JP2006257543A - 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 in which a plated layer is not peeled or cracked when being formed into a battery vessel, which has excellent corrosion resistance to an alkali solution, and with which a battery having excellent battery properties can be made, 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 obtained by applying nickel plating to the side to form into the inside face of a battery vessel in a steel sheet and next applying nickel-cobalt-boron alloy plating to the surface thereof, or a plated steel sheet obtained by applying nickel plating, next applying nickel-cobalt-boron alloy plating, and thereafter performing heat treatment, or a plated steel sheet obtained by applying nickel plating, next applying nickel-cobalt-boron alloy plating to the surface thereof, and applying silver plating to the surface thereof is used as the one for a battery vessel, and the same is formed into a battery vessel, so as to be applied to a 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, 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 that do not reach the steel substrate occur in the plating layer on the battery container inner surface side, and the positive electrode mixture of the alkaline battery and Improved adhesion and contact resistance of the battery container, and can sufficiently exhibit excellent battery performance after long-term storage, a battery container using the plated steel sheet for the battery container, and the battery container It aims at providing the battery using this.

In order to achieve the object of the present invention, a plated steel sheet for a battery container according to the present invention is formed by forming a nickel layer and a nickel-cobalt-boron alloy layer in order from the bottom on a steel sheet on the side that is the battery container inner surface of the steel sheet. An iron-nickel alloy layer, a nickel layer, and a nickel-cobalt-boron alloy layer are arranged in this order from the bottom on the plated steel sheet for battery containers (Claim 1), or on the steel sheet on the side that is the battery container inner surface of the steel sheet. An iron-nickel alloy layer and a nickel-cobalt-boron alloy layer in order from the bottom on a plated steel sheet for battery containers (Claim 2) or a steel sheet on the side of the steel sheet that is the inner surface of the battery container. Formed on a plated steel sheet for battery containers (Claim 3), or a steel sheet on the side of the steel sheet that is the inner surface of the battery container, in order from the bottom, an iron-nickel alloy layer, iron-nickel-co A plated steel sheet for battery containers, characterized in that a Felt-Boron alloy layer is formed (Claim 4), or a steel layer on the side of the steel sheet that will be the battery container inner surface, in order from the bottom, nickel layer, nickel-cobalt- A plated steel sheet for battery containers, wherein a boron alloy layer and a silver layer are formed (Claim 5), or an iron-nickel alloy layer in order from the bottom on a steel sheet on the side that is the battery container inner surface of the steel sheet, A nickel steel layer, a nickel-cobalt-boron alloy layer, and a silver layer are formed on the plated steel sheet for battery containers (Claim 6), or on the steel sheet on the side that is the inner surface of the battery container. An iron-nickel alloy layer, a nickel-cobalt-boron alloy layer, and a silver layer are formed on the plated steel sheet for battery containers (Claim 7), or on the steel sheet on the side that becomes the battery container inner surface of the steel sheet In order from the bottom, an iron-nickel alloy layer, an iron-nickel-cobalt-boron alloy layer, and a silver layer are formed, a plated steel sheet for battery containers (Claim 8), or an inner surface of the battery container of the steel sheet, An iron-nickel alloy layer, an iron-nickel-cobalt-boron alloy layer, a nickel-cobalt-boron alloy layer, and a silver layer are formed on a steel plate on the side in order from the bottom. An iron-nickel alloy layer, a nickel layer, a nickel-cobalt-boron alloy layer, a nickel-cobalt-boron-silver alloy layer in this order from the bottom on the steel plate (Claim 9) or the steel plate on the side that is the battery container inner surface of the steel plate. A plated steel sheet for a battery container (Claim 10), or a steel sheet on the side of the steel sheet that is the inner surface of the battery container, in order from the bottom, an iron-nickel alloy layer, nickel A nickel-cobalt-boron alloy layer, a nickel-cobalt-boron-silver alloy layer, a plated steel sheet for a battery container, characterized in that a silver layer is formed, or an inner surface of the battery container of the steel sheet An iron-nickel alloy layer, a nickel-cobalt-boron alloy layer, and a nickel-cobalt-boron-silver alloy layer are formed on the steel plate on the side in order from the bottom. 12), or an iron-nickel alloy layer, an iron-nickel-cobalt-boron alloy layer, a nickel-cobalt-boron layer-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. An iron-nickel alloy layer, iron-nickel-, in order from the bottom, on a plated steel sheet for battery containers (Claim 13), or on a steel sheet on the side that is to be the battery container inner surface of the steel sheet A steel plate for a battery container, comprising a cobalt-boron alloy layer, a nickel-cobalt-boron alloy layer, a nickel-cobalt-boron-silver alloy layer, or an inner surface of the battery container of the steel plate, An iron-nickel alloy layer, an iron-nickel-cobalt-boron alloy layer, a nickel-cobalt-boron alloy layer, a nickel-cobalt-boron-silver alloy layer, and a silver layer are formed in this order on the steel plate. It is either of the steel plates for battery containers (Claim 15).

  Moreover, the battery container of this invention is a battery container (Claim 16) formed by shape | molding the plated steel plate for battery containers in any one of the said (Claims 1-15) to a bottomed simple shape. And the battery of this invention is a battery (Claim 17) using the battery container of said (Claim 16).

  The plated steel sheet for battery containers according to the present invention is a plated steel sheet obtained by applying nickel plating to the battery container inner surface side of the steel sheet, and then applying nickel-cobalt-boron alloy plating thereon, or also applying nickel plating, A plated steel sheet obtained by performing nickel-cobalt-boron alloy plating and then heat-treating, or further applying nickel plating, and then applying silver plating on the nickel-cobalt-boron alloy plating applied thereon, Alternatively, further nickel plating is performed, and then nickel-cobalt-boron alloy plating is performed thereon, followed by heat treatment, followed by silver plating on the plated steel sheet, or nickel coating, and then on the steel plate. After silver plating on the nickel-cobalt-boron alloy plating With plated steel sheet, one of plated steel sheet formed by heat treatment, it is possible to obtain a battery container plated steel sheet according to the claims 1-15. 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.

  Since the cobalt-containing compound containing boron formed on the battery container inner surface of the plated steel sheet for battery containers of the present invention is hard, microcracks are generated in the process of press-molding the battery container, and manganese dioxide as the positive electrode active material is added. The contact resistance in the alkaline electrolyte can be kept low by increasing the adhesion with the inner surface of the battery container directly or via the conductive agent layer applied to the inner surface of the battery container. It becomes possible to improve load discharge. Further, by forming a silver layer or a cobalt-containing compound containing silver on the cobalt-containing compound containing boron, the heavy load discharge performance can be further improved, and as a result, a conductive agent layer applied to the inner surface of the battery container Even if is omitted, it can be suitably applied as a battery container material excellent in heavy load discharge characteristics after storage that is comparable to or higher than that of a conventional nickel-plated steel sheet provided with a conductive agent layer. At the same time, the generation of gas in the battery can is suppressed by the electrochemical reaction in the alkaline electrolyte of the silver layer of the outermost layer or the cobalt-containing compound containing silver, thereby reducing the gas pressure and reducing the leakage resistance of the battery. Liquidity can be increased.

  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 both surfaces 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 for} the outer surface of the battery can. When the nickel plating thickness is 4.5 g / m ² , the corrosion resistance on the outer surface of the battery can is insufficient, and when it exceeds 30 g / m ² , the corrosion resistance reaches saturation, which is uneconomical. On the other hand, the nickel plating thickness applied to the inner surface of the battery can is preferably a coating amount of 5 to 25 g / m ² . If it is less than 5 g / m ² , the iron exposure of the steel substrate increases when it is press-molded into a battery can, and the battery performance deteriorates. On the other hand, if it exceeds 25 g / m ² , the battery performance reaches saturation and is uneconomical. .

Next, nickel-cobalt-boron alloy plating is applied to both surfaces of the battery container or one surface serving as the inner surface of the battery container. The nickel-cobalt-boron alloy plating includes an electroless method and an electrolysis method, and the electrolysis method is preferably used in the present invention. The plating thickness of the nickel-cobalt-boron alloy plating applied to the inner surface side of the battery container is preferably in the range of 0.5 to 5 g / m ² , more preferably 1 to 3 g / m ² as a plating amount obtained by adding Ni and Co. To do. If it is less than 0.5 g / m < ² >, the thickness of the micro crack formed in the battery can inner surface will be thin, and the improvement of adhesiveness with a positive mix will be small. On the other hand, if it exceeds 5 g / m ² , the depth of the microcracks becomes excessive, the number of cracks reaching the steel substrate increases, and the battery performance deteriorates. Also, the B content of nickel-cobalt-boron alloy plating (Ni, Co, B is measured by the fluorescent X-ray method in units of g / m ² and expressed as B / (Ni + Co + B) × 100) is 1 to 5% by weight. Ranges are preferably used. If the amount is less than 1% by weight, the formation of microcracks is insufficient, so that an effect on the battery performance cannot be obtained. If the amount exceeds 5% by weight, it is difficult to control the boron content of the plating film composition. The cobalt content (Co / (Ni + Co + B) × 100)) is preferably 10 to 40% by weight. If the amount is less than 10% by weight, the effect on the battery performance cannot be obtained. If the amount exceeds 40% by weight, the effect on the battery performance reaches saturation and the difficulty of controlling the cobalt content in the plating film increases. It is. The alloy composition ratios of Ni, Co and B can be obtained by appropriately controlling the bath composition, bath pH, temperature and current density.

In the present invention, excellent battery performance can be obtained with the nickel-cobalt-boron alloy plating applied. However, after the nickel-cobalt-boron alloy plating is applied, heat treatment is performed, or after further heat treatment, When the silver plating is subsequently flash coated, or after the nickel-cobalt-boron alloy plating is applied, the silver plating is subsequently flash coated, or also after the nickel-cobalt-boron alloy plating is applied, the silver plating is continued. An excellent battery forming material can be obtained by applying and then heat-treating. 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.

  When heat treatment is performed after plating, diffusion heat treatment is performed using either a box-type annealing method or a continuous annealing method. In the diffusion heat treatment, the nickel-cobalt-boron alloy plating generates a Ni and B compound and a Co and B compound by the heat treatment, whereby the coating is cured. The heat treatment is accompanied by the formation of these compounds, the nickel plating layer under the nickel-cobalt-boron alloy plating is recrystallized and soft, and a part or all of the nickel plating layer is an iron-nickel diffusion layer (alloy layer). It is a condition that results in conversion to. 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 nickel-boron alloy 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 nickel plating and nickel-cobalt-boron alloy plating are performed, and subsequently heat treatment is performed, or when heat treatment is performed after further silver plating is performed, by controlling the thickness of each plating layer and the heat treatment conditions, FIG. The plated steel sheet for battery containers provided with the cross-sectional structure of FIG. 4 and FIGS. 6-15 is obtained. In addition, FIGS. 1-15 shows the upper layer structure from the steel base of the side used as the battery container inner surface. 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 a plating substrate, hot-rolled low carbon aluminum killed steel (I) or ultra 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-nickel-cobalt-boron alloy plating b) low-carbon aluminum killed steel (I) → Cold rolling one electrolytic cleaning → Annealing (box annealing or continuous annealing) → Temperature rolling → Nickel plating—Nickel-cobalt-boron alloy plating → Silver plating c) Low carbon aluminum killed steel (I) → Cold rolling one electrolysis Cleaning → Annealing (box annealing or continuous annealing) → Temper rolling → Nickel plating-nickel-cobalt-boron alloy plating → Diffusion heat treatment (box annealing or continuous annealing) → Temper rolling d) Low carbon aluminum killed steel (I) → Cold rolling one electrolytic cleaning → annealing (box annealing or continuous annealing) → temper rolling → nickel plating → nickel-cobalt-boron alloy plating → 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) → temper rolling → nickel plating → nickel-cobalt-boron alloy Plating → Silver plating → Heat treatment (box annealing or continuous annealing) → Temper rolling) Ultra low carbon aluminum killed steel (II) → Cold rolling → Electrolytic cleaning → Nickel plating → Nickel-cobalt-boron alloy plating → Silver plating → Heat treatment (box annealing or continuous annealing) → temper rolling

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, nickel plating, nickel-cobalt-boron alloy plating, and silver plating were performed under the following conditions.
<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

<Nickel-cobalt-boron alloy plating>
Bath composition Nickel sulfate 240g / L
Cobalt sulfate 25-50g / L
Nickel chloride 45g / L
Boric acid 30g / L
Trimethylamine borane 3-6g / L
Anode Nickel Pellets (Titanium basket filled with S pellets from INCO Corporation and equipped with polypropylene anode bag)
Agitation Air agitation pH 4-4.6
Bath temperature 50-55 ° C
Current density 1-5A / 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. In addition, when the diffusion heat treatment of the plating layer that also serves to anneal the steel substrate after plating is performed by a single heat treatment, the heat treatment is performed at a heating temperature of 800 ° C. and a heating time of 0.5 to 3 minutes using a continuous annealing method. It was.

Samples (sample numbers 1 to 15) of the plated steel sheets for battery containers shown in Tables 2 and 3 were prepared as described above. In addition, a sample (Sample No. 16) that has been subjected to nickel plating for comparison using low-carbon aluminum killed steel (I), a sample that has been subjected to thermal diffusion treatment after nickel plating (Sample No. 17), and after nickel plating Then, a sample (sample number 18) subjected to nickel-phosphorus alloy plating, and a sample (sample number 19) subjected to heat treatment after nickel-phosphorous alloy plating following nickel plating were prepared. Nickel-phosphorus alloy plating was performed under the following conditions.
<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 blanks were punched out from these samples Nos. 1 to 19 with a diameter of 57 mm, the outer diameter 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 doughnut-shaped positive electrode mixture pellet having a predetermined size, and was press-inserted into a battery container having a conductive material mainly composed of graphite powder applied 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 19 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. 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 3, 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-cobalt-boron alloy plated layer and the plated steel sheet for battery containers that does not form a silver layer on the surface. Superior to short circuit current, 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.

  An iron-nickel alloy layer or / and a nickel layer are formed on the steel plate, and an iron-nickel-cobalt-boron alloy layer and / or a nickel-cobalt-boron alloy layer having excellent corrosion resistance to an alkaline solution is formed on the steel plate. The plated steel sheet for battery containers according to the present invention in which a nickel-cobalt-boron-silver alloy layer or / and a silver layer having excellent conductivity is formed into a container by drawing or drawing and ironing. Since the plating layer does not peel or cracks, and the surface is excellent in alkali resistance and conductivity, it is suitable as a container for high performance batteries and high performance batteries excellent in battery characteristics such as discharge characteristics. Can be applied. 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. Sectional drawing which shows another example of the upper layer formation 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 (17)

A plated steel sheet for a battery container, wherein a nickel layer and a nickel-cobalt-boron alloy 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. An iron-nickel alloy layer, a nickel layer, and a nickel-cobalt-boron 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. An iron-nickel alloy layer and a nickel-cobalt-boron 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. An iron-nickel alloy layer and an iron-nickel-cobalt-boron alloy layer are formed in order from the bottom on a steel plate on the side of the steel plate that is the inner surface of the battery case. A plated steel sheet for a battery container, wherein a nickel layer, a nickel-cobalt-boron alloy 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 nickel-cobalt-boron 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, a nickel-cobalt-boron 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. An iron-nickel alloy layer, an iron-nickel-cobalt-boron 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. An iron-nickel alloy layer, an iron-nickel-cobalt-boron alloy layer, a nickel-cobalt-boron 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. An iron-nickel alloy layer, a nickel layer, a nickel-cobalt-boron alloy layer, and a nickel-cobalt-boron-silver alloy 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. An iron-nickel alloy layer, a nickel layer, a nickel-cobalt-boron alloy layer, a nickel-cobalt-boron-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. A battery comprising an iron-nickel alloy layer, a nickel-cobalt-boron alloy layer, and a nickel-cobalt-boron-silver alloy layer formed in this order from the bottom on a steel plate on the side that is to be the battery container inner surface of the steel plate. Plated steel sheet for containers. An iron-nickel alloy layer, an iron-nickel-cobalt-boron alloy layer, a nickel-cobalt-boron layer-silver alloy 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. An iron-nickel alloy layer, an iron-nickel-cobalt-boron alloy layer, a nickel-cobalt-boron alloy layer, and a nickel-cobalt-boron-silver alloy layer are arranged 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 by being formed. In order from the bottom on the steel sheet on the battery container inner surface side of the steel sheet, the iron-nickel alloy layer, iron-nickel-cobalt-boron alloy layer, nickel-cobalt-boron alloy layer, nickel-cobalt-boron-silver alloy layer, A plated steel sheet for battery containers, wherein a silver layer is formed. The battery container formed by shape | molding the plated steel plate for battery containers in any one of Claims 1-15 in a bottomed simple shape. A battery comprising the battery container according to claim 16.

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