one side of a steel sheet which is to be the inner surface of a battery container sequentially from the steel sheet side and further forming an alloy layer containing silver thereon. A battery container is obtained by shaping this plated steel sheet for battery containers into a tube with a bottom.

Description

Specification

Plated steel plate for battery container, battery container using the plated steel plate for battery container, and battery using the battery container

Technical field

The present invention relates to a plated steel plate for a battery container, and a battery container using the plated steel plate for a battery container.

And a battery using the battery container.

Background art

[0002] In recent years, portable devices have been used in various fields such as audio devices and mobile phones, and alkaline batteries as primary batteries, nickel-metal hydride batteries as secondary batteries, and lithium-ion batteries have been frequently used as operating power sources. ing. These batteries are constantly required to have high output such as high output and long life, and battery containers filled with positive and negative electrode active materials are also required to improve performance as important components of batteries. I have. For example, in order to reduce the contact resistance between the positive electrode active material and the inner surface of the battery container, irregularities are provided on the inner surface of the battery container. The inventors of the present invention have proposed a surface-treated steel sheet having a nickel-tin intermetallic compound formed on the surface thereof, in which irregularities are easily generated on the inner surface of the container (for example, see Patent Document 1). In addition, graphite is dispersed and deposited in the nickel plating formed on the surface of the steel sheet to form irregularities on the surface and expose graphite particles with excellent conductivity to the surface to allow contact between the positive electrode active material and the inner surface of the battery container. The present inventors have also proposed a surface-treated steel sheet with reduced resistance (for example, see Patent Document 2).

[0003] When forming a battery by forming these surface-treated steel sheets into a battery container and filling the positive electrode and the negative electrode active material, it is necessary to reduce contact resistance with the filled negative electrode active material and improve discharge characteristics. However, a paint mainly composed of graphite or the like is applied to the inner surface of the battery container to form a conductive layer. However, when the paint of graphite is applied and dried, the solvent is volatilized and the environment is adversely affected. Is given. For this reason, attempts have been made to use battery containers without the application of graphite paint. However, since the discharge characteristics and the like are reduced, even if the application of the graphite paint is omitted, the battery container plating does not deteriorate. There is a need for steel sheets. [0004] Prior art documents relating to the present invention include the following.

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 07-300695

Patent Document 2: International Publication No. WO00Z05437 pamphlet

Disclosure of the invention

Problems to be solved by the invention

[0006] The present invention relates to a plated steel sheet for a battery container, which can provide a battery having excellent discharge characteristics without forming a conductive layer mainly composed of graphite or the like on the inner surface of the battery container, and an electrode using the same. It is an object to provide a pond container and a battery using the same.

Means for solving the problem

[0007] The plated steel sheet for a battery container of the present invention that solves the above-mentioned problems is characterized in that, in the plated steel sheet for a battery container using a steel sheet as a substrate, an alloy layer containing silver is formed on the outermost surface on the inner surface side of the battery container. A plated steel sheet for a battery container (claim 1). In this case, it is desirable that the alloy layer containing silver is a nickel-tin-silver alloy layer, a nickel-phosphorous-tin "! Good alloy layer or a nickel-cobalt-tin-silver alloy layer (Claim 2).

[0008] In the plated steel sheet for a battery container, an iron-nickel alloy layer and a nickel-tin-silver alloy layer are sequentially formed on the steel sheet on the side serving as the inner surface of the battery container. 3), or

In the plating steel sheet for a battery container, an iron-nickel alloy layer, a nickel layer, and a nickel-tin-silver alloy layer are formed on the steel sheet in order from the bottom on the inner side of the battery container (Claim 4), or

In the plated steel sheet for the battery container, the iron-nickel alloy layer, the iron-nickel-phosphorous alloy layer, and the nickel-phosphorous tin layer are formed on the steel sheet in order from the bottom on the steel sheet ( Claim 5), or

In the steel sheet for the battery case, the iron-nickel alloy layer, iron-nickel-phosphorus alloy layer, nickel-phosphorus alloy layer, and nickel-phosphorus tin-silver alloy layer are formed on the steel sheet in order from the bottom on the inner side of the battery case. (Claim 6) or

In the plating steel sheet for the battery container, on the side that becomes the inner surface of the battery container, an iron-nickel-phosphorus alloy layer and a nickel-phosphorous tin ”! Claim 7), or

In the steel sheet for battery case, the iron-nickel-phosphorus alloy layer, nickel-phosphorus alloy layer, and nickel-phosphorus-tin "! Good alloy layer are formed on the steel sheet in order from the bottom on the inner side of the battery case. (Claim 8) or

In the plated steel sheet for the battery container, the iron-nickel alloy layer, iron-nickel-cobalt alloy layer, and nickel-cobalt-tin alloy layer must be formed in order from the bottom on the inner side of the battery container. (Claim 9), or

On the inner side of the battery case, the iron / nickel alloy layer, the iron / nickel / cobalt alloy layer, the nickel / cobalt alloy layer, and the nickel / cobalt tin / good alloy layer are formed on the steel plate in order from the bottom. (Claim 10), or

In the plated steel sheet for a battery container, an iron-nickel-cobalt alloy layer and a nickel-cobalt-tin "! Good alloy layer must be formed on the steel sheet in order from the bottom on the steel sheet inner side (claim 11). Or

In the plated steel sheet for a battery container, an iron-nickel-cobalt alloy layer, a nickel-cobalt alloy layer, and a nickel-cobalt-tin-silver alloy layer are formed in order from the bottom on the inner side of the battery container (from the claim). Clause 12), or

On the side to be the inner surface of the battery container, an iron-nickel alloy layer, an iron- 12 nickel-rucono-retorin alloy layer, and a nickel-cono-retorin-tin-silver alloy layer are formed on the steel plate in the order from the bottom to the bottom (claim 13). Features, or

On the side that is the inner surface of the battery container, an iron-nickel alloy layer, an iron-nickel-cobalt-phosphorus alloy layer, a nickel-cobalt-phosphorus alloy layer, and a nickel-cobalt-phosphorus-tin-silver alloy layer are sequentially formed on a steel plate in the lower color order. (Claim 14), or

The iron-nickel alloy layer, nickel layer, nickel-cobalt-phosphorous-alloy layer, and nickel-cobalt-phosphorus-tin--good alloy layer are formed on the steel plate in the order from the bottom on the side that is the inner surface of the battery container (claim 15). Features, or

On the side that will be the inner surface of the battery container, an iron-nickel alloy layer, an iron-nickel-lucono-retorin alloy layer, and a nickel-cono-retorin "! Good alloy layer must be formed on a steel plate in the order of lower color ( Claim 16), or

On the side that will be the inner surface of the battery container, an iron-nickel alloy layer, an iron-nickel-cobalt-phosphorus alloy layer, a nickel-cobalt-phosphorus alloy layer, and a nickel-cobalt-phosphorus-silver alloy layer are formed on a steel plate in order from the bottom. (Claim 17), or

An iron-nickel alloy layer, a nickel layer, a nickel-cobalt-phosphorous-alloy layer, and a nickel-cobalt-phosphorus-silver alloy layer are formed on a steel sheet in the order from the bottom to the inner surface of the battery container (claim 18). And again

In the above-mentioned steel sheet for a battery case (claim 118), an iron-nickel alloy layer and a nickel layer are formed in order from the bottom on the steel sheet on the outer surface of the battery case (claim 19). ).

[0010] The battery container of the present invention is formed by molding the steel sheet for battery container according to any one of claims 1 to 19 into a bottomed cylindrical shape. A battery container (Claim 20) characterized by the following:

A battery according to the present invention is a battery (claim 21) characterized in that it is formed using the battery container described above (claim 20).

The invention's effect

In the present invention, a silver-tin alloy layer is formed on the outermost surface of the plated steel sheet for a battery container on the inner surface side of the battery container, so that a paint containing graphite powder as a main component is applied to the inner surface of the container. Even if used without the above, the same or higher discharge characteristics as those of a conventional battery container using a graphite-coated container can be obtained, and the battery life is also improved.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail. First, a steel sheet which is a substrate of the plated steel sheet for a battery container of the present invention will be described. The steel sheet used as the substrate may be a general-purpose low-carbon aluminum-killed steel (carbon content 0.01 to 0.15% by weight) or a non-ageable ultra-low carbon aluminum-killed steel (carbon content 0.01 % By weight). These steels are hot-rolled to remove the scale from the surface by pickling, then cold-rolled, electrolytically cleaned, annealed and temper-rolled, and used as a substrate. After cold rolling and electrolytic cleaning, the substrate may be plated without annealing and then annealed. [0013] A metal layer is formed on both sides of the steel sheet as the substrate obtained in this manner to obtain a plated steel sheet for a battery container of the present invention. Generally, the metal layer formed on the plated steel sheet for battery containers is a nickel plated layer, a nickel alloy plated layer, a cobalt plated layer, a cobalt alloy plated layer, a nickel cobalt alloy plated layer, or After the plating layer is formed, heat treatment is performed. However, in the plated steel sheet for a battery container of the present invention, the uppermost layer of these metal layers formed on the side of the steel sheet that is the inner surface of the battery container is provided. It is characterized in that an alloy layer containing silver is formed. Normally, in order to reduce the contact resistance with the negative electrode active material to be filled and improve the discharge characteristics, the inner surface of the battery container is provided with a steel plate with a metal layer formed on the steel plate for the battery container. The conductive layer is formed by applying a paint mainly composed of graphite or the like on the metal layer on the inner surface side of the container to form a conductive layer. However, when the battery is filled with the positive and negative electrode active materials, an alloy layer containing silver is formed on the outermost surface of the inner surface of the container, so that the battery container coated with the conventional graphite paint without applying the graphite paint is applied. Discharge characteristics equivalent to or better than those obtained by using are obtained. Therefore, the steps of applying and drying the graphite paint can be omitted. In the case where the plated steel sheet for a battery container of the present invention is formed into a battery container and a container having a graphite paint applied to the inner surface of the container is used as in the conventional case, the discharge characteristics are further improved. Also, a secondary effect that the internal resistance is reduced and the battery life is improved can be obtained.

[0014] The metal layer on the inner surface of the container, on which the alloy layer containing silver is formed on the outermost surface of the steel plate on the side to be the inner surface of the battery container, is preferably configured as shown below. That is, in order from the steel sheet side, (a) an iron-nickel alloy layer, a nickel-tin-silver alloy layer, (b) an iron-nickel alloy layer, a nickel layer, a nickel-tin-silver alloy layer, (C) Iron-nickel alloy layer, iron-nickel-phosphorus alloy layer, nickel-phosphorus tin-silver alloy layer, (d) iron-nickel alloy layer, iron-nickel-phosphorus alloy layer, nickel-phosphorus alloy layer, Lurin tin silver alloy layer formed, (e) iron nickel phosphorus alloy layer, -nickel phosphorus tin "! Good alloy layer formed, (f) iron nickel phosphorus alloy layer, nickel phosphorus alloy layer, nickel phosphorus tin (G) iron-nickel alloy layer, iron-nickel-cobalt alloy layer, nickel-cobalt-tin-silver alloy layer, (h) iron-nickel alloy layer, iron-nickel-cobalt alloy layer, Nickel Baltic alloy layer, nickel-Koba Ruto tin silver alloy layer, (i) iron nickel cobalt alloy layer, nickel cobalt tin silver alloy layer formed, (j) iron nickel cobalt alloy layer, nickel cobalt alloy layer, nickel cobalt tin _ good alloy layer (K) iron-nickel alloy layer, iron-nickel-cono-retolin alloy layer, nickel-cono-leto tin-silver alloy layer, (1) iron-nickel alloy layer, iron-nickel-cobalt-phosphorus alloy layer, nickel-cobalt-phosphorus layer Alloy layer, nickel-cobalt-tin "! Good alloy layer formed, (m) Iron-nickel alloy layer, nickel layer, nickel-copper phosphorus alloy layer, nickel-cobalt-tin-silver alloy layer formed, (n) Iron-nickel alloy layer, iron-nickel-cobalt-phosphorus-alloy layer, nickel-cobalt "I Good alloy layer formed, (o) iron-nickel alloy layer, iron-nickel (P) Iron-nickel alloy layer, nickel layer, nickel-cobalt-phosphorus alloy layer, nickel-cobalt-silver alloy layer , It is preferable that it is misaligned. The abundance of silver in the alloy layer containing silver as the outermost surface of the metal layer, 0.1 as silver 05-1. 0 g / m ²ゝpreferably not 0. 05-0. 5g / m ² To be a child! / ,. If the content is less than 0.05 g / m ² , the effect of improving the discharge characteristics is poor. 1. If the content exceeds Og / m ² , the discharge characteristics are not further improved and the cost is not advantageous.

Further, it is preferable to provide an iron-nickel alloy layer and a nickel layer on the steel sheet in order of the downward force on the side of the steel sheet for the battery container which is to be the outer surface of the battery container.

Next, a method for producing the plated steel sheet for a battery container of the present invention will be described. The above-mentioned cold-rolled steel sheet of low-carbon aluminum-killed steel or ultra-low-carbon aluminum-killed steel is used as a substrate. The upper layer is made of a nickel-phosphorus alloy or a nickel-cobalt alloy. A two-layer plating is formed as a base plating layer, and a tin plating layer and a silver plating are formed on one of these base plating layers. Force to form a coating layer, or to apply a nickel-tin alloy coating on one of these base plating layers and form a tin plating layer thereon and a silver plating layer thereon, or After forming a silver-tin alloy plating layer on one of the base plating layers, annealing is performed to form any of the above alloy layers containing silver on the outermost surface. Or one of the above-mentioned substrates on the substrate After forming a layer, annealing is performed, and then a tin plating layer and a silver plating layer are formed on the underlying plating layer after annealing, and a silver-tin alloy is formed on any of these underlying plating layers. After the formation of the plating layer, a re-annealing treatment may be performed to form any of the above alloy layers containing silver on the outermost surface. The step of forming the above-mentioned plating layer on the substrate of these cold-rolled steel sheets and performing the annealing treatment is performed when a cold-rolled steel sheet of low carbon aluminum killed steel is used as a plating substrate (hereinafter, referred to as “Step A”). The use of cold rolled ultra-low carbon aluminum-killed steel sheets as plating substrates (hereinafter referred to as “B process” t) is broadly classified.

[0016] When the plated steel sheet for a battery container is manufactured by the step A, it is performed as follows. When forming a metal layer having the above configuration (a) or (b) on a steel plate, cold-roll low-carbon aluminum-killed steel, electrolytically wash in an aqueous alkaline solution, and then apply nickel plating to both sides. , Box annealing or continuous annealing. Next, after temper rolling, tin plating is applied only to the side that will be the inner surface of the battery container, and silver plating is applied thereon. Alternatively, apply silver-tin alloy. Or, after temper rolling, apply a nickel-tin alloy and then apply silver. Or apply silver-tin alloy. Thereafter, box annealing or continuous annealing is performed again. In this way, a nickel layer and a Z or nickel-iron alloy layer having the structure of (a) or (b) are formed on the inner side of the battery container, and a nickel-tin-silver alloy layer is further formed on the outermost surface. The steel plate for a battery container according to the present invention, which is formed and has an iron-nickel alloy layer and a nickel layer formed on the side to be the outer surface of the battery container, is obtained. If the annealing after cold rolling is performed by box type annealing, it is preferable to perform soaking in the temperature range of 640-680 ° C for 5-20 hours.If continuous annealing is performed, the temperature range is 730-800 ° C. It is preferable to soak 0.5 to 3 minutes. When performing post-plating annealing by box-type annealing, it is preferable to soak in a temperature range of 500 to 530 ° C for 5 to 10 hours.When performing continuous annealing, it is preferable to perform soaking in a temperature range of 730 to 800 ° C. It is preferable to soak for 5 to 3 minutes. Whether to provide the metal layer of the configuration (a) or (b) is appropriately selected from the amount of nickel plating and the annealing conditions (type, temperature, time) after plating.

[0017] In the case of forming a metal layer having the above-mentioned configuration (c) or (d) on a steel plate, the low-carbon aluminum-killed steel is temper-rolled through the same steps as described above, and then becomes the inner surface of the battery container. On the side of the battery case and nickel-phosphorus alloy on top of it, Apply nickel plating and perform box type annealing or continuous annealing. Next, after temper rolling, tin plating is performed only on the side that will be the inner surface of the battery container, and silver plating or silver-tin alloy plating is performed thereon. Thereafter, box annealing or continuous annealing is performed again. In this way, the nickel-iron alloy layer and nickel-phosphorus alloy layer (C) or (d) are

Two layers and two layers of Z or nickel-ferrous alloy layer and nickel-phosphorous iron-iron alloy layer are formed, and a nickel-phosphorus-tin-silver alloy layer is further formed on the outermost surface. Can be obtained a plated steel sheet for a battery container of the present invention, on which an iron-nickel alloy layer and a nickel layer are formed. Annealing conditions after cold rolling and after plating are appropriately selected in the same range as the above annealing conditions after cold rolling. Whether to provide the metal layer of the configuration (c) or (d) is determined by appropriately selecting the amount of nickel-phosphorus alloy deposition and the annealing conditions (type, temperature, time) after plating.

When a metal layer having the structure (e) or (f) is formed on a steel plate, the low-carbon aluminum-killed steel is temper-rolled through the same process as described above, and then becomes the inner surface of the battery container. Apply a nickel-phosphorus alloy to the side, apply nickel plating to the side that will be the outer surface of the battery container, and perform box-type annealing or continuous annealing. Next, after temper rolling, tin plating and silver plating or silver-tin alloy plating are performed only on the side that will be the inner surface of the battery container. Thereafter, box annealing or continuous annealing is performed again. In this way, the nickel-phosphorus alloy layer (e) or (f) and the Z or nickel-phosphorous iron alloy layer are formed on the inner side of the battery container, and the nickel-phosphorus-tin-silver layer is formed on the outermost surface. An alloy layer is formed, and an iron-nickel alloy layer and a nickel layer are formed on the side to be the outer surface of the battery container, thereby obtaining the steel plate for a battery container of the present invention. The annealing conditions after the cold rolling and after the plating are appropriately selected in the same range as the above annealing conditions after the cold rolling. Whether to provide the metal layer of the configuration (e) or (f) is appropriately selected from the amount of nickel-phosphorus alloy deposition and the annealing conditions (type, temperature, and time) after the plating.

When a metal layer having the configuration (g) or (h) is formed on a steel plate, the low-carbon aluminum-killed steel is temper-rolled through the same process as described above, and then becomes the inner surface of the battery container. Apply nickel plating on the side and nickel-cobalt alloy plating thereon, apply nickel plating on the side that will be the outer surface of the battery container, and perform box-type annealing or continuous annealing. Continue to be inside the battery container Apply tin plating only on the side and silver plating or silver-tin alloy plating on it. After that, box annealing or continuous annealing is performed again. In this way, on the side that becomes the inner surface of the battery container, two layers of the nickel-iron alloy layer and the nickel-cobalt alloy layer and the Z or nickel-iron alloy layer and the nickel-cobalt alloy layer of (g) or (h) Two layers of a ferrous alloy layer are formed, and a nickel-cobalt-tin "good alloy layer is formed on the outermost surface, and an iron-nickel alloy layer and a nickel layer are formed on the outer surface of the battery container. The annealing conditions after cold rolling and after plating are appropriately selected within the same range as the annealing conditions after cold rolling described above. As to which metal layer of the configuration of h) is provided, the amount of nickel-cobalt alloy deposition and the annealing conditions (type, temperature, time) after plating are appropriately selected.

[0020] When the metal layer having the configuration (i) or (j) is formed on a steel sheet, the low-carbon aluminum-killed steel is temper-rolled through the same steps as described above, and then becomes the inner surface of the battery container. Apply nickel alloy on one side, apply nickel plating on the side that will be the outer surface of the battery container, and perform box-type annealing or continuous annealing. Subsequently, tin plating is applied only to the inner side of the battery container and silver plating or silver-tin alloy plating is applied thereon. After that, box annealing or continuous annealing is performed again. In this way, on the side that becomes the inner surface of the battery container, the nickel cobalt tin "! Good alloy layer is formed on the outermost surface on the nickel cobalt iron alloy layer of the configuration (i), or the configuration of (j). A nickel-cobalt alloy layer is formed on the nickel-cobalt-iron alloy layer, and a nickel-cobalt-tin "! Good alloy layer is formed on the outermost surface. The plated steel sheet for a battery container of the present invention on which a nickel alloy layer and a nickel layer are formed is obtained. The annealing conditions after cold rolling and after plating are appropriately selected in the same range as the annealing conditions after cold rolling described above. Whether to provide a metal layer in the configuration of (ii) or G) is determined by the amount of nickel-cobalt alloy deposition and the annealing conditions (type, temperature, time) after plating.

[0021] When the metal layer having the configuration (k) or (1) or (m) is formed on a steel sheet, the low-carbon aluminum-killed steel is temper-rolled through the same steps as above, and then the battery container Nickel plating is applied on the inner side and nickel-cobalt-phosphorus alloy is applied on the inner side. Nickel plating is applied on the outer side of the battery container, and box or continuous annealing is performed. Continue to Apply tin plating and silver plating or silver-tin alloy plating only on the inner surface of the pond. Thereafter, box annealing or continuous annealing is performed again. In this way, the nickel-cobalt-phosphorus-tin "! Good alloy layer is formed on the outermost surface of the two layers of the iron-nickel alloy layer having the configuration (k) and the iron-nickel-cobalt-phosphorous alloy layer on the side that will be the inner surface of the battery container. The formed force or iron-nickel alloy layer of the configuration of (1), the iron-nickel-cobalt-phosphorus alloy layer on it, and the nickel-conoreletrin alloy layer on it are further formed on the outermost surface. Nickel Cobalt Phosphorus Tin "! A three-layer structure consisting of a good alloy layer or an iron-nickel alloy layer (m) and a nickel layer on it, and a nickel-cobalttrin alloy layer on it is formed on top. A nickel-cobalt-tin-tin "! Good alloy layer is formed on the surface, and an iron-nickel alloy layer and a nickel layer are formed on the outer surface of the battery container. The conditions for annealing after rolling and after plating are appropriately selected within the same range as the annealing conditions after cold rolling described above, which metal layer of (k) or (1) or (m) is provided. For, select the amount of plating of various metals or alloys and the annealing conditions (type, temperature, time) after plating as appropriate.

When forming a metal layer having the above structure (n) or (o) or (p) on a steel plate, low-carbon aluminum-killed steel is temper-rolled through the same process as above, and then becomes the inner surface of the battery container Nickel plating on the side and nickel-cobalt-phosphorus alloy plating on it, nickel plating on the side that will be the outer surface of the battery container, and box or continuous annealing. Continue to apply silver plating only to the inner side of the battery container. Thereafter, box annealing or continuous annealing is performed again. In this way, on the side that will be the inner surface of the battery container, the nickel-cobalt-phosphorus! Or an iron-nickel alloy layer having the configuration of (o), an iron-nickel-cobalt-phosphorus alloy layer thereon, and a nickel-cobalt-phosphorus alloy layer thereabove, and a nickel-cobalt-phosphorus alloy layer thereover. A nickel-cobalt-phosphorus-silver alloy layer is formed on the surface, or an iron-nickel alloy layer with the composition (p), a nickel layer on it, and a nickel-cobalt-phosphorus alloy layer on it are formed. A nickel cobalt-phosphorus good alloy layer is formed on the outermost surface, and the outer surface of the battery container is The plated steel sheet for a battery container of the present invention on which the iron-nickel alloy layer and the nickel layer are formed is obtained. The annealing conditions after the cold rolling and after the plating are appropriately selected in the same range as the annealing conditions after the cold rolling. Whether the metal layer of (n), (o), or (p) is provided with a misaligned metal layer depends on the amount of plating of various metals or alloys and the annealing conditions (type, temperature, and time) after plating. select.

[0023] When the plated steel sheet for a battery container is manufactured in the step B, the following procedure is performed. When providing a metal layer of the above configuration (a) or (b) on a steel plate, cold roll an ultra-low carbon aluminum killed steel, electrolytically wash in an alkaline aqueous solution, apply nickel plating on both sides, and pull Subsequently, tin plating is applied only to the inner surface of the battery container, and silver plating or silver-tin alloy plating is applied thereon. Alternatively, apply a nickel-tin alloy plating, and then apply a silver plating or a silver-tin alloy plating. Thereafter, continuous annealing is performed, followed by temper rolling. In this way, the nickel layer and the Z or nickel-iron alloy layer having the configuration of (a) or (b) are formed on the side that becomes the inner surface of the battery container, and the nickel-tin-silver alloy layer is formed on the outermost surface. Thus, the plated steel sheet for a battery container of the present invention is obtained in which an iron-nickel alloy layer and a nickel layer are formed on the outer side of the battery container. The continuous annealing is preferably carried out in a temperature range of 730 to 800 ° C for 0.5 to 3 minutes. The amount of nickel plating and the conditions of continuous annealing (temperature and time) are appropriately selected as to which of the metal layers (a) and (b) is provided.

[0024] When the metal layer having the configuration (c) or (d) is provided on the steel sheet, the ultra-low carbon aluminum-killed steel is electrolytically cleaned through the same steps as above, and then the inner surface of the battery container is formed. On the other side, nickel plating and nickel-phosphorous alloy plating are applied, and then tin plating and silver plating or silver-tin alloy plating are applied thereon. On the side that will be the outer surface of the battery container, apply nickel plating. Thereafter, continuous annealing is performed, followed by temper rolling. In this way, on the side serving as the inner surface of the battery container, two layers of the nickel-iron alloy layer and the nickel-phosphorus alloy layer having the configuration (c) or (d) and / or the nickel-iron alloy layer and the nickel-phosphorus iron layer An alloy layer of nickel-phosphorus-tin-silver is formed on the outermost surface of the alloy layer, and an iron-nickel alloy layer and a nickel layer are formed on the outer surface of the battery container. A plated steel sheet for a battery container is obtained. For continuous annealing, it is preferable to soak in a temperature range of 730-800 ° C for 0.5-3 minutes. (C) or (d) nickel layer and Z or nickel alloy Which of the gold layers is provided depends on the amount of nickel plating and continuous annealing conditions (temperature, time).

When a metal layer having the above configuration (e) or (f) is provided on a steel sheet, ultra-low carbon aluminum-killed steel is electrolytically cleaned through the same steps as described above, and then the inner surface of the battery container is formed. On the other side, apply a -Kaknorelin alloy plating, and then apply a tin plating and a silver plating or silver-tin alloy plating thereon. Nickel plating is applied to the side to be the outer surface of the battery container. Thereafter, continuous annealing is performed and then temper rolling. In this way, a nickel-phosphorin alloy layer and / or a nickel-phosphorus-iron alloy layer having the structure (e) or (f) is formed on the inner side of the battery container, and the nickel phosphorous Tin "! A good alloy layer is formed, and a nickel-alloy layer and a nickel layer are formed on the side to be the outer surface of the battery container to obtain the plated steel sheet for battery containers of the present invention. It is preferable to soak for 0.5 to 3 minutes in a temperature range of 800 ° C. U. The nickel layer and / or nickel alloy layer with the configuration (e) or (f) is determined by the amount of nickel plating. , And continuous annealing conditions (temperature, time) are appropriately selected.

[0026] When a metal layer having the above configuration (g) or (h) is provided on a steel plate, ultra-low carbon aluminum-killed steel is electrolytically cleaned through the same steps as described above, and then the inner surface of the battery container is cleaned. On the other side, nickel plating and nickel-cobalt alloy plating are applied, and then tin plating and silver plating or silver-tin alloy plating are applied. Nickel plating is applied to the outer side of the battery container. Thereafter, continuous annealing is performed, followed by temper rolling. In this way, on the side that will be the inner surface of the battery container, two layers of nickel-iron alloy layer and nickel-cobalt alloy layer of (g) or (h) and Z or nickel-iron alloy layer and nickel-cobalt-iron alloy Of the present invention, in which a nickel-cobalt-tin-silver alloy layer is formed on the outermost surface, and an iron-nickel alloy layer and a nickel layer are formed on the outer side of the battery container. A plated steel sheet for a battery container is obtained. The continuous annealing is preferably carried out in a temperature range of 730-800 ° C for 0.5-3 minutes. Whether to provide the nickel layer and / or nickel alloy layer having the configuration of (g) or (h) is appropriately selected from the amount of nickel plating and the continuous annealing conditions (temperature and time).

[0027] When a metal layer having the above-mentioned configuration (i) or (j) is provided on a steel plate, an extremely low carbon aluminum alloy is used. The steel is electrolytically cleaned through the same process as above, and then the nickel-coated nickel alloy is applied to the side that will become the inner surface of the battery container, and then tin and silver are further applied. Apply silver-tin alloy. Nickel plating is applied to the side to be the outer surface of the battery container. After that, continuous annealing and then temper rolling are performed. In this way, the nickel-cobalt alloy layer and the Z or nickel-cobalt-iron alloy layer having the configuration (i) or (j) are formed on the side serving as the inner surface of the battery container, and the nickel cobalt tin The plated steel sheet for a battery container of the present invention is obtained in which a silver alloy layer is formed, and an iron-nickel alloy layer and a nickel layer are formed on the outer surface of the battery container. The continuous annealing is preferably carried out in a temperature range of 730-800 ° C for 0.5-3 minutes. Whether to provide the nickel layer and / or the nickel alloy layer having the configuration (i) or (j) is appropriately selected from the nickel plating amount and the continuous annealing conditions (temperature and time).

When providing a metal layer having the above configuration (k) or (1) or (m) on a steel plate, ultra-low carbon aluminum killed steel is electrolytically washed through the same process as above, and then the inner surface of the battery container Then, apply nickel plating and nickel-cobalt-phosphorus alloy plating on the side to be treated, and then apply tin plating and silver plating or silver-tin alloy plating thereon. Nickel plating is applied to the outer side of the battery container. Thereafter, continuous annealing is performed, followed by temper rolling. In this way, the nickel-cobalt-phosphorus-tin-silver alloy layer is formed on the outermost surface of the two layers consisting of the iron-nickel alloy layer having the configuration (k) and the iron-nickel-cobalt-phosphorus alloy layer on the side that will be the inner surface of the battery container. Nickel-cobalt-phosphorous-tin formed on the outermost surface on three layers consisting of an iron-nickel alloy layer having the constitution of (1), an iron-nickel-cobalt-phosphorus alloy layer thereon, and a nickel-cobalt-phosphorus alloy layer thereon. "! A nickel alloy layer with a good alloy layer formed, or an iron-nickel alloy layer with the composition of (m), a nickel layer on it, and a nickel-cobalt alloy layer on top A plated steel sheet for a battery container according to the present invention, in which a retorin-tin-silver alloy layer is formed and an iron-nickel alloy layer and a nickel layer are formed on the outer surface of the battery container, is obtained. It is preferable to soak for 0.5 to 3 minutes in the temperature range of 730 to 800 ° C. Whether to provide the metal layer of (k) or (1) or (m) depends on the type of metal or The amount of plating of the alloy and the continuous annealing conditions (temperature, time) are appropriately selected. When a metal layer having the structure (n) or (o) or (p) is provided on a steel sheet, the ultra-low carbon aluminum killed steel is electrolytically washed through the same steps as described above, and then Nickel plating and nickel-cobalt-phosphorus alloy plating are applied to the inner side of the battery container, and then tin plating and silver plating are applied. Nickel plating is applied to the side that will be the outer surface of the battery container. Thereafter, continuous annealing is performed, followed by temper rolling. In this way, the outermost surface of the two layers consisting of the iron-nickel alloy layer having the structure (n) and the iron-nickel-cobalt-phosphorus alloy layer on the side serving as the inner surface of the battery container is nickel-cobalt-phosphorous. ! A good alloy layer is formed, or the uppermost surface of the iron-nickel alloy layer with the configuration of (o), the iron-nickel-cobalt-phosphorus alloy layer on it, and the nickel-cobalt-phosphorus alloy layer on it A cobalt-phosphorous alloy with a good alloy layer formed on it, or a three-layer structure consisting of an iron-nickel alloy layer with the configuration of (p), a nickel layer thereabove, and a nickel-cobalt phosphorus alloy layer thereover A nickel-cobalt-phosphor-silver alloy layer is formed on the surface, and an iron-nickel alloy layer and a nickel layer are formed on the outer surface of the battery container. 730—800 ° C It is preferable to soak for 0.5 to 3 minutes in the temperature range.The metal layer of (n) or (o) or (p) is determined by the plating amount of various metals or alloys and continuous annealing. Conditions (temperature, time) are appropriately selected.

[0030] The plated steel sheet for a battery container of the present invention is obtained as described above. The battery container of the present invention is obtained by subjecting the above-mentioned steel sheet for battery container to drawing, drawing and ironing (DI processing), drawing and stretching (DTR), or stretching after drawing and ironing. It is obtained by forming into a bottomed cylindrical shape using the combined processing method. As the cylindrical shape, the bottom surface is a circle, an ellipse, or a polygonal shape such as a rectangle and a square, and the height of the side wall is appropriately selected according to the application, and the cylindrical shape is formed. The battery container thus obtained is filled with a positive electrode, a negative electrode active material and the like to form a battery.

Example

Hereinafter, the present invention will be described in detail with reference to examples.

[Preparation of plated steel sheets for battery containers]

The low-carbon aluminum-killed steel (II) was cold-rolled (thickness 0.25 mm) of low-carbon aluminum-killed steel (I) and ultra-low-carbon aluminum-killed steel (II) whose chemical composition is shown in Table 1. for In the case of the above, through the process indicated by i-iv below, and in the case of using ultra-low carbon aluminum killed steel (II), through the process indicated by V-xvi below, plated steel plates for battery containers were prepared respectively. . In the following i-i xvi process, plating is performed on the side that will be the inner surface of the container. Apply

i) Cold rolling → electrolytic cleaning → nickel plating → annealing (box type or continuous annealing) → temper rolling → tin plating → silver plating (or silver tin alloy plating after temper rolling) → annealing (box type or Is continuous annealing) → Silver-containing alloy layer is formed on the outermost surface

ii) Cold rolling → electrolytic cleaning → nickel plating → annealing (box type or continuous annealing) → temper rolling → plating with a nickel-tin alloy → silver plating (or plating with silver-tin alloy after temper rolling) → annealing (Box type or continuous annealing) → forming an alloy layer containing silver on the outermost surface

iii) Cold rolling → electrolytic cleaning → nickel plating → nickel-phosphorous alloy plating → annealing (box or continuous annealing) → temper rolling → tin plating → silver plating (or silver-tin alloy plating after temper rolling) → Annealing (box or continuous annealing) → forming an alloy layer containing silver on the outermost surface

iv) Cold rolling → electrolytic cleaning → nickel-phosphorus alloy plating → annealing (box or continuous annealing) → temper rolling → tin plating → silver plating (or silver-tin alloy plating after temper rolling) → annealing ( (Box type or continuous annealing) → forming an alloy layer containing silver on the outermost surface

V) Cold rolling → electrolytic cleaning → nickel plating → nickel-conolet alloy plating → annealing (box or continuous annealing) → temper rolling → tin plating → silver plating (or silver-tin alloy plating after temper rolling) → annealing (Box type or continuous annealing) → forming an alloy layer containing silver on the outermost surface

vi) Cold rolling → electrolytic cleaning → nickel-cobalt alloy plating → annealing (box-shaped or continuous annealing) → temper rolling → tin plating → silver plating (or silver-tin alloy plating after temper rolling) → annealing (box (Mold or continuous annealing) → forming an alloy layer containing silver on the outermost surface

vii) Cold rolling → electrolytic cleaning → nickel plating → nickel cobalt phosphorus alloy plating → annealing (box type or continuous annealing) → temper rolling → tin plating → silver plating (or silver-tin alloy plating after temper rolling) ) → annealing (box or continuous annealing) → forming an alloy layer containing silver on the outermost surface

viii) Cold rolling → electrolytic cleaning → nickel plating → nickel cobalt phosphorus alloy plating → Annealing (box or continuous annealing) → temper rolling → silver plating (or silver plating after temper rolling) → annealing (box or continuous annealing) → forming an alloy layer containing silver on the outermost surface

ix) Cold rolling → electrolytic cleaning → nickel plating → tin plating → silver plating (or silver-tin alloy plating after temper rolling) → continuous annealing → temper rolling → forming an alloy layer containing silver on the outermost surface

X) Cold rolling → electrolytic cleaning → nickel plating → nickel-tin alloy plating → silver plating (or silver-tin alloy plating after temper rolling) → continuous annealing → temper rolling → contains silver on the outermost surface Alloy layer formation

xi) Cold rolling → electrolytic cleaning → nickel plating → nickel-phosphorus alloy plating → tin plating → silver plating (or silver-tin alloy plating after temper rolling) → continuous annealing → temper rolling → silver on the outermost surface Alloy layer formation including

xii) Cold rolling → electrolytic cleaning → nickel-phosphorus alloy plating → tin plating → silver plating (or silver-tin alloy plating after temper rolling) → continuous annealing → temper rolling → alloy layer containing silver on the outermost surface Formation

xiii) Cold rolling → electrolytic cleaning → nickel plating → nickel-cobalt alloy plating → tin plating → silver plating (or silver-tin alloy plating after temper rolling) → continuous annealing → temper rolling → contains silver on the outermost surface Alloy layer formation

xiv) Cold rolling → electrolytic cleaning → nickel-cobalt alloy plating → tin plating → silver plating (or silver-tin alloy plating after temper rolling) → continuous annealing → temper rolling → silver on the outermost surface Including alloy layer formation

XV) Cold rolling → electrolytic cleaning → nickel plating → nickel cobalt phosphorus alloy plating → tin plating → silver plating (or silver tin alloy plating after temper rolling) → continuous annealing → temper rolling → silver on the outermost surface Formation of alloy layer containing

xvi) Cold rolling → electrolytic cleaning → nickel plating → nickel cobalt phosphorus alloy plating → silver plating (or silver plating after temper rolling) → continuous annealing → temper rolling → formation of an alloy layer containing silver on the outermost surface

[table 1] Steel grade chemical composition c S i Mil P s A 1 NN b Fe

I 0.04 0.01 0.023 0.006 0.01 0.046 0,0023 0.001 Remainder π 0.002 0.01 0.045 0.08 0.052 0.0021 0.011 Remainder Nickel plating, nickel-phosphorus alloy plating, nickel-conolet alloy plating in the process shown in i-i xvi above Tin plating, nickel-tin alloy plating, silver plating, silver-tin alloy plating were performed under the following conditions.

<-Mitsukusa>

Bath composition Nickel sulfate 300g / L

Nickel chloride 40g / L

Boric acid 30gZL

Pit inhibitor (sodium lauryl sulfate) 0.4mL / L

Anode Nickel pellets (filled in titanium basket,

With bag)

Stir Air stir

pH 4-4.6

Bath temperature 55-60 ° C

Current density 20AZdm ²

Nickel sulfate 250g / L

Nickel chloride 40g / L

Boric acid 30g / L

Phosphorous acid 5-20 g / L

Anode Nickel pellets (filled in a titanium basket and fitted with a polypropylene anode bag)

Stirring Air stirring pH 1.5—2.5

Bath temperature 40-60 ° C

Current density 10—15AZdm ²

[0035] <-Pole plating>

Bath composition Nickel sulfate 250g,

Cobalt sulfate 5—40g / L

Nickel chloride 40 _{g /}

Boric acid 30 _{g /}

Nickel pellets (filled in a titanium basket and fitted with a polypropylene anode bag)

Stir Air stir

PH 1.5—2.5

Bath temperature 40-60. C

Current density 10—15AZdm ²

[0036] <Tin plating>

Bath composition stannous sulfate 30g

60 g of phenol sulfone

Ethoxylated α-naphthol 5g

Tin plate

Circulation

Current density lOAZdm ²

[0037] <Nickel-tin alloy plating>

Bath composition Stannous chloride 50g

300 g of nickel chloride

Sodium fluoride 30g

Ammonium fluoride 35g

Nickel-28% tin alloy plate Agitation Circulation of plating bath

Bath temperature 65 ° C

pH 4.5

Current density 4AZdm ²

[0038] Silver Mesh>

Bath composition Silver-containing organic salt (Dyne Silva NEC Corporation) 200g / L

Organic acid (complex: Dynesilva-AGI) 500g, L

Organic additive (Dyne Silva-AGH) 25g / L Anode Silver plate

Agitation Circulation of plating bath

pH 3—3.5

Bath temperature 40-45 ° C

Current density lAZdm ²

[0039] Plated with silver-tin alloy>

Bath composition Silver-tin alloy plating bath (Dipsol TS-3200 (for Sn-3.5wt% Ag eutectic alloy, Dipsol Co., Ltd.)

Anode Tin plate

Stirring Plating bath circulation Bath temperature 22-285 ° C

Current density 20AZdm ²

As described above, the samples of the plated steel sheets for battery containers shown in Table 2 (sample numbers 127) were prepared. As shown in Table 3, for comparison, V samples (Sample Nos. 28-33) having no silver or silver-containing compound formed on the outermost surface were prepared.

[0040] [Table 2]

¾0041 After blanking a blank with a diameter of 57 mm from these sample Nos. 1 and 23, the side with only the iron-nickel alloy layer and the nickel layer is the outer surface of the container. It was formed into a cylindrical LR6 type battery (AA battery) container with an outer diameter of 13.8 mm and a height of 49.3 mm.

[0043] [Creation of battery]

Using this battery container, an alkaline manganese battery was prepared as follows. Manganese dioxide and graphite were collected at a ratio of 10: 1, and potassium hydroxide (10 mol) was added and mixed to prepare a positive electrode mixture. Next, the positive electrode mixture was pressurized in a mold to form a donut-shaped positive electrode mixture pellet having a predetermined size, and was press-inserted into the battery container. Some of the battery containers used had inner surfaces coated with paint containing graphite powder as a main component. Next, the negative electrode plate on which the negative electrode current collector was spot-welded was mounted on the battery container. Next, a vinylon woven fabric separator having a strong force is inserted along the inner periphery of the positive electrode mixture pellet pressed into the battery container, and the zinc oxide and potassium hydroxide are saturated with zinc oxide. The negative electrode gel was filled in the battery container. Furthermore, an insulator gasket was attached to the negative electrode plate, inserted into the battery container, and then subjected to a cashmere process to produce an alkaline manganese battery.

[Characteristic evaluation]

The characteristics of the battery prepared using the battery container prepared from the sample cap of Sample No. 133 as described above were evaluated as follows.

[0045] <Short circuit current>

After leaving the battery at 80 ° C for 3 days, an ammeter was connected to the battery, a closed circuit was provided, and the current value was measured. This was defined as the short-circuit current. The higher the short-circuit current, the better the characteristics.

After leaving the battery at 80 ° C for 3 days, the battery was discharged to a constant current of 1.5 A, and the time until the voltage reached 0.9 V was measured as the discharge time. The longer the discharge time, the better the discharge characteristics.

[0047] <Intermittent discharge characteristics>

As an evaluation of the intermittent discharge of the weighted potato, discharge at 2A for 0.5 seconds and then discharge at 0.25A for 29.5 seconds This operation was repeated as one cycle, and the number of cycles until the voltage reached 1. OV was measured. The more cycles, the better the intermittent discharge characteristics.

[0048] Table 4 shows the results of these characteristic evaluations.

[Table 4]

Characteristic evaluation results

Short circuit zero current

Electric cloth

(AJ I 'Kamema

1 11.4 420 25 Yes The present invention

2 Π.0 410 23 Yes The present invention

3 11.1 410 24 Yes The present invention

4 10.8 395 22 Yes Present invention

5 10.5 375 21 Yes Present invention

6 11.2 415 24 Ex.

7 11.5 425 25 Yes The present invention

8 10.9 415 23 Yes Present invention

9 10.8 415 23 Yes Present invention

10 10.7 410 23 Arimoto Akira

Π 10.9 410 24 Yes Present invention

12 10.3 400 21 Yes The present invention

! 3 11.1 420 24 Yes Present invention

14 8.0 200 17 4ff The present invention

15 7.5 195 15 The present invention

16 7.6 195 16 ¾ £ The present invention

17 8.9 365 22 to the present invention

18 7.5 195 14 The present invention

19 7.5 190 14 The present invention

20 7.7 195 15 The present invention

21 7.9 195 16 The present invention

22 \ ϊ.1 450 30 Yes Present invention

23 Π.9 445 30 Yes Present invention

24 8.4 235 22 The present invention

25 ΙΖ.1 450 30 Yes Present invention

26 12.0 445 29 Yes Present invention

27 8.3 230 21 is the present invention

28 6.7 170 [2 St Comparative Example

29 3.7 115 3 Comparative example

30 5.2 140 4 Comparative example

31 4.9! 25 3 Comparative example

32 5.2 140 4 in Comparative example

33 4.9 125 3 Comparative Example As shown in Table 4, in the battery using the plated steel sheet for a battery container of the present invention in which an alloy layer containing silver was formed on the outermost surface on the side to be the inner surface of the battery container, Graphite paint is applied to the inner surface of a battery container that uses a steel plate for battery containers that does not have an alloy layer containing silver As a result, short-circuit current, discharge characteristics, and intermittent discharge characteristics equivalent to or higher than those obtained were obtained. In addition, when the graphite coating was applied to the inner surface of the battery using the plated steel sheet for battery containers of the present invention, the short-circuit current, discharge characteristics, and intermittent discharge characteristics were further improved.

Industrial applicability

The battery according to the present invention, which uses the plated steel sheet for a battery container having an alloy layer containing a trace amount of silver formed on the outermost surface on the side to be the inner surface of the battery container, does not apply graphite paint to the inner surface of the container. However, it exhibits short-circuit current, discharge characteristics, and intermittent discharge characteristics that are equal to or higher than those of a conventional container with graphite paint applied to the inner surface. Therefore, the steps of applying and drying the graphite paint can be omitted, and the battery can be manufactured at low cost. Further, when a graphite paint is applied to the inner surface of the battery container using the steel sheet for battery containers of the present invention, short-circuit current, discharge characteristics, and intermittent discharge characteristics are further improved, so that a high-performance battery can be provided. You.

Claims

The scope of the claims

[1] A plated steel sheet for a battery container, comprising a steel plate as a substrate, wherein an alloy layer containing silver is formed on an outermost surface on a side to be an inner surface of the battery container.

[2] The alloy layer containing silver is nickel-tin "! An excellent alloy layer, nickel-phosphorus-tin"! 2. The plated steel sheet for a battery container according to claim 1, wherein the steel sheet is a good alloy layer or nickel cobalt tin.

[3] In the case of a plated steel sheet for a battery container using a steel sheet as a substrate, the iron-nickel alloy layer and the nickel-tin "! A plated steel sheet for a battery container, characterized in that a steel sheet is formed.

[4] With regard to the plated steel sheet for a battery container having a steel sheet as a substrate, the iron-nickel alloy layer, the nickel layer, and the nickel-tin-silver layer are formed on the steel sheet in the order from the bottom to the inner side of the battery container. A plated steel sheet for a battery container, characterized in that the alloy layer is formed! / ヽ.

[5] With respect to the steel plate for a battery container having a steel plate as a substrate, an iron-nickel alloy layer, an iron-nickel-phosphorus alloy layer, a nickel- A plating steel sheet for a battery container, wherein a phosphor-tin-silver alloy layer is formed.

[6] In the case of a plated steel sheet for a battery container having a steel sheet as a substrate, the iron-nickel alloy layer, the iron-nickel-phosphorus alloy layer, the nickel-phosphorus alloy layer, A plating steel sheet for a battery container, comprising a phosphorus alloy layer and a nickel phosphorus tin silver alloy layer.

[7] With regard to the plated steel sheet for a battery container having a steel plate as a substrate, the iron-nickel-phosphorus alloy layer and the nickel-phosphorus-tin layer are arranged on the steel plate on the side to be the inner surface of the battery container. ! Plated steel sheet for battery containers, characterized by forming a good alloy layer.

[8] With respect to the plated steel sheet for a battery container having a steel plate as a substrate, the iron-nickel-phosphorus alloy layer, the nickel-phosphorus alloy layer, the nickel-phosphorus alloy layer, A plating steel sheet for a battery container, wherein a phosphor-tin-silver alloy layer is formed.

[9] In the case of a steel plate for a battery container having a steel plate as a substrate, the iron-nickel alloy layer, the iron-nickel-cobalt alloy layer, the nickel- A plated steel sheet for a battery container, comprising a cobalt tin silver alloy layer.

[10] In the plated steel sheet for a battery container using a steel sheet as the substrate, the iron-nickel alloy layer, the iron-nickel-cobalt alloy layer, and the nickel-cobalt alloy A plated steel sheet for a battery container, characterized in that a coated layer comprises a nickel cobalt tin silver alloy layer.

[11] In the plated steel sheet for a battery container that uses a steel sheet as the substrate, the iron-nickel-cobalt alloy layer and the nickel-cobalt-tin alloy layer are successively placed on the steel plate on the side that is the inner surface of the battery container. A plated steel sheet for a battery container, characterized by being formed.

[12] In the plated steel sheet for a battery container having a steel plate as a substrate, the iron-nickel-cobalt alloy layer, the nickel-cobalt alloy layer, and the A plated steel plate for a battery container, comprising a tin-silver alloy layer.

[13] In the plated steel sheet for a battery container having a steel plate as a substrate, the iron-nickel alloy layer, the iron-nickel-cobalt-phosphorus alloy layer, and the A steel sheet for a battery container, wherein a lucono-retorin tin-silver alloy layer is formed.

[14] In the plating steel sheet for a battery container having a steel plate as a substrate, the iron-nickel alloy layer, the iron-nickel-cobalt-phosphorus alloy layer, and the A plated steel sheet for a battery container, comprising a rucobalt-phosphorus alloy layer and a nickel cobalt-phosphorus tin-silver alloy layer formed thereon.

[15] In the plated steel sheet for a battery container using a steel sheet as a substrate, the iron-nickel alloy layer, the nickel layer, the nickel-cobalt-phosphorous alloy layer, the nickel-cobalt layer, A plated steel sheet for a battery container, characterized in that a phosphorus tin _ good alloy layer is formed thereon.

[16] In the plated steel sheet for a battery container having a steel plate as a substrate, the iron-nickel alloy layer, the iron-nickel-cobalt-phosphorus alloy layer, and the LUCONO RETOLIN ~ A plated steel sheet for battery containers, wherein a good alloy layer is formed.

[17] In the plated steel sheet for a battery container using a steel sheet as a substrate, The iron-nickel alloy layer, the iron-nickel-cobalt-phosphorus alloy layer, the nickel-cobalt-phosphorous alloy layer, and the nickel-cobalt-phosphorus layer are formed on the plate in this order. Steel plate for battery containers.

[18] In the plated steel sheet for a battery container using a steel sheet as the substrate, the iron-nickel alloy layer, the nickel layer, the nickel-cobalt-phosphorus alloy layer, and the nickel A plated steel sheet for a battery container, wherein a phosphor silver alloy layer is formed.

[19] The plating steel sheet for a battery container according to any one of claims 1 to 18, wherein an iron-nickel alloy layer and a nickel layer are formed in order from the bottom on the steel sheet on the side to be the outer surface of the battery container. A plated steel sheet for a battery container, characterized in that:

[20] A battery container obtained by forming the plated steel sheet for a battery container according to any one of claims 1 to 19 into a bottomed cylindrical shape.

[21] A battery comprising the battery container according to claim 20.