JP2006093094A - Plated steel sheet for battery container, battery container using same, and battery using battery container - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plated steel sheet for a battery container capable of forming a battery having excellent battery characteristics by forming minute cracks when forming it into a battery container by applying squeezing work and drawing work, and by enhancing adhesiveness to a positive electrode mixture of an alkaline battery, and to provide a battery container using the plated steel sheet for a battery container, and a battery using its battery container. <P>SOLUTION: The plated steel sheet for a battery container is formed by applying nickel plating to a side to be the inner face of the battery container of the steel sheet, subsequently applying tin plating on it, and applying diffusion heat treatment after applying silver plating on the above; or, by applying a nickel plating, and applying diffusion treatment after applying a silver particle dispersed tin plating on the above; forming an iron-nickel alloy layer on the above steel plate, and forming a nickel layer and/or an iron-nickel-tin alloy layer and/or a nickel-tin alloy layer on the above; and furthermore forming a nickel-tin-silver alloy layer or/and a silver layer on the above. The above plated steel plate is formed into a battery container and applied to the battery. <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, 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, for the purpose of extending the life, a surface-treated steel sheet for a battery case in which a nickel-phosphorus alloy layer is formed on the inner surface side of the battery case in order to improve the corrosion resistance against the alkaline solution used in the electrolyte (patent Document 1) has been proposed.

  However, since the nickel-phosphorus alloy layer directly formed on the steel plate surface used for the battery container inner surface is very hard and brittle, the base steel is formed when the container is formed by press processing such as drawing or ironing. As a result, the corrosion resistance of the alkaline solution used in the electrolytic solution is reduced, and the discharge characteristics may be deteriorated or gas generation may be increased.

Prior art document information relating to the present application includes the following.
International Publication WO99 / 03161 Pamphlet

  In the present invention, when forming into a container by drawing or squeezing and ironing, the plating layer is not peeled off or cracks reaching the base steel are generated, and it has excellent corrosion resistance against alkaline solutions and excellent battery characteristics. It is an object of the present invention to provide 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 order to achieve the object of the present invention, a plated steel sheet for a battery container of the present invention is an iron-nickel alloy layer, a nickel layer, a nickel-tin alloy layer, A nickel-tin-silver alloy layer and a silver layer are formed on the plated steel sheet for battery containers (Claim 1), or on the steel sheet on the side that becomes the battery container inner surface of the steel sheet in order from the bottom. A plated steel sheet for battery containers, wherein a nickel alloy layer, a nickel-tin alloy layer, a nickel-tin-silver alloy layer, and a silver layer are formed (Claim 2), or the side of the steel sheet that is the inner surface of the battery container An iron-nickel alloy layer, an iron-nickel-tin alloy layer, a nickel-tin alloy layer, a nickel-tin-silver alloy layer, and a silver layer are formed on the steel plate in order from the bottom. Plated steel sheet (Claim 3), or steel sheet An iron-nickel alloy layer, a nickel layer, a nickel-tin alloy layer, and a nickel-tin-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. An iron-nickel alloy layer, an iron-nickel-tin alloy layer, a nickel-tin alloy layer, nickel-tin-silver, in order from the bottom on the plated steel plate (Claim 4), or the steel plate on the side of the battery container that is the inner surface of the battery container An alloy layer is formed, and a plated steel sheet for battery containers (Claim 5), or an iron-nickel alloy layer and a nickel-tin alloy in order from the bottom on the steel sheet on the side that is the battery container inner surface of the steel sheet Layer, a nickel-tin-silver alloy layer formed on a plated steel sheet for battery containers (Claim 6), or a steel sheet on the side that becomes the battery container inner surface of the steel sheet, in order from the bottom, iron-nickel Alloy layer, nickel layer, nickel A tin-alloy layer and a silver layer are formed, and a plated steel sheet for battery containers (Claim 7), or an iron-nickel alloy layer in order from the bottom on the steel sheet on the side that becomes the battery container inner surface of the steel sheet A nickel-tin alloy layer and a silver layer are formed on the plated steel sheet for battery containers (Claim 8), or on the steel sheet on the side that is the inner surface of the battery container. An alloy layer, an iron-nickel-tin alloy layer, a nickel-tin alloy layer, or a silver layer is formed on any one of the plated steel sheets for battery containers (claim 9).

The battery container of the present invention is a battery container (Claim 10) obtained by forming the plated steel sheet for a battery container according to any one of the above (Claims 1 to 9) into a bottomed cylindrical shape.
And the battery of this invention is a battery (Claim 11) using the battery container of said (Claim 10).
Further, the method for producing a plated steel sheet for battery containers according to the present invention comprises applying a nickel plating to at least the side of the steel sheet that is the inner surface of the battery container, and then performing a heat treatment after the silver particle-dispersed tin plating is performed. An iron-nickel alloy layer is formed on the steel substrate on the side to be formed, a nickel layer or an iron-nickel-tin alloy layer is formed thereon, and a nickel-tin alloy layer is further formed thereon. Alternatively, a nickel-tin-silver alloy layer and / or a silver layer is formed on an iron-nickel alloy layer formed on a steel substrate (claim). 12).

  The plated steel sheet for battery containers of the present invention is obtained by subjecting the steel sheet to the inner surface of the battery container with nickel plating, then tin plating thereon, further silver plating thereon, and then diffusion heat treatment or nickel After performing plating, and then applying silver particle-dispersed tin plating thereon followed by diffusion heat treatment, an iron-nickel alloy layer on the steel sheet, a nickel layer or / and an iron-nickel-tin alloy layer or / and A nickel-tin alloy layer is formed, and a nickel-tin-silver alloy layer and / or a silver layer is further formed thereon. This plated steel sheet for battery containers has an excellent iron-nickel alloy layer formed immediately above the steel sheet, and is excellent in adhesion to the iron-nickel-tin alloy layer and nickel-tin alloy layer formed thereon. Therefore, even when microcracks occur on the surface of the hard and brittle iron-nickel-tin alloy layer or nickel-tin alloy layer when forming into a battery container, the crack does not reach the surface of the underlying steel plate, The steel sheet surface is not attacked by the alkaline electrolyte. In addition, since a silver layer rich in conductivity and spreadability is formed on the iron-nickel-tin alloy layer or the nickel-tin alloy layer in which micro cracks are generated on the surface, nickel-tin in an alkaline electrolyte Suppresses the deterioration of contact resistance due to the passive film formed on the surface of the alloy layer, and has excellent battery characteristics due to the synergistic effect of adhesion with the positive electrode mixture due to microcracks and the silver layer being a conductive film It can be suitably applied as a battery container material. At the same time, the hydrogen layer generated by the electrochemical reaction with the alkaline electrolyte is converted into water by the silver layer formed on the outermost surface, so that the internal pressure of the battery is less likely to increase. Furthermore, even if the graphite coating inside the battery container, which has been conventionally performed to improve battery characteristics, is omitted, the same or better battery performance can be obtained, and even better when the graphite coating is performed inside the battery container of the present invention. Battery performance is obtained.

  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, and then cold-rolled and then subjected to electrolytic cleaning, annealing, and temper rolling are used as the substrate (A). Cold rolling and electrolytic cleaning may be followed by plating as a substrate (B) without annealing, followed by annealing for both diffusion heat treatment and softening of the steel sheet.

  When using a board | substrate (A), nickel plating is first given to both surfaces of the steel plate which is a board | substrate. Next, tin plating is performed only on one surface which is the inner surface of the battery container, and then silver plating is performed. Or after giving nickel plating used as the inner surface of a battery container, silver particle dispersion | distribution tin plating is given. Thereafter, diffusion heat treatment is performed using a box-type annealing method or a continuous annealing method. By this heat treatment, a part or all of the nickel plating layer is converted into an iron-nickel alloy layer. The amount to be converted into the iron-nickel alloy layer can be appropriately adjusted depending on the nickel plating amount and the heat treatment conditions. Further, the tin plating layer or the silver particle-dispersed tin plating layer is entirely converted into an iron-nickel-tin alloy layer or / and a nickel-tin alloy layer or / and a nickel-tin-silver alloy layer. The amount to be converted into an iron-nickel-tin alloy layer or / and a nickel-tin alloy layer or / and a nickel-tin-silver alloy layer depends on the tin plating amount, silver plating amount, silver particle-dispersed tin plating amount, and heat treatment conditions. Can be adjusted. In the case of using the substrate (B), nickel plating is performed on both surfaces, then tin plating is performed only on one surface which is the inner surface of the battery container, and after silver plating is performed thereon or again, nickel plating is performed on both surfaces. Next, after silver particle-dispersed tin plating is applied only to one surface which is the inner surface of the battery container, an iron-nickel alloy layer and / or an iron-nickel-tin alloy layer and / or nickel A tin alloy layer or / and a nickel-tin-silver alloy layer is produced. Furthermore, after nickel plating, then tin plating, diffusion heat treatment, silver plating may be applied thereon to form a silver layer.

It is preferable that the coating amount of nickel plating applied to the outer surface of the battery container of the steel plate as the substrate is a coating amount of 5 to 25 g / m ² . When the nickel plating thickness is less than 5 g / m ² , the corrosion resistance on the outer surface of the battery container is not sufficient, and when it exceeds 25 g / m ² , the corrosion resistance reaches saturation, which is uneconomical. The amount of nickel plating applied to the inner surface of the battery container is preferably a coating amount of 5 to 25 g / m ² . If the nickel plating thickness is less than 5 g / m ² , cracks that reach the steel substrate may occur during press forming, and the battery performance may be deteriorated such that the amount of gas generated increases due to iron exposure. If it exceeds 25 g / m ² , the effect on battery performance reaches saturation, which is uneconomical.

A known tin plating bath can be used for the tin plating applied to the inner surface side of the battery container following the nickel plating. It is more preferable to use a phenolsulfamine bath. Tin coating weight of tin plating is preferably in a range of from 0.5 to 5 g / ^{m 2,} and more preferably in the range of 1 to 4 g / ^{m 2.} If it is less than 0.5 g / m ² , the thickness of the hard nickel tin compound layer generated by heat treatment is thin, and the size and depth of microcracks generated during press molding are small, so that the battery performance cannot be improved. . On the other hand, if the amount of tin adhesion exceeds 5 g / m ² , the size and depth of the microcracks become excessive, and there is a risk of cracks reaching the steel substrate. Further, it is more preferable that the nickel plating thickness is higher than that of nickel plating 2: tin plating 1 or more with respect to the nickel plating thickness of the base and the tin plating of the upper layer. If the tin plating is made thicker than this ratio, the thickness of the thermal diffusion treatment layer (iron-nickel alloy layer (diffusion layer) or soft recrystallized nickel layer formed on the iron-nickel alloy layer (diffusion layer)) The thickness becomes relatively thin and the risk of inducing the exposure of the steel substrate is increased.

It is preferable that the plating adhesion amount of the silver plating to be applied after the silver plating subsequently applied after the tin plating, the nickel plating or the tin plating and then the heat treatment is 0.05 to 1.0 g / m ² . Little effect of reducing the electrical conductivity is less than 0.05 g / ^{m 2,} also effect exceeds 1.0 g / ^{m 2} reaches saturation, is uneconomical because it is expensive silver.

Instead of silver plating on tin plating, a plating bath for silver particle-dispersed tin plating on nickel plating can be obtained by adding silver nitrate to a bath in which tin sulfate is added to potassium pyrophosphate. It is done. When a silver nitrate solution is added to a tin pyrophosphate complex ion solution, silver particles having a nanoparticle size are dispersedly formed in the bath, and silver particles in the bath are taken into the tin plating film by cathodic electrolysis. The silver in the dispersion plating film varies depending on the electrolysis conditions (bath composition, bath pH, current density, bath temperature, stirring conditions) but is contained in an amount of about 2 to 6% (silver adhesion amount / total adhesion amount of silver and tin). be able to. A current density of 1 to ^{2 A} / dm ² is appropriate as a current density range. The plating adhesion amount of the silver particle-dispersed tin plating is preferably in the range of 0.5 to 5.0 g / m ² . When it is less than 0.5 g / m ^2, the thickness of the tin-nickel intermetallic compound layer formed after the heat treatment is insufficient, and a sufficient effect for improving the adhesion with the positive electrode mixture cannot be obtained. Moreover, when it exceeds 5.0 g / m < ² >, since a hard tin-nickel intermetallic compound will become thick too much, the crack which reaches | attains a steel base will be induced and a steel base may be exposed excessively, and it is not preferable. The plating thickness ratio of the underlying nickel plating thickness to the silver particle dispersion plating thereon is the same as in the above-described method of tin plating subsequent to nickel plating, so that the risk of inducing exposure of the steel substrate is suppressed. It is more preferable to increase the nickel plating thickness to one or more silver particle dispersion plating. When nickel particle-dispersed tin plating is applied after nickel plating, and then heat treatment is performed, the silver particles dispersed as fine particles in the tin plating layer are solid-diffused into the outermost layer, and the surface layer is a tin layer or a tin-nickel-silver alloy. A layer forms.

In this way, an iron-nickel alloy layer or a nickel layer is formed on the iron-nickel alloy layer on one side which is the outer surface of the battery container, and the following A is formed on the other side which is the inner surface of the battery container. ) To J), that is, in order from the steel sheet side, A) iron-nickel alloy layer, nickel layer, nickel-tin alloy layer, nickel-tin-silver alloy layer, silver layer,
B) Iron-nickel alloy layer, nickel-tin alloy layer, nickel-tin-silver alloy layer, silver layer,
C) Iron-nickel alloy layer, iron-nickel-tin alloy layer, nickel-tin alloy layer, nickel-tin-silver alloy layer, silver layer,
D) Iron-nickel alloy layer, nickel layer, nickel-tin alloy layer, nickel-tin-silver alloy layer, silver layer,
E) Iron-nickel alloy layer, iron-nickel-tin alloy layer, nickel-tin alloy layer, nickel-tin-silver alloy layer,
F) Iron-nickel alloy layer, nickel-tin alloy layer, nickel-tin-silver alloy layer,
G) Iron-nickel alloy layer, nickel layer, nickel-tin alloy layer, silver layer,
H) Iron-nickel alloy layer, nickel-tin alloy layer, silver layer,
I) A plated steel sheet in which any one of an iron-nickel alloy layer, an iron-nickel-tin alloy layer, a nickel-tin alloy layer, and a silver layer is formed is obtained. The plated steel sheet is temper-rolled as necessary to obtain a plated steel sheet for battery containers of the present invention. In addition, instead of forming the nickel layer on the iron-nickel alloy layer or the iron-nickel alloy layer on one side which is the outer surface of the battery container of the steel plate, the above is formed on the other one surface which is the inner surface of the battery container. Each layer of A) to I) may be formed.

  The nickel plating layer, the tin plating layer, and the silver plating layer can be formed by electroless plating or electrolytic plating, respectively, but are preferably formed by electrolytic plating that allows easy control of the plating film composition and the amount of adhesion. The heat treatment is performed as follows. That is, as a steel plate to be a plated substrate, when using a steel plate that has been subjected to electrolytic cleaning, annealing, and temper rolling after cold rolling, it is composed of 5.5% hydrogen and 94.5% nitrogen, with a dew point of -20 to -40. Using either the box-type annealing method in which the temperature is soaked at 640 to 680 ° C. for 5 to 20 hours in a reducing atmosphere at 0 ° C. or the continuous annealing method in which heating is performed at 730 to 800 ° C. for 0.5 to 3 minutes. Annealing. In the case of performing diffusion heat treatment after performing the above plating using the substrate annealed after this cold rolling, a box annealing method of soaking at 500 to 530 ° C. for 3 to 8 hours in the same atmosphere as above, or Diffusion heat treatment is performed using any one of the continuous annealing methods of heating at 750 to 800 ° C. for 0.5 to 3 minutes.

  When the above-mentioned plating is performed on the substrate after the electrolytic cleaning after cold rolling as the steel plate to be the plated substrate, a heat treatment that combines softening of the substrate and diffusion of the plating layer is performed after plating. That is, the annealing method of either the box-type annealing method soaking at 640 to 680 ° C. for 5 to 20 hours in the same atmosphere as described above or the continuous annealing method of heating at 730 to 800 ° C. for 0.5 to 3 minutes is performed. Use for annealing and diffusion heat treatment. After performing any diffusion heat treatment in this manner, temper rolling is performed at a rolling rate of 1.0 to 1.5% in order to prevent the occurrence of stretcher strain. Thus, the plated steel sheet for battery containers of this invention can be obtained.

  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 substrates, cold-rolled plates of low-carbon aluminum killed steel (Table 1 shows the steel type I) and extremely low carbon aluminum killed steel (Table 1 shows the steel type II) shown in Table 1 are used. When aluminum killed steel (the steel type is shown as I in Table 1) was used, the ultra low carbon aluminum killed steel (the steel type was shown as II in Table 1) was used after the steps shown in any of 1) to 3) below. In each case, a plated steel sheet for a battery container was prepared through the steps shown in any of 4) to 6) below. In the following steps 1) to 6), the case where plating is performed on the side that becomes the inner surface of the container is shown, and on the side that becomes the outer surface of the container, in any one of the following steps 1) to 3) After annealing, in any of the steps 4) to 6), nickel plating was performed simultaneously with the side that became the inner surface of the container after electrolytic cleaning.
1) Cold rolling → Electrolytic cleaning → Annealing (box annealing or continuous annealing) → Nickel plating → Tin plating → Silver plating → Diffusion heat treatment (box annealing or continuous annealing) → Temper rolling 2) Cold rolling → Electrolytic cleaning → Annealing (box annealing or continuous annealing) → Nickel plating → Tin plating → Diffusion heat treatment (box annealing or continuous annealing) → Temper rolling → Silver plating 3) Cold rolling → Electrolytic cleaning → Annealing (box annealing or continuous annealing) Annealing) → Nickel plating → Silver particle dispersed tin plating → Diffusion heat treatment (box annealing or continuous annealing) → Temper rolling 4) Cold rolling → Electrolytic cleaning → Nickel plating → Tin plating → Silver plating → Annealing and diffusion heat treatment (box) Die annealing or continuous annealing) → Temper rolling 5) Cold rolling → Electrolytic cleaning → Nickel plating → Tin plating → Annealing and diffusion heat treatment (box annealing or continuous annealing) → Temper rolling → silver plating 6) Cold rolling → Electrolytic cleaning → Nickel-plated → silver dispersion tin-plated → diffusion heat treatment (box-type annealing or continuous annealing) → temper rolling

The nickel plating, tin plating, silver particle-dispersed tin plating and silver plating in the steps shown in the above 1) to 6) 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)
Agitation Air agitation pH 4 to 4.6
Bath temperature 55-60 ° C
Current density 15A / dm ²

<Tin plating>
Bath composition Stannous sulfate 30g / L
Phenolsulfonic acid 60g / L
Ethoxylated α-naphthol 5g / L
Anode Tin plate Agitation Plating bath circulation Bath temperature 45-50 ° C
Current density 5A / dm ²

<Silver particle dispersed tin plating>
Bath composition Stannous sulfate 0.1 mol / L
Silver nitrate 0.01mol / L
Potassium pyrophosphate 0.2mol / L
Polyethylene glycol (# 6000) 1g / L
Anode Tin plate Stirring Circulation of plating bath Bath temperature 50-55 ° C
Current density 1-3 A / 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))
500g / 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

  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. In Table 2, sample number 9 was not annealed after cold rolling. For comparison, a sample not subjected to tin plating (sample number 11), a sample not subjected to silver plating (sample number 12), and a sample subjected only to conventional nickel plating (sample number 13) were also prepared.

[Create battery container]
After blanking a blank with a diameter of 57 mm from the samples of Sample Nos. 1 to 13, the outer diameter 13 is obtained by ten-stage drawing so that the side on which only the iron-nickel alloy layer and the nickel layer are provided becomes 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 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 circumference 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 put 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 13 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 intermittent discharge, an operation of discharging at 2A for 0.5 seconds and then discharging at 0.25A at 29.5 seconds is one cycle, this cycle is repeated, and the number of cycles until the voltage reaches 1.0 V is measured. did. It shows that a intermittent discharge characteristic is so favorable that there are many cycles.

<Gas generation>
The battery is partially discharged (3.9Ω, 1.5 hours), then left at 70 ° C. for 2 weeks, then opened while immersed in water, and the gas generated and retained inside the battery is graduated The gas was collected in a burette and the amount of gas generated was measured. These evaluation results are shown in Table 4.

  As shown in Table 4, the plated steel sheet for battery containers of the present invention is compared with the plated steel sheet for battery containers that does not form a nickel plating layer or tin plating layer, or the plated steel sheet for battery containers that does not form a silver layer on the surface. Excellent short circuit current, discharge characteristics, intermittent discharge characteristics, and gas generation. 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 ductile iron-nickel alloy layer on a steel sheet, a nickel layer or / and a hard and brittle iron-nickel-tin alloy layer or / and a nickel-tin-silver alloy layer on a nickel-tin alloy layer or The plated steel sheet for battery containers according to the present invention in which a silver layer excellent in conductivity and spreadability is formed is a hard and brittle iron-nickel-tin alloy layer or nickel-tin alloy when being formed into a battery container. By forming microcracks on the surface of the layer, adhesion with the positive electrode mixture is improved. In addition, since a nickel-tin-silver alloy layer and / or a silver layer is formed on the iron-nickel-tin alloy layer or nickel-tin alloy layer in which micro cracks are generated on the surface, The resistance with the positive electrode mixture to be filled decreases, and the internal resistance decreases. As a result, the battery has excellent discharge characteristics after storage and can be suitably applied as a plated steel sheet for battery containers used in high performance batteries. Further, by forming the silver layer, the hydrogen gas generated by the electrochemical reaction with the alkaline electrolyte is converted to water with silver oxide, so there is no possibility that the pressure inside the battery will increase. In addition, the performance degradation after long-term storage of the battery is small and the discharge characteristics are excellent, so it is possible to omit the conventional process of applying black smoke, carbon black, etc. to the inner surface of the container, and the high-performance battery at low cost Can be manufactured. Furthermore, when the graphite coating is applied to the inside of the battery container of the present invention, further excellent battery performance can be obtained.

Claims (12)

An iron-nickel alloy layer, a nickel layer, a nickel-tin alloy layer, a nickel-tin-silver alloy layer, and a silver layer are formed in order from the bottom on the steel plate on the side that becomes the battery container inner surface of the steel plate. Plated steel sheet for battery containers. A battery container comprising an iron-nickel alloy layer, a nickel-tin alloy layer, a nickel-tin-silver alloy layer, and a silver layer formed in order from the bottom on a steel sheet on the side that is the inner surface of the battery container. Plated steel sheet. An iron-nickel alloy layer, an iron-nickel-tin alloy layer, a nickel-tin alloy layer, a nickel-tin-silver alloy layer, and a silver layer are formed in order from the bottom on the steel plate on the side that is the battery container inner surface of the steel plate. A plated steel sheet for battery containers, characterized in that A battery container comprising an iron-nickel alloy layer, a nickel layer, a nickel-tin alloy layer, and a nickel-tin-silver alloy layer formed in order from the bottom on a steel sheet on the side of the battery container that is the inner surface of the battery container. Plated steel sheet. An iron-nickel alloy layer, an iron-nickel-tin alloy layer, a nickel-tin alloy layer, and a nickel-tin-silver alloy layer are formed in this order from the bottom on the steel plate on the side that is the battery container inner surface of the steel plate. A plated steel sheet for battery containers. An iron-nickel alloy layer, a nickel-tin alloy layer, and a nickel-tin-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 layer, a nickel-tin 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-tin 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. A battery container comprising an iron-nickel alloy layer, an iron-nickel-tin alloy layer, a nickel-tin alloy layer, and a silver layer formed in order from the bottom on a steel sheet on the side that is the inner surface of the battery container. Plated steel sheet. The battery container formed by shape | molding the plated steel plate for battery containers in any one of Claims 1-9 in a bottomed cylindrical shape. A battery comprising the battery container according to claim 10. An iron-nickel alloy layer is formed on the surface of the steel sheet on the side of the battery container inner surface by applying nickel plating to at least the side of the steel sheet inner surface of the battery container and then performing silver particle-dispersed tin plating and heat treatment Then, a nickel layer or an iron-nickel-tin alloy layer is formed thereon, and a nickel-tin alloy layer is further formed thereon, or an iron-nickel alloy layer is formed on the steel base. A nickel-tin-silver alloy layer and / or a silver layer is formed thereon, and a method for producing a plated steel sheet for battery containers.