JP2006348362A - Plated steel sheet for battery receptacle, battery receptacle using the plated steel sheet, and battery using the battery receptacle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plated steel sheet for a battery receptacle, which reduces the leakage of a liquid due to an increasing amount of gas generated along with improvement in battery characteristics, while improving the battery characteristics; a battery receptacle with the use of the plated steel sheet for the battery receptacle; and the battery with the use of the battery receptacle. <P>SOLUTION: A method for manufacturing the plated steel sheet for the battery receptacle comprises the steps of: forming a layer of a metal including titanium on a steel sheet, by plating the surface of the steel sheet to be an inner surface of the battery receptacle with a nickel-titanium alloy; and forming a plated layer of nickel or a nickel alloy on the above surface, or further heat-treating the plated steel sheet to make titanium exist in a boundary between a steel matrix and the plated layer formed thereon. The battery receptacle is made by forming the steel sheet, 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, with the development of portable AV equipment and mobile phones such as digital cameras, CD players, MD players, liquid crystal televisions, game machines, etc., alkaline batteries as primary batteries and nickel metal hydride batteries as secondary batteries as heavy load operating power sources Lithium ion batteries are often used. In these batteries, there is a 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. Yes. Conventionally, as these battery container materials, in order to make it possible to maintain corrosion resistance against a strong alkaline electrolyte and low contact resistance at the interface between the inner surface of the battery container and the positive electrode mixture, nickel plating is applied to the cold-rolled steel sheet in advance. A formed nickel-plated steel sheet is formed into a battery container, or a cold-rolled steel sheet is formed into a battery container, and then the inner and outer surfaces of the battery container are nickel-plated by barrel plating. In addition, for nickel-plated steel sheets, in order to improve the adhesion between the nickel-plated layer and the steel substrate, and to suppress the exposure of iron during the forming process, heat treatment is performed after the nickel plating, and iron is interposed between the steel substrate and the nickel-plated layer. -Although the thermal diffusion treatment method provided with a nickel alloy layer (diffusion layer) is adopted, if the nickel layer remains on the outermost layer when forming the diffusion layer by heat treatment, the surface of the nickel layer is solid In order to inhibit the contact resistance due to the presence of an oxide film, a method of converting the entire nickel layer into an iron-nickel alloy layer (diffusion layer) has been proposed (for example, see Patent Document 1). In addition, hard gloss nickel plating with an organic brightener added to the inner surface of the battery container causes wedge-shaped cracks during press molding, increasing the positive electrode mixture and adhesion, and increasing the contact area. A method for reducing the internal resistance of the battery has been proposed (see, for example, Patent Document 2). Furthermore, the present inventors use a steel plate in which a nickel-tin alloy layer is formed on a nickel layer or an iron-nickel alloy layer (diffusion layer), so that fine cracks are not formed when the battery container is formed. A method has been proposed in which an uneven surface is formed on the inner surface of a battery container to reduce the internal resistance of the battery by increasing the contact area with the positive electrode mixture or the conductive coating (see, for example, Patent Document 3).

  When cracking occurs in the plating layer on the inner side of the battery container when the battery container is formed by drawing or ironing, the steel substrate is locally exposed. When the steel substrate is exposed, the exposed part comes into direct contact with a strong alkaline electrolyte, and in the vicinity of the steel plate substrate, nickel of the nickel plating layer, which is a noble metal than iron, manganese dioxide of active material, and oxygen are present. Therefore, iron dissolution occurs. When the eluted iron ions move to the negative electrode made of zinc, hydrogen gas is generated by reaction with the zinc. The gas generated in this way increases the battery internal pressure and causes leakage. Further, it is known that the battery performance is better as the thickness of the nickel plating layer is thinner. However, the degree of exposure of the steel base is increased, and there is a problem that the liquid leakage due to gas generation increases. In addition, as described in Patent Document 2 and Patent Document 3, when the plating film is hardened, the discharge characteristics are improved, but when the battery container is formed, cracks reaching the steel base are induced. The risk of increasing gas generation is increased.

Prior art document information relating to the present application includes the following.
Japanese Patent Application Laid-Open No. 08-017406 Japanese Patent Publication No. 2810257 Japanese Patent No. 2877957

  In the present invention, a method of improving the battery characteristics by reducing the plating thickness of the nickel-plated steel sheet, or a microcrack when forming a hard plating layer and heat-treating the plating film to form a battery container by heat treatment after plating. In conventional methods, such as improving the battery performance by increasing the adhesion with the positive electrode active material, while maintaining the improvement in battery performance, the liquid leakage due to gas generation associated with these methods is maintained. The purpose is to reduce.

In order to achieve the object of the present invention, the plated steel sheet for battery containers according to the present invention is characterized in that a metal layer containing titanium is formed on a steel sheet on the side that is the battery container inner surface of the steel sheet. A steel plate (claim 1),
In the plated steel sheet for battery containers of the above (Claim 1), a nickel layer is formed on the metal layer containing titanium (Claim 2), or on the metal layer containing titanium, A nickel alloy layer is formed (Claim 3), and in the plated steel sheet for battery containers according to (Claim 2 or 3), carbonaceous matter is dispersed in the nickel layer or the nickel alloy layer. (Claim 4), and in the above (Claim 3 or 4), the nickel alloy is a nickel-tin alloy, a nickel-phosphorus alloy, a nickel-cobalt alloy, It is any one of a nickel-cobalt-phosphorus alloy, a nickel-boron alloy, and a nickel-cobalt-boron alloy (Claim 5).

Moreover, the battery container of the present invention is a battery container (Claim 6) formed by processing the plated steel sheet for a battery container according to any one of the above (Claims 1 to 5) into a bottomed cylindrical shape,
The battery of the present invention is a battery (Claim 7) using the battery container of (Claim 6) described above.

  The plated steel sheet for battery containers of the present invention forms a metal layer containing titanium on the steel sheet by performing nickel-titanium alloy plating on at least the inner surface of the steel sheet, and nickel plating or nickel alloy on the upper layer. Titanium is made to exist in the boundary part of a steel base and the plating layer on it by plating, or by heat-processing after plating. When titanium is present on the steel substrate, since titanium has a lower potential than iron, dissolution of iron can be suppressed by sacrificial dissolution of titanium. Therefore, when the plating film such as nickel plating on the steel substrate is thin, or when pinholes in the plating layer or hard layers such as bright nickel plating or nickel-tin alloy layer are formed and processed, micro cracks occur and the steel substrate Hard nickel-tin alloy, which has improved gas leakage from the negative electrode due to dissolution of iron, improves leakage resistance, and has poor battery leakage performance even though it has excellent battery discharge performance. The problem in the conventional method of forming nickel alloy plating such as can be solved.

  The contents of the present invention will be described below. As a steel plate used as the substrate of the plated steel plate for battery containers of the present invention, low carbon aluminum killed steel for drawing (carbon content 0.01 to 0.15% by weight), or deep drawing for adding niobium or titanium. Non-aging ultra-low carbon 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 after cold rolling and then electrolytically cleaning can be used as a substrate.

  First, nickel-titanium alloy plating is performed on one surface which is the inner surface of a battery container of a steel plate as a substrate. Next, either nickel plating, nickel alloy plating, carbonaceous dispersion nickel plating, carbonaceous dispersion nickel alloy plating is applied to the upper layer of the nickel-titanium alloy plating applied to one side and the inner surface of the battery container of the steel plate, Alternatively, nickel plating is performed, and subsequently, nickel alloy plating, carbonaceous dispersion nickel plating, carbonaceous dispersion nickel alloy plating, or tin plating is applied thereon. After the tin plating is performed, a heat treatment is performed after the plating. However, for each plating other than the tin plating, the heat treatment may be performed after the plating, or the plating may be left as it is.

As a plating bath used for nickel-titanium alloy plating, a plating bath in which titanium fluoride is used as an ion source of titanium, nickel sulfate, and an organic complexing agent such as glycine as a complexing agent is added thereto is used. It is preferable to perform plating by an electroplating method. The plating adhesion amount is preferably in the range of 0.1 to 1.0 g / m ² . If it is less than 0.1 g / m ² , the effect of suppressing the iron dissolution of the exposed steel substrate in the sacrificial dissolution of titanium is small. On the other hand, if it exceeds 1.0 g / m ² , the suppression effect reaches saturation and is not satisfactory. Become an economy. A nickel-titanium alloy plating film having a titanium content of 10 to 30% can be obtained, although it varies depending on the applied plating bath composition, pH, electrolysis conditions, and the like.

When nickel plating is performed after nickel-titanium alloy plating, it is preferable to perform matte nickel plating using a Watt bath, or semi-bright nickel plating in which an organic additive is added to the Watt bath. The amount of nickel plating attached is preferably ² g / m ² or more. If it is less than 2 g / m ² , the steel substrate is exposed excessively due to pinholes in the plating film and wrinkles when forming into the battery container, and iron ions are dissolved in the alkaline electrolyte by sacrificial dissolution of titanium It becomes difficult to deter. The upper limit of the nickel plating adhesion amount can be appropriately determined depending on economy. Heat treatment may be performed after nickel plating. By the heat treatment, an iron-nickel-titanium alloy layer is formed in order from the steel substrate side, an iron-nickel alloy layer or an iron-nickel-titanium alloy layer is formed thereon, and an iron-nickel alloy layer is further formed thereon. In addition, a nickel layer is formed thereon.

When nickel alloy plating is performed after nickel-titanium alloy plating, a hard layer or a hard layer with improved conductivity is obtained. Examples of nickel alloy plating that can provide a hard layer include nickel-phosphorus alloy plating, nickel-cobalt alloy plating, nickel-cobalt-phosphorus alloy plating, nickel-boron alloy plating, and nickel-cobalt-boron alloy plating. . The plating adhesion amount of these nickel alloy platings is preferably in the range of 0.5 to 5 g / m ² as the nickel amount in any nickel alloy plating. If it is less than 0.5 g / m ² , the effect of improving battery discharge characteristics cannot be obtained. On the other hand, if it exceeds 5 g / m ² , fine cracks are excessively formed when the battery container is molded, and titanium is sacrificed and dissolved. As a result, it becomes impossible to prevent the elution of iron from occurring, and thus the effect of improving the leakage resistance cannot be obtained.

  When nickel-phosphorus alloy plating is used as nickel alloy plating, it is preferable to use a bath obtained by adding phosphorous acid to a matte nickel plating bath. The phosphorus content (P / (Ni + P) × 100) of the nickel phosphorus alloy plating is preferably 1 to 12%. If it is less than 1%, the nickel-phosphorus alloy plating is not sufficiently hardened. On the other hand, if it exceeds 12%, the deposition efficiency is lowered, so that stable plating work becomes difficult.

  When nickel-cobalt alloy plating is used as the nickel alloy plating, it is preferable to use a bath in which cobalt sulfate is added to the watt bath. The cobalt content (Co / (Ni + Co) × 100) of the nickel-cobalt alloy plating is preferably in the range of 2.5 to 50%. If it is less than 2.5%, the effect of suppressing the deterioration of conductivity after battery storage by containing cobalt is small. On the other hand, if it exceeds 50%, the effect of suppressing the deterioration of conductivity reaches saturation and becomes uneconomical.

  When nickel-cobalt-phosphorus alloy plating is used as the nickel alloy plating, it is preferable to use a bath in which cobalt sulfate and phosphorous acid are added to the Watt bath. The cobalt content (Co / (Ni + Co + P) × 100) of the nickel-cobalt-phosphorus alloy plating is preferably set to a range of 2.5 to 50% for the same reason as in the case of using the nickel-cobalt alloy plating. . The phosphorus content (P / (Ni + Co + P) × 100) is preferably in the range of 1 to 12% for the same reason as in the case of using the nickel-phosphorus alloy plating.

  When nickel-boron alloy plating is used as the nickel alloy plating, it is preferable to use a bath in which trimethylamine borane is added to the Watt bath. The boron content (B / (Ni + B) × 100) of the nickel-boron alloy plating is preferably in the range of 1 to 5%. If it is less than 1%, the nickel-boron alloy plating is not sufficiently hardened, and if it exceeds 5%, it is difficult to lower the deposition efficiency of the plating film and to control the film composition.

  When nickel-cobalt-boron alloy plating is used as the nickel alloy plating, it is preferable to use a bath in which cobalt sulfate and trimethylamine borane are added to the Watt bath. The cobalt content (Co / (Ni + Co + B) × 100) of the nickel-cobalt-boron alloy plating is preferably in the range of 2.5 to 50% for the same reason as in the case of using the nickel-cobalt alloy plating. . Further, the boron content (B / (Ni + Co + B) × 100) is preferably in the range of 1 to 5% for the same reason as in the case of using the nickel-boron alloy plating.

  The various nickel alloy platings described above may be performed directly on the nickel-titanium alloy plating, or may be performed on the nickel-titanium alloy plating and then the nickel plating.

  Further, on the nickel-titanium alloy layer formed as described above, or on the nickel-titanium alloy layer and the nickel layer formed thereon, the above nickel plating bath and various nickel alloy plating baths Carbonaceous dispersion nickel plating or carbonaceous dispersion nickel alloy plating may be applied using a dispersion plating bath in which carbonaceous material is dispersed and contained. Examples of carbonaceous materials include natural graphite powder having a particle size of 1 to 10 μm, artificial graphite powder, fine carbonaceous materials composed of carbon black such as channel black, thermal black, furnace black, ketjen black, acetylene black, and carbon nanotubes. Fine carbonaceous materials or a mixture of two or more of these can be used. Since the ultrafine carbonaceous material is expensive, it is more preferable to use a fine carbonaceous material made of carbon black such as ketjen black having an average diameter of 10 to 60 nm or acetylene black having an average diameter of 50 to 200 nm. The carbonaceous content in the plating film of carbonaceous dispersed nickel plating or carbonaceous dispersed nickel alloy plating is preferably in the range of 0.1 to 5% by weight (ratio of carbonaceous content to the total amount of metals). More preferably, it is dispersed in an amount of from 5 to 3% by weight. Since these carbonaceous materials are hydrophobic, they are dispersed in the plating solution using a surfactant. By performing an electrolytic treatment using a plating solution in which these carbonaceous materials are dispersed, a dispersion plating in which these carbonaceous materials are dispersed in the plating layer is obtained.

The plating adhesion amount of these carbonaceous dispersed nickel plating or carbonaceous dispersed nickel alloy plating is preferably in the range of 0.5 to 5 g / m ² as the nickel amount. If it is less than 0.5 g / m ² , the effect of the battery discharge characteristics cannot be obtained. On the other hand, if it exceeds 5 g / m ² , microcracks are excessively formed when molding the battery, and iron due to sacrificial dissolution of titanium. Elution cannot be suppressed and a sufficient effect on leakage resistance cannot be obtained.

As described above, in addition to the method of performing hard nickel alloy plating on the nickel-titanium alloy layer, nickel plating is applied on the nickel-titanium alloy layer, and further tin plating is applied thereon, followed by heat treatment. There is also a method of applying a hard nickel-tin alloy layer. The amount of tin plating applied after nickel plating is preferably in the range of 0.5 to 5 g / m ² . If it is less than 0.5 g / m ² , the thickness of the nickel-tin alloy layer formed by heat treatment is thin, and when formed into a battery container, microcracks are not sufficiently formed, and sufficient adhesion to the positive electrode active material is achieved. Is not obtained, and the effect of improving the battery discharge characteristics is insufficient. On the other hand, if it exceeds 5 g / m ² , the thickness of the nickel-tin alloy layer becomes too thick, and the extent to which microcracks reach the steel substrate becomes excessive, exceeding the limit of the iron dissolution inhibiting effect due to the sacrificial dissolution of titanium. As a result, the leakage resistance deteriorates. The ratio between the amount of tin plating and the amount of nickel plating below it is necessary that the amount of tin deposited is equal to or greater than the elemental ratio of nickel-tin alloy (Ni ₂ Sn). When tin that is not alloyed remains in the outermost layer, the tin is eluted into the alkaline electrolyte and the battery performance is deteriorated. The heat treatment is preferably performed at a heating temperature of 500 ° C. or higher for 1 hour or longer. Heat treatment conditions outside this range are not preferable because tin-rich Ni ₂ Sn ₂ and Ni ₂ Sn ₄ are produced as a nickel-tin alloy and the amount of tin dissolved in the alkaline electrolyte increases.

  Apply nickel-titanium alloy plating, apply nickel-titanium alloy plating other than the method of heat treatment after applying nickel plating and tin plating on the nickel-titanium alloy plating, and then apply nickel plating on the nickel-titanium alloy plating. When plating, carbonaceous dispersion nickel plating, or carbonaceous dispersion nickel alloy plating is applied, the plating may be left as it is, or as described above, heat treatment after nickel-titanium alloy plating and nickel plating are performed. Then, any of nickel alloy plating, carbonaceous dispersed nickel plating, and carbonaceous dispersed nickel alloy plating may be applied thereon. Or you may heat-process, after giving nickel-titanium alloy plating, nickel plating, then nickel alloy plating, carbonaceous dispersion nickel plating, and carbonaceous dispersion nickel alloy plating. When heat treatment is performed after these platings, either a box-type annealing method or a continuous annealing method is used. When the box annealing method is used as the heat treatment condition, the nickel plating layer is not softened and the iron-nickel alloy layer (diffusion layer) is not formed by heating at less than 450 ° C. On the other hand, when heated at a temperature exceeding 700 ° C., the iron-nickel alloy layer (diffusion layer) is sufficiently formed, but the steel substrate becomes too soft and undesirably deteriorates the strength of the battery container. 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.

  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 was used.

A hot rolled sheet of the above steel grade I or II is subjected to cold rolling and electrolytic cleaning by a conventional method to obtain a cold rolled sheet having a thickness of 0.25 mm. The following various types of plating are applied to an annealed plate that has been subjected to annealing at a soaking temperature of 640 to 680 ° C. for 8 hours using a method, and the plating is used as it is, or after plating, using a box-type annealing method. Heat treatment was applied at ˜550 ° C. and an overheating time of 6 to 8 hours. Moreover, about some steel types I, after performing various plating shown below to the unannealed board which performed electrolytic cleaning, the heat processing temperature 650 degreeC and the heat processing for 2 minutes were performed by the continuous annealing furnace method. In the case of steel type II, the following various platings were applied to the unannealed plate that had been subjected to electrolytic cleaning, and then heat treatment was performed at a heating temperature of 780 ° C. and a heating time of 2 minutes by a continuous annealing furnace method. Thus, the plated steel plate for battery containers was created through the process shown to following i) -nu).
B) Low carbon aluminum killed steel (I) → Cold rolling → Electrolytic cleaning → Annealing (box annealing method) → Temper rolling → Nickel plating (inside and outside side)
B) Low carbon aluminum killed steel (I) → Cold rolling → Electrolytic cleaning → Annealing (box annealing method) → Temper rolling → Nickel plating (inner and outer surfaces) → Heat treatment (box annealing method) → Temper rolling ) Low carbon aluminum killed steel (I) → cold rolling → electrolytic cleaning → annealing (box annealing) → temper rolling → nickel-titanium alloy plating (inner side) → nickel plating (inner and outer side) → tin plating ( Inner side) → Heat treatment (box annealing method) → Temper rolling d) Low carbon aluminum killed steel (I) → Cold rolling → Electrolytic cleaning → Annealing (box annealing method) → Temper rolling → Nickel plating (inner and outer surfaces) Side) → tin plating (inside surface) → heat treatment (box annealing method) → temper rolling e) ultra-low carbon aluminum killed steel (II) → cold rolling → electrolytic cleaning → nickel-titanium alloy plating (inside side) → nickel Plating (inside and outside) → Nickel alloy plating (inside) → Heat treatment Continuous annealing method) → Temper rolling f) Ultra-low carbon aluminum killed steel (II) → Cold rolling → Electrolytic cleaning → Nickel plating (inside and outside) → Nickel alloy plating (inside) → Heat treatment (continuous annealing) → Tempered rolling g) Low carbon aluminum killed steel (I) → Cold rolling → Electrolytic cleaning → Annealing (box annealing method) → Temper rolling → Nickel-titanium alloy plating (inner side) → Nickel plating (inner and outer side) → Carbon dispersion nickel plating (inner side)
H) Low carbon aluminum killed steel (I) → Cold rolling → Electrolytic cleaning → Annealing (box annealing method) → Temper rolling → Nickel plating (inside and outside) → Carbon dispersion nickel plating (inside)
B) Low carbon aluminum killed steel (I) → cold rolling → electrolytic cleaning → annealing (box annealing) → temper rolling → nickel titanium alloy plating (inner side) → nickel plating (inner and outer side) → carbon dispersion Nickel alloy plating (inner surface side) → Heat treatment (box annealing method) → Temper rolling n) Low carbon aluminum killed steel (I) → Cold rolling → Electrolytic cleaning → Annealing (box annealing method) → Temper rolling → Nickel plating (Inner, outer surface side) → carbon-dispersed nickel alloy plating (inner surface side) → heat treatment (box-type annealing method) → temper rolling Each plating treatment in the steps a) to n) was performed under the following conditions.

<Nickel plating>
Bath composition Nickel sulfate 300g / L
Nickel chloride 35g / L
Boric acid 40g / L
Bit inhibitor (sodium lauryl sulfate) 0.4mL / L
Anode Nickel Beret (Stainless steel pellets from INCO Co., Ltd. in a titanium basket)
Filled with polypropylene anode bag)
Stirring air stirring
pH 4.0-4.6
Bath temperature 55-60 ° C
Current density 15A / dm ²

<Nickel-titanium alloy plating>
Bath composition Nickel sulfate 8g / L
Potassium fluoride titanium 24g / L
L-glutamic acid 8g / L
Glycine 10g / L
Anode Nickel Beret (Stainless steel pellets from INCO Co., Ltd. in a titanium basket)
Filled with polypropylene anode bag)
Stirring air stirring
pH 5.0-5.5
Bath temperature 55-60 ° C
Current density 5A / 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

<Nickel-phosphorus alloy plating>
Bath composition Nickel sulfate 300g / L
Nickel chloride 35g / L
Boric acid 20g / L
Phosphorous acid 5-20g / L
Bit inhibitor (sodium lauryl sulfate) 0.4mL / L
Anode Nickel Beret (Stainless steel pellets from INCO Co., Ltd. in a titanium basket)
Filled with polypropylene anode bag)
Stirring air stirring
pH 4.0-4.6
Bath temperature 55-60 ° C
Current density 15A / dm ²

<Nickel-cobalt alloy plating>
Bath composition Nickel sulfate 250g / L
Cobalt sulfate 5-40g / L
Nickel chloride 40g / L
Boric acid 30g / L
Anode Nickel Beret (Stainless steel pellets from INCO Co., Ltd. in a titanium basket)
Filled with polypropylene anode bag)
Stirring air stirring
pH 1.5-2.5
Bath temperature 40-60 ° C
Current density 10-15A / dm ²

<Nickel-cobalt-boron alloy plating>
Bath composition Nickel sulfate 250g / L
Cobalt sulfate 30g / L
Nickel chloride 40g / L
Trimethylamine borane 10g / L
Boric acid 20g / L
Anode Nickel Beret (Stainless steel pellets from INCO Co., Ltd. in a titanium basket)
Filled with polypropylene anode bag)
Stirring air stirring
pH 1.5-2.5
Bath temperature 40-60 ° C
Current density 10-15A / dm ²

<Carbon dispersion nickel plating>
Bath composition Nickel sulfate 300g / L
Nickel chloride 35g / L
Boric acid 40g / L
Ketjen black (average particle size 40nm) 10-20g / L
Dispersant TKDA-10 10-20 g / L from Gokoku Color Co., Ltd.
(Naphthalene sulfonic acid condensate system)
Bit inhibitor (sodium lauryl sulfate) 0.4mL / L
Anode Nickel Beret (Stainless steel pellet made by INCO Co., Ltd. in a titanium basket)
Filled with polypropylene anode bag)
Stirring air stirring
pH 4.5-5.0
Bath temperature 55-60 ° C
Current density 5-10 A / dm ²

<Carbonaceous dispersed nickel-cobalt-phosphorus alloy plating>
Bath composition Nickel sulfate 250g / L
Cobalt sulfate 30g / L
Nickel chloride 40g / L
Phosphorous acid 15g / L
Boric acid 20g / L
Carbon black (average particle size 180nm) 10-20g / L
Dispersant TKDA-10 10-20 g / L from Gokoku Color Co., Ltd.
(Naphthalene sulfonic acid condensate system)
Bit inhibitor (sodium lauryl sulfate) 0.4mL / L
Anode Nickel Beret (Stainless steel pellets from INCO Co., Ltd. in a titanium basket)
Filled with polypropylene anode bag)
Stirring air stirring
pH 4.5-5.0
Bath temperature 55-60 ° C
Current density 5-10 A / dm ²

<Carbon dispersion nickel-boron alloy plating>
Bath composition Nickel sulfate 240g / L
Nickel chloride 40g / L
Trimethylamine borane 6-12g / L
Boric acid 30g / L
Acetylene black (average particle size 120 nm) 10-20 g / L
Dispersant TKDA-10 10-20 g / L from Gokoku Color Co., Ltd.
(Naphthalene sulfonic acid condensate system)
Bit inhibitor (sodium lauryl sulfate) 0.4mL / L
Anode Nickel Beret (Stainless steel pellets from INCO Co., Ltd. in a titanium basket)
Filled with polypropylene anode bag)
Agitation Agitation of plating solution
pH 4.5-5.0
Bath temperature 55-60 ° C
Current density 1-5A / dm ²
Samples (sample numbers 1 to 16) of the plated steel sheets for battery containers shown in Tables 2 and 3 were prepared as described above. In Sample Nos. 15 to 16, no heat treatment was performed.

[Create battery container]
After blanking a blank with a 57 mm diameter from the samples of sample numbers 1 to 16, a cylindrical LR6 type battery (AA type battery) having an outer diameter of 13.8 mm and a height of 49.3 mm by drawing with 10 steps. Molded into a container.

[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. A conductive material mainly composed of graphite powder was applied to the inner surface of the battery container. Subsequently, the positive electrode mixture beret previously produced was press-inserted into the battery container. 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.

<Leakage evaluation>
After preparing 100 batteries, the battery was inserted into a 90 ° C., RH 50% constant temperature and humidity atmosphere, and the leakage rate (%) of the electrolyte after 5 days, 10 days, 15 days and 20 days was determined.

  As shown in Table 4, it is recognized that all of the batteries using the plated steel sheet for the battery container in which the nickel-titanium alloy plating is applied to the battery container inner surface side according to the present invention are remarkably improved in leakage resistance. .

After a nickel-titanium alloy plating layer is formed in advance on the battery vessel inner surface of the steel sheet, nickel plating, various nickel-alloy platings, carbon-dispersed nickel, or various nickel-alloy platings in which carbon is dispersed, etc. When hard plating is applied, even if the nickel plating layer formed thereon is thin and pinholes are present, or cracking occurs in the hard plating layer when forming into a battery container, Even if it is exposed, the leakage resistance is improved. As a result, it is possible to improve the discharge performance of the battery by forming a hard plating layer on the inner side of the battery case, causing cracks when forming the battery case, and improving the adhesion with the positive electrode active material. On the other hand, the conflicting problem that iron is exposed and leakage resistance is liable to deteriorate due to excessive cracks is solved by using the plated steel sheet for battery containers of the present invention. That is, it is possible to improve the discharge performance of the battery without impairing the leakage resistance of the battery.

Claims (7)

A plated steel sheet for a battery container, wherein a metal layer containing titanium is formed on a steel sheet on the side of the steel sheet that is the inner surface of the battery container. The plated steel sheet for battery containers according to claim 1, wherein a nickel layer is formed on the metal layer containing titanium. The plated steel sheet for battery containers according to claim 1, wherein a nickel alloy layer is formed on the metal layer containing titanium. The plated steel sheet for battery containers according to claim 2, wherein carbonaceous matter is dispersed in the nickel layer or the nickel alloy layer. The nickel alloy is any one of a nickel-tin alloy, a nickel-phosphorus alloy, a nickel-cobalt alloy, a nickel-cobalt-phosphorus alloy, a nickel-boron alloy, and a nickel-cobalt-boron alloy, Item 5. A plated steel sheet for battery containers according to Item 3 or 4. The battery container formed by shape | molding the plated steel plate for battery containers in any one of Claims 1-5 in a bottomed cylindrical shape. A battery comprising the battery container according to claim 6.