JP2005310452A - Plated steel sheet for battery case, battery case using the plated steel sheet for battery case, and battery using the battery case - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plated steel sheet for a battery case capable of manufacturing a battery having high discharge characteristics without forming a conductive layer mainly comprising graphite or the like on the inner surface of the battery case, and to provide a battery case using the plated steel sheet, and to provide a battery using the battery case. <P>SOLUTION: A dispersed plated layer formed by dispersing fine carbonaceous materials in the plated layer is formed on the side being the inner surface of the battery case of the plated steel sheet for the battery case, heat treatment is conducted to form a metallic layer, a layer comprising silver or a compound containing silver is formed on the metallic layer to form the plated steel sheet for the battery case, and the battery case is manufactured by working the plated steel sheet for the battery case in a bottomed cylindrical shape. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

  In recent years, portable devices such as audio devices and mobile phones have been used in various fields, and alkaline batteries that are primary batteries, nickel-hydrogen batteries that are secondary batteries, lithium ion batteries, and the like are frequently used as operating power sources. In these batteries, higher output such as higher output and longer life is always required, and battery containers filled with positive electrode and negative electrode active materials are also required to improve performance as important components of the battery. . For example, by dispersing and precipitating fine carbonaceous materials such as graphite and carbon black during nickel plating to be formed on the surface of the steel sheet, irregularities are formed on the surface, and graphite particles having excellent conductivity are exposed on the surface, so that the positive electrode active material The present applicant has proposed a surface-treated steel sheet in which the contact resistance between the battery and the inner surface of the battery container is reduced (see, for example, Patent Documents 1, 2, and 3).

  When these surface-treated steel sheets are formed into a battery container and filled with a positive electrode and a negative electrode active material to form a battery, the contact resistance with the negative electrode active material to be filled is reduced and the discharge characteristics are improved. In addition, it is possible to omit the step of forming a conductive layer by applying a paint mainly composed of graphite on the inner surface of the battery container in order to reduce the contact resistance. When a coating mainly composed of graphite or the like is applied on the plating layer on which the fine carbonaceous material is dispersed and deposited, the battery performance is further improved. However, in applying and drying graphite paint, the solvent is volatilized and adversely affects the environment. Further, an extra painting process is required and the cost is increased. There is a need for a plated steel sheet for battery containers capable of exhibiting performance.

  Prior art documents relating to the present invention include the following.

International Publication No. WO00 / 05437 Pamphlet JP 2002-180296 A JP 2004-076118 A

  The present invention provides a plated steel sheet for a battery container that can be used as 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 a battery container using the same. It aims at providing the used battery.

The plated steel sheet for battery containers of the present invention that solves the above problems is formed by diffusing dispersed nickel and iron in which fine carbonaceous materials are dispersed in the layers in order from the bottom on the steel sheet that is the inner surface of the battery container. A battery comprising: a nickel-iron diffusion layer; a nickel-tin diffusion layer formed by diffusing dispersed nickel and tin in which fine carbonaceous material is dispersed; and a layer made of silver or a silver-containing compound. Nickel-iron diffusion, in which dispersed nickel and iron in which fine carbonaceous materials are dispersed in the layers are diffused in order from the bottom on the plated steel sheet for containers (Claim 1) or on the steel sheet on the battery container inner surface side. A layer, a dispersed nickel layer in which fine carbonaceous material is dispersed in the layer, a nickel-tin diffusion layer in which dispersed nickel and tin in which fine carbonaceous material is dispersed in the layer, and a layer made of silver or a silver-containing compound are formed. Electricity characterized by being The nickel-iron diffusion layer and the dispersed nickel and iron in which fine carbonaceous materials are dispersed are diffused in order from the bottom on the plated steel plate for the pond container (Claim 2), or on the steel plate on the battery container inner surface side. A nickel-iron diffusion layer, a nickel-tin diffusion layer in which dispersed nickel and tin in which fine carbonaceous materials are dispersed in the layer, and a layer made of silver or a silver-containing compound are formed. A plated steel sheet for battery containers (Claim 3), or a nickel-iron diffusion layer, a nickel layer, and dispersed nickel in which fine carbonaceous materials are dispersed in the steel sheet on the side that is to be the inner surface of the battery container. A plated steel sheet for battery containers, comprising a layer, a nickel-tin diffusion layer formed by diffusing dispersed nickel and tin in which fine carbonaceous material is dispersed, and a layer made of silver or a silver-containing compound. (Claim 4)
In the plated steel sheet for a battery container according to the above (Claims 1 to 4), the fine carbonaceous material is carbon black and / or graphite (Claim 5), and the battery according to the above (Claims 1 to 5). In the plated steel sheet for containers, the carbon black and / or graphite is dispersed in an amount of 0.1 to 5% by weight in the nickel-iron diffusion layer, nickel-tin diffusion layer, and dispersed nickel layer ( (6).

And the battery container of this invention is a battery container (Claim 7) formed by processing the plated steel sheet for battery containers of any of the above (Claims 1-6) into a bottomed cylindrical shape,
The battery of the present invention is a battery (invention 8) using the battery container of the above (invention 7).

  In the present invention, a dispersion plating layer in which fine carbonaceous materials are dispersed in the plating layer is formed on the side of the plated steel sheet for the battery container, which is the inner surface of the battery container, and then a heat treatment is performed to form a metal layer. By using a plated steel sheet with a conventional dispersed plating layer formed on the inner surface of the container without applying a paint mainly composed of graphite powder by forming a layer made of silver or a compound containing silver on the container. Furthermore, after being formed into a battery container, discharge characteristics equivalent to or higher than those of a battery using a container having an inner surface coated with graphite can be obtained. In addition, battery life is improved.

  Hereinafter, the present invention will be described in detail. First, the steel plate which is a board | substrate of the plated steel plate for battery containers of this invention is demonstrated. The steel plate used as the substrate is a general-purpose low-carbon aluminum killed steel (carbon content 0.01 to 0.15% by weight) or non-aging ultra-low carbon aluminum killed steel added with niobium or titanium (carbon content 0.01% by weight). Less than). These steels are pickled from a hot-rolled plate to remove scale on the surface, then cold-rolled, and then subjected to electrolytic cleaning, annealing, and temper rolling as a substrate. After cold rolling and electrolytic cleaning, the substrate may be plated without annealing, and then annealed.

  A metal layer is formed on both surfaces of the steel plate, which is the substrate thus obtained, to obtain a plated steel plate for battery containers of the present invention. In general, as a metal layer formed by plating a plated steel sheet for battery containers and then performing diffusion heat treatment, a nickel plated layer, various nickel alloy plated layers, or after forming these plated layers on the steel sheet, heat treatment is performed. There are things that have been given. On the other hand, in the plated steel sheet for battery containers of the present invention, a dispersed nickel plated layer in which fine carbonaceous materials such as graphite and carbon black are dispersed in a nickel plated layer on at least the inner surface side of the battery container is provided on the steel sheet. Then, a tin plating layer is formed thereon, followed by diffusion heat treatment to form a nickel-iron diffusion layer and a nickel-tin diffusion layer in which fine carbonaceous materials are dispersed in the layer, and further nickel-tin It is characterized in that a layer made of silver or a compound containing silver is formed on the diffusion layer. On the outer surface side of the battery container, a normal nickel plating layer, various nickel alloy plating layers, or a layer formed by heat treatment after these plating layers are formed on a steel plate may be provided. A layer to be formed on the inner surface of the battery container may be provided. Usually, in order to reduce the contact resistance with the negative electrode active material to be filled and improve the discharge characteristics on the inner surface of the battery container, a plated layer or the above-mentioned dispersed plating layer is formed on the steel plate, or further heat treatment is performed. A plated steel sheet for a battery container in which a diffusion layer is formed between the steel sheet and these plated layers is formed into a battery container, and a paint mainly composed of graphite is applied on the plated layer on the inner surface of the container. A conductive layer is formed. On the other hand, when the plated steel sheet for a battery container of the present invention is formed into a battery container and filled with a positive electrode and a negative electrode active material to form a battery, a layer made of silver or a compound containing silver on the outermost surface of the container inner surface As a result, the discharge characteristics equal to or better than those obtained when a conventional battery container coated with graphite paint is used can be obtained without applying graphite paint. Therefore, the application and drying steps of this graphite paint can be omitted. When the plated steel sheet for battery containers 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 as in the conventional case, the discharge characteristics are further improved. In addition, a secondary effect of reducing the internal resistance and improving the battery life can be obtained.

  It is preferable that the metal layer formed on the steel plate on the side that is the inner surface of the container on which the layer made of silver or a compound containing silver is formed on the outermost surface is configured as shown below. That is, in order from the bottom from the steel sheet side, (a) a nickel-iron diffusion layer in which fine nickel is dispersed in a layer and nickel-iron diffusion layer, and fine nickel in the layer are dispersed nickel and tin. A nickel-tin diffusion layer formed by diffusion of silver, a layer formed of silver or a silver-containing compound, (b) nickel formed by diffusion of dispersed carbon and fine carbon in the layer and iron -An iron diffusion layer, a dispersed nickel layer in which fine carbonaceous material is dispersed in the layer, a nickel-tin diffusion layer in which dispersed nickel and tin in which fine carbonaceous material is dispersed in the layer are diffused, silver or a silver-containing compound (C) Nickel-iron diffusion layer, nickel-iron diffusion layer in which nickel and iron are dispersed in which fine carbonaceous matter is dispersed in the layer, and fine carbonaceous matter is dispersed in the layer. Ni which is formed by diffusion of dispersed nickel and tin. Kel-tin diffusion layer, layer formed of silver or silver-containing compound, (d) nickel-iron diffusion layer, nickel layer, dispersed nickel layer in which fine carbonaceous material is dispersed, fine in layer A nickel-tin diffusion layer formed by diffusing dispersed nickel and tin in which carbonaceous material is dispersed, or a layer formed of silver or a silver-containing compound is preferably used. It is preferable that the metal layer formed on the steel plate on the side that becomes the outer surface of the battery container is formed with a nickel-iron diffusion layer and a nickel layer in order from the bottom from the steel plate side.

  In order to form the above metal layer, the metal constituting each metal layer is plated on the steel sheet, and then heat treatment is performed to form a diffusion layer. That is, in the case of (a) and (b) above, dispersed nickel plating is applied on a steel plate, tin plating is applied thereon, and then heat treatment is performed. In the case of the above (c) and (d), nickel plating is performed on the steel sheet, dispersed nickel plating is applied thereon, and tin plating is further applied thereon, followed by heat treatment.

  As fine carbonaceous matter dispersed in the dispersion plating layer, it is preferable to use carbon black having an average particle size of 10 to 200 nm. As the carbon black, channel black, thermal black, furnace black, acetylene black, ketjen black, etc. can be used. Ketjen black having an average particle size of 10 to 60 nm or carbon black having an average particle size of 50 to 200 nm can be used. It is preferable to use it. In addition to these extremely fine carbon blacks, graphite particles having an average particle diameter of 1 to 10 μm may be mixed and dispersed during plating. These fine carbonaceous materials are preferably dispersed in an amount of 0.5 to 5% by weight during plating. Since these fine carbonaceous materials are hydrophobic, they are dispersed in the plating solution using a surfactant. By performing electrolytic treatment using a plating solution in which these fine carbonaceous materials are dispersed, a dispersed plating in which these fine carbonaceous materials are dispersed during plating can be obtained.

The abundance of silver in the layer made of a compound containing silver such as silver or silver oxide formed on the outermost surface of the metal layer formed on the battery vessel inner surface side of the steel plate is 0.01 to It is preferable that it is 1.0 g / m < ² >, Preferably it is 0.05-0.5 g / m < ² >. Is less than 0.01 g / ^{m 2} poor effect of improving the discharge characteristics, discharge characteristics more exceed 1.0 g / ^{m 2} is not improved, it is not cost-effective.

  Next, the manufacturing method of the plated steel sheet for battery containers of this invention is demonstrated. Cold-rolled steel sheets of the above-mentioned low carbon aluminum killed steel or extremely low carbon aluminum killed steel are used as substrates, and the above carbon black, channel black, thermal black, furnace black, acetylene black, ketjen black are applied to these substrates during the nickel plating described above. Or a nickel-plated layer formed by dispersing a fine carbonaceous material such as graphite and a tin-plated layer thereon, or the nickel-plated layer and the above-mentioned The dispersed nickel plating layer and a tin plating layer are further formed thereon, and heat treatment is performed. In this way, a nickel-iron diffusion layer and a nickel-tin diffusion layer in which fine carbonaceous matter is dispersed in the layer are formed, or a nickel-iron diffusion layer, or a nickel-iron diffusion layer and a nickel layer thereon are formed. On top of this, a nickel-tin diffusion layer in which fine carbonaceous materials are dispersed in the layer is formed, and then a wet plating method such as a flash plating method, a vapor deposition method, a sputtering method, and an ion plating method are further formed on these metal layers. A layer made of silver or a silver-containing compound is formed using a dry plating method such as. Or after forming a metal layer as mentioned above and then forming the layer which consists of silver or a silver containing compound, it heat-processes again, and the layer which consists of a silver containing compound may be formed in the outermost surface. In addition, or after applying dispersed nickel plating and tin plating, or nickel plating, dispersed nickel plating and tin plating on the substrate as described above, and subsequently forming a layer made of silver or a silver-containing compound thereon A diffusion heat treatment may be performed. The process of forming the above-mentioned plating layer on these steel sheets and performing the annealing treatment includes the case where a cold rolled steel sheet of low carbon aluminum killed steel is used as a plating substrate (hereinafter referred to as “A process”) and the cooling of ultra low carbon aluminum killed steel. It is roughly divided into cases where a rolled steel sheet is used as a plating substrate (hereinafter referred to as B process).

  When manufacturing the plated steel sheet for battery containers by A process, it carries out as follows. In the case of forming a metal layer having the structure (a) or (b) on a steel plate, the low carbon aluminum killed steel is cold-rolled, electrolytically washed in an alkaline aqueous solution, and then subjected to box-type annealing or continuous annealing. After carrying out quality rolling, nickel plating is applied to the battery container outer surface, the above-mentioned dispersed nickel plating and tin plating is applied to the battery container inner surface, and diffusion heat treatment is performed again by the box-type annealing method or the continuous annealing method. Subsequently, silver plating or silver-tin alloy plating is applied only to the side that becomes the inner surface of the battery container. Alternatively, reheating treatment is performed as heat treatment thereafter. Alternatively, dispersed nickel plating and tin plating are performed, and after only silver plating or silver-tin alloy plating is performed only on the inner side of the battery container, diffusion heat treatment is performed. Thus, an alloy layer containing silver is formed on the outermost surface of the metal layer having the structure (a) or (b) on the side that becomes the inner surface of the battery case, and nickel- The plated steel sheet for battery containers of this invention in which the iron diffusion layer and the nickel layer were formed is obtained. When annealing after cold rolling is performed by box annealing, it is preferable to soak for 5 to 20 hours in a temperature range of 640 to 680 ° C, and when performing annealing by continuous annealing, 0.5 ° C is performed at a temperature range of 730 to 800 ° C. It is preferable to soak for -3 minutes. When the diffusion heat treatment after plating is performed by box-type annealing, it is preferable to soak for 5 to 10 hours in a temperature range of 500 to 530 ° C., and when performed by continuous annealing, 0.5 to about 730 to 800 ° C. It is preferable to soak for 3 minutes. The reheating treatment is preferably performed at a temperature range of 400 to 500 ° C. for 0.5 to 3 minutes when the diffusion heat treatment after plating is performed, and at 730 to 800 ° C. when the diffusion heat treatment after plating is not performed. It is preferable to soak for 0.5 to 3 minutes in the temperature range. Whether the metal layer having the configuration (a) or (b) is formed is appropriately selected from the amount of dispersed nickel plating, the amount of tin plating, and annealing conditions and diffusion heat treatment conditions (type, temperature, time).

  In the case of forming a metal layer having the constitution (c) or (d) above on a steel plate, cold rolling of the low carbon aluminum killed steel, electrolytic cleaning in an alkaline aqueous solution, box annealing or continuous annealing, and then adjustment are performed. And then nickel plating on the outer surface of the battery container, nickel plating, dispersion nickel plating and tin plating on the inner surface of the battery container, and diffusion heat treatment by box-type annealing or continuous annealing again. Then, silver plating or silver-tin alloy plating is applied only to the side that is the inner surface of the battery container. Alternatively, reheating treatment is performed as heat treatment thereafter. Alternatively, nickel plating, dispersed nickel plating, and tin plating are performed, and then only the side that becomes the inner surface of the battery container is subjected to silver plating or silver-tin alloy plating, followed by diffusion heat treatment. Thus, an alloy layer containing silver is formed on the outermost surface of the metal layer having the structure (c) or (d) on the side that becomes the inner surface of the battery case, and nickel- The plated steel sheet for battery containers of this invention in which the iron diffusion layer and the nickel layer were formed is obtained. When annealing after cold rolling is performed by box annealing, it is preferable to soak for 5 to 20 hours in a temperature range of 640 to 680 ° C, and when performing annealing by continuous annealing, 0.5 ° C is performed at a temperature range of 730 to 800 ° C. It is preferable to soak for -3 minutes. When the diffusion heat treatment after plating is performed by box-type annealing, it is preferable to soak for 5 to 10 hours in a temperature range of 500 to 530 ° C., and when performed by continuous annealing, 0.5 to about 730 to 800 ° C. It is preferable to soak for 3 minutes. The reheating treatment is preferably performed at a temperature range of 400 to 500 ° C. for 0.5 to 3 minutes when the diffusion heat treatment after plating is performed, and at 730 to 800 ° C. when the diffusion heat treatment after plating is not performed. It is preferable to soak for 0.5 to 3 minutes in the temperature range. (C) or (d), which metal layer is formed, the nickel plating amount, the dispersed nickel plating amount, the tin plating amount, and the annealing conditions and diffusion heat treatment conditions (type, temperature, time) are appropriately selected. To do.

  When manufacturing the plated steel plate for battery containers by B process, it carries out as follows. When a metal layer having the above-described configuration (a) or (b) is provided on a steel plate, the ultra-low carbon aluminum killed steel is subjected to electrolytic cleaning through the same process as described above, and nickel plating is performed on the outer side of the battery container. Then, disperse nickel plating and tin plating are applied to the inner side of the battery container, followed by continuous annealing and then temper rolling. Then, silver plating or silver-tin alloy plating is performed only on the side that becomes the inner surface of the battery container. Alternatively, dispersed nickel plating and tin plating are performed, and then silver plating or silver-tin alloy plating is performed, followed by continuous annealing and then temper rolling. In this way, an alloy layer containing silver is formed on the outermost surface of the metal layer having the structure (a) or (b) on the side that becomes the inner surface of the battery case, and iron- The plated steel sheet for battery containers according to the present invention in which a nickel diffusion layer and a nickel layer are formed is obtained. The continuous annealing is preferably performed at a temperature range of 730 to 800 ° C. for 0.5 to 3 minutes. Whether the metal layer having the configuration (a) or (b) is formed is appropriately selected from the amount of dispersed nickel plating, the amount of tin plating, and annealing conditions and diffusion heat treatment conditions (type, temperature, time).

  When a metal layer having the above-described configuration (c) or (d) is provided on a steel plate, the ultra-low carbon aluminum killed steel is subjected to electrolytic cleaning through the same process as described above, and nickel plating is performed on the side that becomes the outer surface of the battery container. Then, nickel plating, dispersed nickel plating, and tin plating are applied to the side that becomes the inner surface of the battery container, and then continuous annealing is performed, followed by temper rolling. Then, silver plating or silver-tin alloy plating is performed only on the side that becomes the inner surface of the battery container. Alternatively, nickel plating, dispersed nickel plating, and tin plating are performed, and then silver plating or silver-tin alloy plating is performed thereon, followed by continuous annealing, and then temper rolling. Thus, an alloy layer containing silver is formed on the outermost surface of the metal layer having the structure (c) or (d) on the side that becomes the inner surface of the battery case, and iron- The plated steel sheet for battery containers according to the present invention in which a nickel diffusion layer and a nickel layer are formed is obtained. The continuous annealing is preferably performed at a temperature range of 730 to 800 ° C. for 0.5 to 3 minutes. (C) or (d), which metal layer is formed, the nickel plating amount, the dispersed nickel plating amount, the tin plating amount, and the annealing conditions and diffusion heat treatment conditions (type, temperature, time) are appropriately selected. To do.

  The plated steel sheet for battery containers of the present invention is obtained as described above. The battery container of the present invention uses the above-described plated steel sheet for a battery container in combination with a drawing process, a drawing and ironing process (DI process method), a drawing stretch process (DTR process method), or a drawing process and a stretch process. Using a processing method, it is obtained by molding into a bottomed cylindrical shape. As the cylindrical shape, the bottom surface is a circle, an ellipse, or a polygonal shape such as a rectangle or a square, and is molded into a cylindrical shape in which the height of the side wall is appropriately selected according to the application. The battery container thus obtained is filled with a positive electrode, a negative electrode active material, and the like to obtain a battery.

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

[Preparation of plated steel sheet for battery containers]
As the substrate, low carbon aluminum killed steel (I) and extremely low carbon aluminum killed steel (II), whose chemical compositions are shown in Table 1, are used, and low carbon aluminum killed steel (I) is used. In the case of using an ultra-low carbon aluminum killed steel (II), a plated steel plate for a battery container was prepared through the steps shown in 7-10 below. In the following steps 1 to 10, the case of plating on the side that becomes the inner surface of the container is shown, and on the side that becomes the outer surface of the vessel, after annealing in the following steps 1 to 6, In the process, nickel plating is applied after electrolytic cleaning.
1) Cold rolling → Electrolytic cleaning → Annealing (box type or continuous annealing) → Temper rolling → Dispersed nickel plating → Tin plating → Diffusion heat treatment (box type or continuous annealing) → Silver plating or silver-tin alloy plating → Alloy layer formation with silver on the outermost surface 2) Cold rolling → Electrolytic cleaning → Annealing (box type or continuous annealing) → Temper rolling → Dispersed nickel plating → Tin plating → Diffusion heat treatment (box type or continuous annealing) ) → Silver plating or silver-tin alloy plating → Reheating treatment (box type or continuous annealing) → Formation of alloy layer containing silver on the outermost surface 3) Cold rolling → Electrolytic cleaning → Annealing (box type or continuous annealing) → Temper rolling → Dispersed nickel plating → Tin plating → Silver plating or silver-tin alloy plating → Reheating treatment (box type or continuous annealing) → Formation of alloy layer containing silver on the outermost surface 4) Cold rolling → Electrolytic cleaning → annealing (box type or continuous annealing) → temper rolling → nickel plating →
Dispersion nickel plating → tin plating → diffusion heat treatment (box type or continuous annealing) → silver plating or silver-tin alloy plating → formation of alloy layer containing silver on the outermost surface 5) Cold rolling → electrolytic cleaning → annealing (box type) Or continuous annealing) → temper rolling → nickel plating →
Dispersion nickel plating → tin plating → diffusion heat treatment (box type or continuous annealing) → silver plating or silver-tin alloy plating → reheating treatment (box type or continuous annealing) → formation of an alloy layer containing silver on the outermost surface 6 ) Cold rolling → Electrolytic cleaning → Annealing (box type or continuous annealing) → Temper rolling → Nickel plating →
Dispersion nickel plating → tin plating → silver plating or silver-tin alloy plating → reheating treatment (
Box type or continuous annealing) → Formation of alloy layer containing silver on the outermost surface 7) Cold rolling → Electrolytic cleaning → Dispersed nickel plating → Tin plating → Continuous annealing → Temper rolling → Silver plating or silver-tin alloy plating → Formation of alloy layer containing silver on the outermost surface 8) Cold rolling → Electrolytic cleaning → Dispersed nickel plating → Tin plating → Silver plating or silver-tin alloy plating → Continuous annealing → Temper rolling → Formation of alloy layer containing silver on the outermost surface 9) Cold rolling → Electrolytic cleaning → Nickel plating → Dispersed nickel plating → Tin plating → Continuous annealing → Temper rolling → Silver plating or silver-tin alloy plating → Formation of alloy layer containing silver on the outermost surface
10) Cold rolling-> Electrolytic cleaning-> Nickel plating-> Dispersed nickel plating-> Tin plating-> Silver plating or silver-tin alloy plating-> Continuous annealing-> Temper rolling-> Formation of an alloy layer containing silver on the outermost surface

  Nickel plating, dispersed nickel plating, tin plating, silver plating, and silver-tin alloy plating in the steps shown in the above 1 to 10 were performed under the following conditions.

<Nickel plating>
Bath composition Nickel sulfate 300g / L
Nickel chloride 40g / L
Boric acid 30g / L
Pit inhibitor (sodium lauryl sulfate) 0.4mL / L
Anode Nickel pellet (filled in titanium basket, polypropylene anode
(With bag)
Agitation Air agitation pH 4 to 4.6
Bath temperature 55-60 ° C
Current density 20A / dm ²

<Dispersed nickel plating (A)>
Bath composition Nickel sulfate 300g / L
Nickel chloride 40g / L
Boric acid 30g / L
Ketjen black (average particle size 25nm) 1g / L
Sodium benzenesulfonate (dispersant) 5mL / L
Pit inhibitor (sodium lauryl sulfate) 2mL / L
Anode Nickel pellet (filled in titanium basket, polypropylene anode
(With bag)
Agitation Air agitation pH 4 to 4.6
Bath temperature 55-60 ° C
Current density 10A / dm ²

<Dispersed nickel plating (B)>
Bath composition Nickel sulfate 300g / L
Nickel chloride 40g / L
Boric acid 30g / L
Acetylene black (average particle size 120 nm) 1 g / L
Sodium benzenesulfonate (dispersant) 5mL / L
Pit inhibitor (sodium lauryl sulfate) 2mL / L
Anode Nickel pellet (filled in titanium basket, polypropylene anode
(With bag)
Agitation Air agitation pH 4 to 4.6
Bath temperature 55-60 ° C
Current density 10A / dm ²

<Dispersed nickel plating (C)>
Bath composition Nickel sulfate 300g / L
Nickel chloride 40g / L
Boric acid 30g / L
Carbon black (average particle size 180nm) 1g / L
Sodium benzenesulfonate (dispersant) 5mL / L
Pit inhibitor (sodium lauryl sulfate) 2mL / L
Anode Nickel pellet (filled in titanium basket, polypropylene anode
(With bag)
Agitation Air agitation pH 4 to 4.6
Bath temperature 55-60 ° C
Current density 10A / dm ²

<Dispersed nickel plating (D)>
Bath composition Nickel sulfate 300g / L
Nickel chloride 40g / L
Boric acid 30g / L
Carbon black (average particle size 180nm) 1g / L
Graphite (average particle size 1.3μm) 4g / L)
Sodium benzenesulfonate (dispersant) 5mL / L
Pit inhibitor (sodium lauryl sulfate) 2mL / L
Anode Nickel pellet (filled in titanium basket, polypropylene anode
(With bag)
Agitation Air agitation pH 4 to 4.6
Bath temperature 55-60 ° C
Current density 10A / dm ²

<Tin plating>
Bath composition Stannous sulfate 30g / L
Phenolsulfonic acid 60g / L
Ethoxylated α-naphthol 5g / L
Boric acid 30g / L
Anode Tin plate Stirring Plating bath circulation Bath temperature 55-60 ° C
Current density 10A / dm ²

<Silver plating>
Bath composition Silver-containing organic powder (Dyne Silver-NEC) 200g / L
Organic acid (complex salt: Dyne Silver-AGI) 500g / L
Organic additive (Dyne Silver-AGH) 25g / L
Anode Silver plate Agitation Plating bath circulation pH 2.5-3.5
Bath temperature 40-45 ° C
Current density 1A / dm ²

<Silver-tin alloy plating>
Bath composition Silver-tin alloy plating bath (Dipsole TS-3200 (for Sn-3.5wt% Ag eutectic alloy,
Dip Sole Co., Ltd.)
Anode Tin plate Agitation Plating bath circulation Bath temperature 22-45 ° C
Current density 2A / dm ²

  Samples (sample numbers 1 to 10) of the plated steel sheets for battery containers shown in Tables 2 and 3 were prepared as described above. As shown in Tables 4 and 5, for comparison, a sample that does not form a metal layer in which a carbonaceous material is dispersed in the layer (sample numbers 11, 13, and 15) and a sample that does not form silver or a silver-containing compound on the outermost surface ( Sample numbers 12, 14, 16) were prepared. Further, a metal layer in which the carbonaceous material was dispersed in the layer and a sample that did not form silver or a silver-containing compound (conventional product: sample number 17) were also prepared.

[Create battery container]
After punching blanks with a diameter of 57 mm from these samples Nos. 1 to 17, the outer surface of the container was formed by ten-stage drawing so that the side on which only the iron-nickel alloy layer and the nickel layer were provided was the outer surface of the container. It was molded into a cylindrical LR6 type battery (AA battery) container having a height of .8 mm and a height of 49.3 mm.

[Create 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. In addition, some battery containers used what applied the coating material which has graphite powder as a main component on the inner surface. Next, the negative electrode plate spot-welded with the negative electrode current collector rod was attached to the battery container. Next, a separator made of vinylon woven cloth is inserted along the inner periphery of the positive electrode mixture pellet press-inserted into the battery container, and the negative electrode gel made of potassium hydroxide saturated with zinc particles and zinc oxide is added to the battery. The container was filled. Further, an insulating gasket was attached to the negative electrode plate and inserted into the battery container, and then caulking was performed to prepare an alkaline manganese battery.

[Characteristic evaluation]
The characteristics of the batteries prepared using the battery containers prepared from the samples Nos. 1 to 18 as described above were evaluated as follows.

<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, which was defined as a short-circuit current. It shows that a characteristic is so favorable that a short circuit current is large.

<Discharge 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.

<Intermittent discharge characteristics>
As an evaluation of the double-added intermittent discharge, an operation of discharging at 2A for 0.5 seconds and then discharging at 0.25A at 29.5 seconds is defined as one cycle, and this cycle is repeated until the voltage reaches 1.0V. Was measured. It shows that a intermittent discharge characteristic is so favorable that there are many cycles. These characteristic evaluation results are shown in Table 6.

  As shown in Table 6, while using the plated steel sheet for battery containers of the present invention in which a metal layer containing fine carbonaceous matter is formed on the inner side of the battery container and an alloy layer containing silver is formed on the outermost surface In the conventional battery, a plated steel plate for a battery container in which only a metal layer containing fine carbonaceous matter is formed, or a battery in which an alloy layer containing silver is formed on the outermost surface on a metallic layer not containing fine carbonaceous matter. Short circuit current, discharge characteristics, and intermittent discharge characteristics superior to those obtained when using the plated steel sheet for containers were obtained. Moreover, when the graphite paint was applied to the inner surface of the battery container 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.

  A battery using a plated steel sheet for a battery container in which a metal layer containing fine carbonaceous matter is formed on the battery container inner surface side of the present invention and an alloy layer containing a trace amount of silver on the outermost surface is formed. Even if it is used without applying a graphite paint to the inner surface of the container, it exhibits superior short circuit current, discharge characteristics, and intermittent discharge characteristics as compared with the case of using a container with a graphite paint applied to the inner surface of a conventional container. Therefore, it becomes possible to omit the process of applying and drying the graphite paint, and the battery can be manufactured at low cost. In addition, when a graphite paint is applied to the inner surface of a battery container using the plated steel sheet for a battery container of the present invention, the short-circuit current, discharge characteristics, and intermittent discharge characteristics are further improved, so that a high-performance battery can be provided. .

Claims (8)

  A nickel-iron diffusion layer in which dispersed nickel and iron in which fine carbonaceous matter is dispersed in the layer is diffused in order from the bottom on the steel plate on the battery vessel inner surface side of the steel plate, and fine carbonaceous matter is dispersed in the layer. A plated steel sheet for battery containers, comprising a nickel-tin diffusion layer formed by diffusion of dispersed nickel and tin and a layer formed of silver or a silver-containing compound.   A nickel-iron diffusion layer in which dispersed nickel and iron in which fine carbonaceous matter is dispersed in the layer is diffused in order from the bottom on the steel plate on the battery vessel inner surface side of the steel plate, and fine carbonaceous matter is dispersed in the layer. A battery container comprising: a dispersed nickel layer; a nickel-tin diffusion layer formed by diffusing dispersed carbon and tin in which fine carbonaceous material is dispersed; and a layer made of silver or a silver-containing compound. Plated steel sheet.   A nickel-iron diffusion layer, a nickel-iron diffusion layer in which dispersed nickel and iron, in which fine carbonaceous material is dispersed, are diffused in order from the bottom on the steel plate on the side that is the inner surface of the battery container of the steel plate, A plated steel sheet for battery containers, comprising a nickel-tin diffusion layer formed by diffusing dispersed nickel and tin in which fine carbon is dispersed, and a layer made of silver or a silver-containing compound.   In order from the bottom on the steel sheet on the battery container inner surface side of the steel sheet, the nickel-iron diffusion layer, the nickel layer, the dispersed nickel layer in which the fine carbonaceous material is dispersed in the layer, the dispersed nickel in which the fine carbonaceous material is dispersed in the layer, and A plated steel sheet for battery containers, comprising a nickel-tin diffusion layer formed by diffusion of tin and a layer made of silver or a silver-containing compound.   The plated steel sheet for battery containers according to any one of claims 1 to 4, wherein the fine carbonaceous material is carbon black and / or graphite.   2. The carbon black and / or graphite is dispersed in an amount of 0.1 to 5% by weight in the nickel-iron diffusion layer, nickel-tin diffusion layer, and dispersed nickel layer. The plated steel sheet for battery containers as described in any one of -5.   The battery container formed by shape | molding the plated steel plate for battery containers of any one of Claims 1-6 in a bottomed cylindrical shape.   A battery comprising the battery container according to claim 5.