JP2006283185A - Plated steel sheet for battery vessel, battery vessel using the plated steel sheet for battery vessel, and battery using the battery vessel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plated steel sheet for a battery vessel which allows a battery to have excellent battery properties, to provide a battery vessel using the plated steel sheet for a battery vessel, and to provide a battery using the battery vessel. <P>SOLUTION: A plated steel sheet is obtained by applying bismuth plating to the side to form into the inside surface of a battery vessel in the steel sheet, and next applying silver plating to the surface thereof; alternatively, a plated steel sheet is obtained by applying nickel plating to the surface thereof, next applying bismuth plating to the surface thereof, and successively applying silver plating to the surface thereof; alternatively, a steel sheet is obtained by applying nickel plating to the surface thereof, thereafter performing heat treatment, next applying bismuth plating to the surface thereof, and successively applying silver plating to the surface thereof; alternatively, a plated steel sheet is obtained by applying nickel plating, next applying bismuth plating to the surface thereof, thereafter performing heat treatment, and successively applying silver plating to the surface thereof, so as to be the plated steel sheet for a battery vessel, and the same is subjected to forming into a battery vessel, and is applied to a battery. <P>COPYRIGHT: (C)2007,JPO&INPIT

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, along with the development of portable AV equipment and mobile phones such as digital cameras, CDs, MD players, liquid crystal televisions, game machines, etc., alkaline batteries as primary batteries, nickel-metal hydride batteries as secondary batteries, lithium as operating power sources for heavy loads Ion batteries are often used. In these batteries, there is a constant demand for higher performance such as higher output and longer life, and battery containers filled with positive and negative electrode active materials are also required to have improved performance as important components of the battery. ing. For example, in the case of an alkaline battery, a surface-treated steel sheet for a battery container in which a nickel-phosphorus alloy layer is formed on the inner surface of the battery case in order to improve the corrosion resistance against an alkaline solution that is an electrolytic solution for the purpose of extending the life ( Patent Document 1) has been proposed.

  In addition, in order to prevent the high capacity of the battery and the deterioration of heavy load characteristics after storage, a nickel-silver alloy plating layer or a nickel-chromium alloy plating layer is formed on the rolled steel plate material on the surface that becomes the inner surface of the can, Press squeezing and ironing to create fine cracks to form an uneven surface, increase the contact area with the positive electrode mixture and conductive coating (Patent Document 2), nickel plating After forming a layer and forming a silver plating layer thereon, heat treatment is carried out to form a nickel-silver plating layer, thereby consolidating the crystals of the plating to increase the hardness and further increasing the spacing between cracks. Thus, a battery can (Patent Document 3) has been proposed in which the contact area with the positive electrode mixture or the conductive coating is further increased to reduce the internal resistance of the battery.

  However, since the nickel-phosphorus alloy layer directly formed on the steel plate surface used for the battery container inner surface is hard and brittle, when forming into a container by drawing or drawing ironing, the underlying steel is exposed and electrolyzed. There is a possibility that the corrosion resistance to the alkaline solution which is a liquid may be lowered. Similarly, in the battery cans described in Patent Document 2 and Patent Document 3, if a fine crack is generated by press drawing, the steel base may be exposed and the corrosion resistance against the alkaline solution used for the electrolyte may be reduced. is there.

Prior art document information relating to the present application includes the following.
International Publication No. WO99 / 03161 JP-A-11-102671 JP 2001-325924 A

  In the present invention, when the battery container is pressed by drawing or squeezing and ironing, micro cracks are generated in the steel substrate on the inner surface of the battery container, and the adhesion to the positive electrode mixture of the alkaline battery Contact resistance is improved, and a plated steel sheet for a battery container that can sufficiently exhibit excellent battery performance after long-term storage, a battery container using the plated steel sheet for the battery container, and a battery using the battery container The purpose is to provide.

In order to achieve the object of the present invention, the plated steel sheet for a battery container according to the present invention is characterized in that a bismuth layer and a silver layer are formed in order from the bottom on the steel sheet on the side that is the inner surface of the battery container. A plated battery for a battery container (Claim 1), or a nickel container, a bismuth layer, and a silver layer formed in this order from the bottom on the steel sheet on the side that is the battery container inner surface of the steel sheet. An iron-nickel alloy layer, a nickel layer, a bismuth layer, and a silver layer are formed in order from the bottom on a steel plate (Claim 2), or a steel plate on the side that is the inner surface of the battery case. Plated steel sheet (Claim 3),
An iron-nickel alloy layer, a bismuth layer, and a silver layer are formed in order from the bottom on the steel plate that is the inner surface of the battery case of the steel plate (Claim 4), or steel plate An iron-nickel alloy layer, a nickel layer, a nickel-bismuth alloy layer, and a silver layer are formed in order from the bottom on the steel plate on the side that is the inner surface of the battery case. 5), or a plated steel sheet for battery containers, wherein an iron-nickel alloy layer, a nickel-bismuth alloy layer, and a silver layer are formed in order from the bottom on the steel sheet on the side that is the battery container inner surface of the steel sheet ( 6. A battery container comprising an iron-nickel alloy layer, an iron-nickel-bismuth alloy layer, and a silver layer formed in this order from the bottom on the steel sheet on the side that is the battery container inner surface of the steel sheet. Plated steel sheet ( Claim 6), or a plated steel sheet for battery containers, wherein an iron-nickel-bismuth alloy layer and a silver layer are formed in order from the bottom on the steel sheet on the side of the inner surface of the battery container. 8), or an iron-nickel alloy layer, a nickel layer, a bismuth layer, and a bismuth-silver alloy layer are formed in order from the bottom on the steel plate that is the inner surface of the battery case. An iron-nickel alloy layer, a nickel-bismuth alloy layer, and a nickel-bismuth-silver alloy layer are formed in order from the bottom on the plated steel plate (Claim 9) or on the steel plate on the side that is the battery container inner surface of the steel plate. An iron-nickel alloy layer, an iron-nickel-bismuth alloy layer, nickel-bisma on a plated steel plate for a battery container (Claim 10), or a steel plate on the side that is to be the battery container inner surface of the steel plate in order from the bottom. A silver alloy layer is formed, and a plated steel sheet for battery containers (Claim 11), or a steel sheet on the side of the steel sheet that is to be the battery container inner surface, in order from the bottom, an iron-nickel alloy layer and a nickel layer A nickel-bismuth alloy layer or a bismuth-silver alloy layer is formed on any one of the plated steel sheets for battery containers (claim 12).

  The battery container of the present invention is a battery container (Claim 13) formed by forming the plated steel sheet for a battery container according to any of the above (Claims 1 to 12) into a bottomed cylindrical shape. And the battery of this invention is a battery (Claim 14) using the battery container of said (Claim 13).

  The plated steel sheet for battery containers of the present invention is a plated steel sheet formed by applying bismuth plating on the side of the steel sheet that is the inner surface of the battery container, and then silver-plated thereon, or nickel plated, and then bismuth plated thereon. And then a plated steel sheet with silver plating on it, or further with nickel plating, followed by heat treatment, then bismuth plating on it, and then further silver plating on it. After applying a plated steel sheet or nickel plating, and then applying bismuth plating thereon, heat treatment is performed, and subsequently, a plated steel sheet or silver plating is further applied thereon, followed by nickel plating, Bismuth plating is applied on it, followed by further silver plating on it, followed by heat treatment. With plated steel sheet comprising, either plated steel sheet, it is possible to obtain a battery container plated steel sheet according to the claims 1-12. Moreover, it becomes possible to provide the battery excellent in the discharge performance after a battery preservation | save by using the battery container formed by shape | molding the plated steel plate for battery containers.

  The bismuth layer or bismuth alloy layer formed on the battery container inner surface of the plated steel sheet for battery containers of the present invention is hard and brittle, so that when the battery container is molded, minute cracks are generated on the inner surface of the battery container. In addition, the adhesion when contacting the positive electrode mixture directly or through the conductive material applied to the inner surface of the battery container is improved, and deterioration of the contact resistance after storage is suppressed, and it is caused by micro cracks. The contact resistance is reduced by the small unevenness and the heavy load discharge performance is improved. In addition, it is possible to further improve the conductivity by flash-coating silver on the bismuth layer or by performing heat treatment after the flash coating. Also, when forming into a battery container, the powder surface is resistant to powdering. It is also possible to improve the performance.

  The contents of the present invention will be described below. As a steel plate used as a substrate for the plated steel plate for battery containers of the present invention, general-purpose low carbon aluminum killed steel (carbon content 0.01 to 0.15 wt%), or non-aging ultra-low carbon added with niobium or titanium. Aluminum killed steel (carbon content less than 0.01% by weight) is used. These steel hot-rolled plates are pickled to remove surface scales, then cold-rolled by a conventional method, and then subjected to electrolytic cleaning, annealing, and temper rolling as a substrate. Alternatively, an unannealed material that has been cold-rolled and then subjected to electrolytic cleaning can be used as a substrate. In this case, after the plating treatment, the diffusion heat treatment of the plating layer that also serves as the annealing of the steel substrate is performed by one heat treatment.

First, nickel plating is performed on one surface, which is the outer surface of a battery container of a steel plate as a substrate. For nickel plating, it is preferable to use a matte bath or a semi-gloss bath containing an organic additive. When a bright bath containing a brightener containing a sulfur component is used, the heat treatment after plating causes embrittlement of the coating film due to the sulfur component, which is not preferable. The plating thickness of the nickel plating is preferably a coating amount of 4.5 to 30 g / m ² . When the nickel plating thickness is 4.5 g / m ² , the corrosion resistance on the outer surface of the battery container is not sufficient, and when it exceeds 30 g / m ² , the corrosion resistance reaches saturation, which is uneconomical.

Next, one side which is the inner surface of the battery container of the battery container is subjected to bismuth plating on the steel plate directly or after nickel plating. Bismuth plating dissolves easily in high-concentration potassium hydroxide aqueous solution, which is an electrolytic solution, but bismuth is an electrochemically noble metal, and manganese dioxide, which is a positive electrode active material, coexists with manganese dioxide rather than bismuth. The inventors found that the bismuth of the plating film formed on the steel sheet did not dissolve and did not cause gas generation, which is an important factor harmful to the battery configuration, through experiments. . It is preferred bismuth plating is film of 0.5 to 10 g / ^{m 2.} When the coating amount is less than 0.5 g / m ^2, the depth of micro cracks generated when the battery container is molded is reduced, and the effect of improving battery performance is poor. On the other hand, when the coating amount exceeds 10 g / m ² , the crack is small. The depth of the crack becomes too large, the crack reaches the steel substrate, the steel substrate is excessively exposed, iron oxide is generated, the coloring resistance increases, and the risk of gas generation also increases.

Since the bismuth layer or bismuth alloy layer is hard and brittle, nickel plating is used as the lower layer of these layers in order to prevent the microcracks that occur when forming into the battery container from reaching the steel substrate and exposing the steel substrate. It may be applied to form a nickel layer or an iron-nickel alloy layer. The nickel plating preferably has a coating amount of ^{2 to} 25 g / m ² . When the coating amount is less than 2 g / m ^{2, the} effect of suppressing the exposure of the steel substrate becomes poor. On the other hand, when the amount of coating exceeds 25 g / m ² , the effect of suppressing the exposure of the steel substrate is saturated and economically undesirable.

In this invention, it can be set as the outstanding battery formation material by providing either a silver layer, a bismuth-silver alloy layer, or a nickel-bismuth-silver alloy layer in the outermost surface by the side which becomes a battery container inner surface. . By providing a silver layer or a layer containing these silvers, smut generation of the bismuth plating layer and powdering when forming into the battery container are suppressed, conductivity is improved, and when forming into the battery container. In addition, a finer crack is generated in the bismuth layer or the layer containing bismuth to improve the adhesion between the inner surface of the battery container and the positive electrode mixture, thereby providing a more excellent battery material. For the silver plating, either a cyan bath or a non-cyan bath can be used. In the present invention, it is preferable to use a non-cyan bath silver plating bath from the viewpoint of toxicity. As the coating amount of silver plating, it is possible to bring about good electrical conductivity and low gas generation with an amount of about flash coating, preferably 0.05 to 0.5 g / m ² (thickness is 0). 0.005 to 0.05 μm). Is less than 0.05 g / m ² is insufficient effect on battery performance, the effect exceeds 0.5 g / m ² along with reaches saturation, the silver is uneconomical because it is expensive. The bismuth-silver alloy layer or the nickel-bismuth-silver alloy layer can be formed by plating bismuth or nickel and bismuth on the steel plate substrate, followed by heat treatment as shown below.

  When heat treatment is performed after plating, diffusion heat treatment is performed using either a box-type annealing method or a continuous annealing method. The film is cured by converting nickel and bismuth into a nickel-bismuth alloy by heat treatment. The heat treatment is accompanied by the formation of iron-nickel alloy, iron-nickel-bismuth alloy, bismuth-silver alloy, nickel-bismuth-silver alloy, etc., recrystallization softening of the nickel plating layer below the bismuth plating layer, and nickel The condition is such that a part or all of the plating layer is converted into an iron-nickel diffusion layer (alloy layer). That is, when the box-type annealing method is used, heating at less than 450 ° C. does not soften the nickel plating layer, and at the same time, no iron-nickel diffusion layer (alloy layer) is formed. On the other hand, when heated at a temperature exceeding 700 ° C., the iron-nickel diffusion layer (alloy layer) is sufficiently formed, but the steel substrate becomes too soft. The nickel plating layer becomes soft. For this reason, the heat treatment temperature is 450 to 650 ° C, preferably 500 to 600 ° C. The heating time is preferably soaking for 1 to 6 hours in the above temperature range. When using a continuous annealing method, it is preferable to set it as the heating time of 1 to 5 minutes at the heating temperature of 600-850 degreeC. When bismuth plating or nickel plating is applied on top of bismuth plating and subsequently heat treatment, or when further heat treatment is performed after silver plating, the thickness and heat treatment conditions of each plating layer are controlled. The plated steel sheet for battery containers provided with the cross-sectional structure of 2-7 and FIGS. 8-12 is obtained. 1 to 12 show the upper layer structure from the steel substrate on the side that is the inner surface of the battery case. The layer structure on the side corresponding to the outer surface of the battery container includes a nickel layer on the steel base, an iron nickel diffusion layer (alloy layer) on the steel base, or an iron nickel diffusion layer (alloy layer) on the steel base and its A nickel layer is formed on top.

  In these plated steel sheets, when heat treatment is performed after plating, the steel sheet is usually temper-rolled at a rolling rate of 1.0 to 1.5% to obtain the plated steel sheet for battery containers of the present invention. If the stretcher strain generated during the process does not hinder, temper rolling can be omitted. In addition, it may replace with the plating layer only of nickel plating on the single side | surface used as the outer surface of the battery container of a steel plate, and may form each plating layer similar to the above given to the other one side used as the inner surface of a battery container.

  The battery container of the present invention is obtained by subjecting the above-described plated steel sheet for a battery container to a drawing process, a drawing ironing process (DI processing method), a drawing stretch processing method (DTR processing method), or a drawing process as a stretching process. It is obtained by forming into a bottomed cylindrical shape using the processing method used in combination. 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 with the side wall height appropriately selected according to the application. The battery container thus obtained is filled with a positive electrode mixture, 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.
[Creation of plated steel sheets for battery containers]
As the plating substrate, hot-rolled low carbon aluminum killed steel (I) or extremely low carbon aluminum killed steel (II) whose chemical composition is shown in Table 1 is used, and the battery container is subjected to the steps shown in the following a) to f). A plated steel sheet was created.
B) Low carbon aluminum killed steel (I) → Cold rolling → Electrolytic cleaning → Annealing (box annealing or continuous annealing) → Temper rolling → Nickel plating (outside) → Bismuth plating → Silver plating b) Low carbon aluminum killed steel ( I) → Cold rolling one electrolytic cleaning → Annealing (box annealing or continuous annealing) → Tempered rolling → Nickel plating → Bismuth plating → Silver plating c) Low carbon aluminum killed steel (I) → Cold rolling one electrolytic cleaning → Annealing (Box annealing or continuous annealing) → Temper rolling → Nickel plating → Diffusion heat treatment (Box annealing or continuous annealing) → Temper rolling → Bismuth plating → Silver plating d) Low carbon aluminum killed steel (I) → Cold rolling Electrolytic cleaning → annealing (box annealing or continuous annealing) → temper rolling → nickel plating → bismuth → diffusion heat treatment (box annealing or continuous annealing) → temper rolling → silver plating e) Low carbon aluminum killed steel (I ) → Cold rolling → Electrolytic cleaning → Annealing (box annealing or continuous annealing) → Temperature rolling → Nickel plating → Bismuth plating → Silver plating → Heat treatment (box annealing or continuous annealing) → Temperature rolling) Aluminum killed steel (II)-> cold rolling-> electrolytic cleaning-> nickel plating-> bismuth plating-> silver plating-> heat treatment (box annealing or continuous annealing)-> temper rolling Note that the nickel plating in the process becomes the outer surface of the substrate container The nickel plating in steps (b) to (f) was performed on both sides of the substrate, and the bismuth plating and silver plating were applied only on one side serving as the inner surface of the container of the substrate.

After hot rolling plate of the above steel grade I or II is subjected to cold rolling and electrolytic cleaning by a conventional method to form a cold rolled plate having a thickness of 0.25 mm, in the case of steel grade I, box annealing In a furnace, annealing was performed at a soaking temperature of 640 to 680 ° C. for 8 hours, and in the case of steel type II, annealing was performed in a continuous annealing furnace at a heating temperature of 780 ° C. and a heating time of 2 minutes. Next, bismuth plating, nickel plating, and silver plating were performed under the following conditions.
<Bismuth plating>
Bath composition LMP-bismuth (Okuno Pharmaceutical Co., Ltd.) 200g / L
LMP-acid bismuth (Okuno Pharmaceutical Co., Ltd.) 100g / L
LMP-SG (Okuno Pharmaceutical Co., Ltd.) 10g / L
Anode Bismuth plate Agitation Plating bath circulation pH 0.3-1.5
Bath temperature 35-45 ° C
Current density 5A / dm ²

<Nickel plating>
Bath composition Nickel sulfate 300g / L
Nickel chloride 40g / L
Boric acid 40g / L
Pit inhibitor (sodium lauryl sulfate) 0.4mL / L
Anode Nickel Pellet (Titanium basket filled with S pellets from INCO Corporation and equipped with polypropylene anode bag)
Stirring air stirring
pH 4 to 4.6
Bath temperature 55-60 ° C
Current density 15A / dm ²

<Silver plating>
Bath composition Silver-containing organic acid salt (Dyne Silver NEC (manufactured by Daiwa Kasei Laboratories))
200g / L
Organic acid (complex salt) (Dyne Silver AGI (manufactured by Daiwa Kasei Laboratories)) 500 g / L
Organic additive (smoothing agent) (Dyne Silver AGH (manufactured by Daiwa Kasei Laboratories))
25g / L
Anode Silver plate Stirring Circulation of plating bath Bath temperature 35-40 ° C
Current density 1A / dm ²

  In the processes shown in the above a) to f), when a thermal diffusion treatment is performed after plating, or when a box-type annealing method is used, a soaking temperature of 500 to 650 ° C. in a nitrogen-hydrogen protective gas atmosphere is set. Heat treatment was performed for 6 to 8 hours. When the continuous annealing method was used, heat treatment was performed at a heating temperature of 650 ° C. and a heating time of 2 minutes in a nitrogen-hydrogen protective gas atmosphere. Further, when the diffusion heat treatment of the plating layer that also serves as the annealing of the steel substrate after the plating is performed by a single heat treatment, the heat treatment was performed at a heating temperature of 800 ° C. and a heating time of 2 to 3 minutes using a continuous annealing method.

As described above, samples (sample numbers 1 to 12) of plated steel sheets for battery containers shown in Table 2 were prepared. Further, a sample (Sample No. 13) that has been subjected to nickel plating for comparison using the low carbon aluminum killed steel (I), a sample that has been subjected to thermal diffusion treatment after the nickel plating (Sample No. 14), and after the nickel plating has been performed A sample (sample No. 15) subjected to nickel-phosphorus alloy plating, and a sample (sample) subjected to heat treatment after nickel-phosphorus alloy plating was applied following nickel plating using ultra low carbon aluminum killed steel (II) Number 16) was created. Nickel-phosphorus alloy plating was performed under the following conditions. Table 3 shows the layer structure on the steel substrate.
<Nickel-phosphorus alloy plating>
Bath composition Nickel sulfate 300g / L
Nickel chloride 45g / L
Boric acid 40g / L
Phosphorous acid 10g / L
Anode Nickel Pellet (Titanium basket filled with S pellets from INCO Corporation and equipped with polypropylene anode bag)
Stirring air stirring
pH 1.5-2.0
Bath temperature 55-60 ° C
Current density 10A / dm ²

[Create battery container]
After punching blanks with a diameter of 57 mm from the samples of Sample Nos. 1 to 16, an outer diameter of 13 was obtained 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 size battery) container having a height of 4 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, this positive electrode mixture was pressed in a mold to form a donut-shaped positive electrode mixture beret having a predetermined size, and was press-inserted into a battery container having a conductive material mainly composed of graphite powder applied to 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 fabric is inserted along the inner periphery of the positive electrode mixture beret pressure-inserted into the battery container, and a negative electrode gel made of potassium hydroxide saturated with zinc particles and zinc oxide is inserted into the battery container. Filled in. Further, an insulating gasket was attached to the negative electrode plate and inserted into the battery container, followed by caulking 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 16 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 at 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. A high number of cycles indicates that the intermittent discharge characteristics are good. These evaluation results are shown in Table 4.
As shown in Table 4, the plated steel sheet for battery containers of the present invention has a short circuit current compared to a plated steel sheet for battery containers that does not form a nickel-bismuth alloy layer and a plated steel sheet for battery containers that does not form a silver layer on the surface. It excels in both discharge characteristics and intermittent discharge characteristics. Moreover, when the graphite paint was applied to the inner surface of the battery container using the plated steel sheet for the battery container of the present invention, the short circuit current, the discharge characteristics, and the intermittent discharge characteristics were further improved.

  A bismuth layer and a silver layer are formed on the steel plate, or an iron-nickel alloy layer or / and a nickel layer are formed on the steel plate, and a bismuth layer and a silver layer are further formed thereon. Or an iron-nickel alloy layer or an iron-nickel alloy layer and a nickel layer on a steel plate, a nickel-bismuth alloy layer thereon and a silver layer thereon, or an iron on the steel plate A nickel alloy layer and an iron-nickel-bismuth alloy layer formed thereon or not formed, and a silver layer formed thereon, or an iron-nickel alloy layer and its A nickel-bismuth alloy layer or iron-nickel-bismuth alloy layer is formed thereon, and a nickel-bismuth-silver alloy layer is further formed thereon. The plated steel sheet for battery containers according to the present invention is formed by forming a layer and a nickel layer thereon, forming a bismuth layer or a nickel-bismuth alloy layer thereon, and forming a bismuth-silver alloy layer thereon. In addition, the plating layer does not peel or crack when it is formed into a container by drawing or ironing, and the surface has excellent alkali resistance and electrical conductivity. It can be suitably applied as a container for a high-performance battery excellent in the above and a high-performance battery. In addition, since the battery characteristics are superior to those of conventional containers with graphite paint applied to the inner surface of the container, it is possible to omit the step of applying and drying the graphite paint, which makes it possible to manufacture high performance batteries at low cost. it can.

Sectional drawing which shows an example of an upper layer structure from the steel base of the side used as the battery container inner surface of the plated steel plate for batteries of this invention. Sectional drawing which shows another example of an upper layer structure from the steel base of the side used as the battery container inner surface of the plated steel plate for batteries of this invention. Sectional drawing which shows another example of an upper layer structure from the steel base of the side used as the battery container inner surface of the plated steel plate for batteries of this invention. Sectional drawing which shows another example of an upper layer structure from the steel base of the side used as the battery container inner surface of the plated steel plate for batteries of this invention. Sectional drawing which shows another example of an upper layer structure from the steel base of the side used as the battery container inner surface of the plated steel plate for batteries of this invention. Sectional drawing which shows another example of an upper layer structure from the steel base of the side used as the battery container inner surface of the plated steel plate for batteries of this invention. Sectional drawing which shows another example of an upper layer structure from the steel base of the side used as the battery container inner surface of the plated steel plate for batteries of this invention. Sectional drawing which shows another example of an upper layer structure from the steel base of the side used as the battery container inner surface of the plated steel plate for batteries of this invention. Sectional drawing which shows another example of an upper layer structure from the steel base of the side used as the battery container inner surface of the plated steel plate for batteries of this invention. Sectional drawing which shows another example of a layer structure above from the steel base of the side used as the battery container inner surface of the plated steel plate for batteries of this invention. Sectional drawing which shows another example of a layer structure above from the steel base of the side used as the battery container inner surface of the plated steel plate for batteries of this invention. Sectional drawing which shows another example of a layer structure above from the steel base of the side used as the battery container inner surface of the plated steel plate for batteries of this invention.

Claims (14)

A plated steel sheet for a battery container, wherein a bismuth layer and a silver layer are formed in order from the bottom on the steel sheet on the side of the steel container that is the inner surface of the battery container. A plated steel sheet for a battery container, wherein a nickel layer, a bismuth layer, and a silver layer are formed in order from the bottom on the steel sheet on the side that is the inner surface of the battery container. An iron-nickel alloy layer, a nickel layer, a bismuth layer, and a silver layer are formed in order from the bottom on a steel plate that is the inner surface of the battery case of the steel plate. An iron-nickel alloy layer, a bismuth layer, and a silver layer are formed in order from the bottom on a steel plate that is the inner surface of the battery case of the steel plate. An iron-nickel alloy layer, a nickel layer, a nickel-bismuth alloy layer, and a silver layer are formed in order from the bottom on a steel plate that is the inner surface of the battery case of the steel plate. An iron-nickel alloy layer, a nickel-bismuth alloy layer, and a silver layer are formed in order from the bottom on a steel plate on the side that is the inner surface of the battery case of the steel plate. An iron-nickel alloy layer, an iron-nickel-bismuth alloy layer, and a silver layer are formed in this order from the bottom on a steel plate on the side that is the inner surface of the battery case. An iron-nickel-bismuth alloy layer and a silver layer are formed in order from the bottom on a steel plate on the side of the steel plate that becomes the inner surface of the battery case. An iron-nickel alloy layer, a nickel layer, a bismuth layer, and a bismuth-silver alloy layer are formed in order from the bottom on a steel plate on the side that is the inner surface of the battery case of the steel plate. An iron-nickel alloy layer, a nickel-bismuth alloy layer, and a nickel-bismuth-silver alloy layer are formed in order from the bottom on a steel plate on the side that is the inner surface of the battery case of the steel plate. . An iron-nickel alloy layer, an iron-nickel-bismuth alloy layer, and a nickel-bismuth-silver alloy layer are formed in order from the bottom on the steel plate on the side that is the inner surface of the battery case of the steel plate. Plated steel sheet. An iron-nickel alloy layer, a nickel layer, a nickel-bismuth alloy layer, and a bismuth-silver alloy layer are formed in order from the bottom on a steel plate on the side that is the inner surface of the battery case of the steel plate. steel sheet. The battery container formed by shape | molding the plated steel plate for battery containers in any one of Claims 1-12 in a bottomed cylindrical shape. A battery comprising the battery container according to claim 13.

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