JP4995140B2 - Ni-plated steel sheet for containers, container manufactured thereby, and method for manufacturing the same - Google Patents

Description

  The present invention relates to a Ni-plated steel sheet, a container manufactured using the same, and a method for manufacturing the same.

  Until now, steel cans for batteries have been mainly manufactured for primary batteries. Normally, Ni plating is applied to the battery can for corrosion resistance of the outer surface and contents. The manufacturing method can be roughly divided into two, one is a method called a post-plating method, and the other is a method called a pre-plating method.

  In the post-plating method, a steel plate that has not been plated is punched out, formed into a can shape by a press, and then plated. In this method, plating is mainly performed by barrel plating. In barrel plating, the outer surface can be uniformly plated, but it is difficult to ensure the uniformity of the inner surface. If the plating on the inner surface is not uniform, corrosion due to the contents tends to proceed, but it may not be a big problem for primary battery applications. In addition, there is also a method of ensuring the plating uniformity on the inner surface even in the post-plating method, and Patent Document 1 introduces a method of performing electrolysis by placing an anode electrode inside the can.

  In the pre-plating method, plating is performed on both sides with a plating line, the steel sheet is punched out, and formed into a can shape by pressing. In this method, a uniform plating layer can be obtained on both the inner and outer surfaces. When hard plating is applied, cracks may occur in the plating layer during processing, exposing the iron core, and corrosion there may be a problem. For this reason, as in Patent Document 2, there is one in which an Fe—Ni diffusion layer is formed by heating after plating, and the followability of the plating layer to the steel sheet is improved.

  In addition, a method of forming a plating layer by pre-plating only on the inner surface by press molding as in Patent Document 3, and forming a plating layer by barrel plating on the outer surface after pressing, or both surfaces as in Patent Document 4 There is also a method of forming a plating layer and forming the plating layer by barrel plating on the outer surface after pressing.

JP 2007-277634 A JP 61-235595 A Japanese Patent No. 2940732 JP 2007-122940 A

  Until now, steel cans for batteries have been manufactured mainly for primary batteries with a recommended use period of 1.5 to 5 years, so even if there are some uneven plating or uncoated parts, It was not a big problem. However, in recent years, the amount of secondary batteries used has increased, and steel cans have also been increasingly used for secondary batteries that are used over a long period of time. Accordingly, durability of the steel can is required, and it is required that the inner surface, the outer surface, and the end of the can have a uniform plating layer. For this purpose, post-plating is effective by the method of Patent Document 1, but this method is disadvantageous when the amount of use increases and mass production is required because the anode electrode must be put inside the can.

  In the pre-plating method, the method of Patent Document 2 is effective for improving the uniformity of the plating layer, but in the case of having a plating layer, the plating layer on the outer surface of the can is easily scraped, and the plating layer can be scraped. As a result, the press mold may be damaged, and it may be necessary to increase the replacement frequency of the mold rather than pressing a non-plated steel sheet, which is disadvantageous when mass production is required. Further, in the pre-plating method, the end portion of the steel plate is exposed no matter how the plating is performed, and therefore the end portion may be exposed depending on the shape of the battery.

  In addition, in the case of having a plating layer only on one side as in Patent Document 3, a can having a relatively uniform Ni plating layer on both the inner and outer surfaces can be manufactured as a final product, but until the plating treatment after pressing is performed, Ni Since the potential difference between the plated surface and the surface without the plating layer becomes large, depending on the handling, the problem that the surface without the plating layer is more likely to corrode than the steel plate without the plating layer on both sides. There is a die having a thick plating layer on both sides as in Patent Document 4, but corrosion during handling is less likely to occur, but galling occurs in the plating layer during continuous pressing. There was a problem of severe damage.

  The present invention has been made in view of the above-described situation, and an object thereof is to provide a can having a uniform plating layer on the inner surface, the outer surface, and the end, and a method for manufacturing such a can more easily.

  As a result of diligent investigations to solve the above problems, the present inventors have found that the steel plate has an inner surface on which it is difficult to obtain a uniform plating layer by post-plating. In order to further suppress the occurrence of cracks in plating due to processing, diffusion treatment by heating is performed, and the surface that becomes the outer surface is given a primary rust prevention function by reducing the potential difference with the surface that becomes the inner surface, In order to suppress the occurrence of galling during pressing and reduce the aggressiveness to the mold, Ni plating is applied very thinly, and the Ni is diffused inside the steel sheet by heating, and after press molding, barrel plating It has been found that cans having uniform plating layers on the inner surface, outer surface, and end portions can be produced by plating, and the present invention has been completed based on such knowledge.

That is, the gist of the present invention is as follows.
(1) Having a Fe—Ni diffusion layer with a thickness of 0.5 μm or more and 4 μm or less on the surface that becomes the inner surface of the container by press molding, and further having a Ni layer with a thickness of 0.25 μm or more and 4 μm or less The outer surface of the container has Ni with an adhesion amount of 0.05 g / m ² or more and less than 1.5 g / m ² , the Ni is diffused inside, and the Ni / (Fe + Ni) mass of the surface layer A Ni-plated steel sheet for containers, wherein the ratio is 0.1 or more and 0.9 or less.
(2) The base material is a steel plate, the inner surface has a Fe-Ni diffusion layer with a thickness of 0.5 μm or more and 4 μm or less, and further has a Ni layer with a thickness of 0.25 μm or more and 4 μm or less, A container having an Fe—Ni diffusion layer having a thickness of 0.1 μm or more and 0.5 μm or less on an outer surface, and further having a Ni layer having a thickness of 0.5 μm or more and 5 μm or less on the Fe—Ni diffusion layer.
(3) The steel plate described in (1) is pressed so that the surface having the Ni layer and the Fe—Ni diffusion layer becomes the inner surface, and Ni plating with a thickness of 0.5 μm or more and 5 μm or less is applied to the outer surface of the container by barrel plating. A method for producing a container characterized by the above.
(4) The steel plate described in (1) is pressed so that the surface having the Ni layer and Fe—Ni diffusion layer is the inner surface, and Ni plating with a thickness of 0.5 μm or more and 5 μm or less is applied to the outer surface of the container by barrel plating. A container characterized by being applied.
(5) A battery in which the container according to (2) or (4) is filled with at least an electrolytic solution, an electrode, and a separator.

  According to the present invention, a can having a uniform plating layer on the inner surface, outer surface, and end portion can be efficiently manufactured. As a result, mass production of cans having sufficient durability even when used as a container for a battery used for a long period of time, such as a secondary battery, has become possible. Therefore, it can be said that the present invention is an extremely industrial invention.

  If the inner surface is plated after press molding, it is difficult to obtain uniform plating with general barrel plating. To obtain uniform plating, there are methods such as electrolysis by placing electrodes inside each can and inside the can. It is necessary and productivity decreases. On the other hand, if the surface to be the inner surface is pre-plated before pressing, it is easy to obtain a uniform plating layer on the inner surface of the container after pressing. Further, during press forming, sliding between the steel plate surface and the mold, which is the inner surface of the can, is only due to deformation of the steel plate, so that galling is unlikely to occur. Therefore, if the plating is highly adhesive and flexible, the damage caused by processing is small. Therefore, if there is an Fe—Ni diffusion layer that enhances adhesion between the steel plate and the soft Ni pre-plated layer on the inner surface of the can, damage due to processing during pressing may be prevented.

  On the other hand, if the outer surface has the same pre-plated layer as the inner surface, the outer surface slides more severely with the mold during pressing than the inner surface. Therefore, it is difficult to ensure the uniformity of the plating layer as compared with the inner surface, and there is a possibility that the mold is damaged during continuous pressing due to galling. However, if there is no plating layer on the outer surface, the potential difference between the inner surface with the plating layer and the inner surface becomes large, and therefore corrosion tends to proceed on the outer surface that is lower than the inner surface. In the present invention, this decrease in corrosion resistance can be eliminated by thinly pre-plating Ni on the surface that becomes the outer surface of the container. It has been found that galling during pressing is less likely to occur than with a treated steel sheet, and damage to the mold during continuous pressing can be reduced.

  Therefore, the outer surface may be thinly plated with Ni before pressing, and then subjected to a diffusion treatment. When plating on the outer surface of the can is performed by barrel plating after pressing, a plating layer having no defect may be formed.

  The present invention will be described in detail below.

  The steel plate of the present invention will be described. With respect to the surface which becomes the inner surface after press molding, sufficient adhesion cannot be obtained unless the thickness of the Fe—Ni diffusion layer is 0.5 μm or more. On the other hand, when the thickness of the Fe—Ni diffusion layer exceeds 4 μm, cohesive failure of the alloy layer is likely to occur, resulting in a decrease in adhesion. Therefore, the thickness of the Fe—Ni diffusion layer is preferably 0.5 μm or more and 4 μm or less.

  In addition, if the Ni layer has a certain thickness or more, the surface cannot be completely covered after pressing, and sufficient corrosion resistance may not be obtained. The thickness of the Ni layer is preferably 0.25 μm or more. On the other hand, if the Ni layer is too thick, the plating layer cannot follow the deformation of the steel sheet, and the plating layer is peeled off. The thickness of the Ni layer may be 4 μm or less.

  As a more preferable range, when the Ni layer is thicker than 2 μm, the improvement rate of the corrosion resistance by increasing the Ni layer is lower than that when the Ni layer is 2 μm or less. Further, when the Fe—Ni diffusion layer is 0.7 μm or more and 2 μm or less and the Ni layer is 0.5 μm or more and 2 μm or less, the adhesion and corrosion resistance of the plating and the economic efficiency can be balanced at a high level. More preferred.

  The surface that will be the outer surface after the other press molding, if there is no Ni on the surface, depending on the management method, corrosion is likely to occur during transportation and storage, so there was Ni for primary rust prevention Is good. However, in general, if there is a Ni plating layer on the outer surface after pressing, Ni plating is galling during pressing, which causes damage to the mold, and the frequency of changing the mold is higher than pressing a steel sheet without plating. It is known that Therefore, when we examined a method that can achieve both primary rust prevention and continuous pressability, the Ni galvanized and heat-diffusion one is superior to the original steel plate due to the Ni effect. It was found that the surface was hardened by a slight diffusion of Ni into the steel sheet, the galling of the steel sheet surface was less than that of a solid steel sheet, and excellent continuous pressability was exhibited.

The diffusion range is such that the adhesion amount of Ni is 0.05 g / m ² or more and less than 1.5 g / m ² and the Ni / (Fe + Ni) mass ratio of the surface layer is 0.1 or more and 0.9 or less. Good. The lower limit of the Ni adhesion amount is determined by the fact that there is almost no difference from a steel plate with solid corrosion resistance if there is no Ni above a certain level. The upper limit of the Ni adhesion amount is cracked in the diffusion layer if the hard diffusion layer is too thick. The lower limit of the Ni / (Fe + Ni) mass ratio of the surface layer is determined from the fact that there is almost no difference from a steel plate with a solid corrosion resistance, like the lower limit of the adhesion amount, and the Ni / (Fe + Ni) mass of the surface layer is determined. The upper limit of the ratio is determined by the fact that Ni alone is softer than the surface of a solid steel plate, so that Fe must be diffused to the surface in order to prevent galling of the press.

More preferable range is that the Ni adhesion amount is 0.1 g / m ² or more and 1.0 g / m ² or less, and the Ni / (Fe + Ni) mass ratio of the surface layer is 0.3 or more and 0.7 or less. preferable. When the adhesion amount of Ni is 0.1 g / m ² or more or the Ni / (Fe + Ni) mass ratio of the surface layer is 0.3 or more, the primary rust prevention effect is enhanced, but it is more oxidized than the solid steel plate. The film is difficult to grow, and adhesion of plating can be enhanced when plating after molding. When the adhesion amount of Ni is 1.0 g / m ² or less or the Ni / (Fe + Ni) mass ratio of the surface layer is 0.7 or less, the diffusion layer having a high Ni concentration is thin. It is easy to follow the deformation, and it is difficult for the diffusion layer to be deeply cracked or peeled off. Further, in the range of 1.0 g / m ² Ni deposition amount is from 0.8 g / m ^2, since there is little performance difference, the 0.8 g / m ² in terms of economy may be the upper limit.

  The thickness of the Ni layer and the Fe—Ni diffusion layer here is analyzed by GDS (glow discharge emission spectroscopic analyzer) from the surface to the inside of the steel plate, and the strength of Fe becomes maximum as shown in FIG. As a standard, the Fe strength is in the range of 80% or more and 100% or less of the reference value, and the range of Fe strength is 20% or more and less than 80% of the reference value. The diffusion layer and the range d in which the strength of Fe is less than 20% of the reference value can be obtained as the Ni layer. Further, the Ni adhesion amount can be quantified by covering the surface not to be measured with a resin, dissolving the plating layer on the measurement surface with an acid, and subjecting it to ICP. The Ni / (Fe + Ni) mass ratio of the surface layer can be determined by measuring the electron extraction angle at 45 ° from the normal direction of the sample with an AES (Auger Electron Spectrometer).

  The base steel sheet is not particularly limited as long as it can be Ni-plated, but considering that it can be used for processing into battery cans, Ti, Nb, etc. added to ultra low carbon steel alone or in combination, Low carbon Al killed steel, B-added low carbon steel and the like are preferable. Further, it can be used for non-recrystallized steel sheets after cold rolling, steel sheets after recrystallization annealing, and steel sheets after temper rolling, but in the present invention, the presence of an Fe-Ni diffusion layer is essential. Therefore, it is preferable from an economical viewpoint that the diffusion treatment and the recrystallization annealing of the base steel sheet are simultaneously performed after the Ni plating. From this viewpoint, the most advantageous embodiment of the present invention is to use a non-recrystallized steel sheet after cold rolling as the base steel sheet.

  The pretreatment for plating is not particularly limited as long as it is a pretreatment for performing Ni plating, and ordinary treatment degreasing, pickling, etc. may be performed.

  The type of plating is not particularly limited as long as it is mainly Ni, and hard gloss plating may be used, but hard plating may easily cause cracks in the plating layer depending on the molding method. The battery can of the present invention is assumed to be used as an internal part of HEVs and electric vehicles, and since it does not touch the eyes of general users on a daily basis like a primary battery, it must have a glossy appearance. Therefore, soft pure Ni plating by a normal watt bath is preferable.

The formation method of the Fe-Ni diffusion layer on the surface serving as the container inner surface and the Ni diffused region on the surface serving as the container outer surface is particularly limited as long as Ni and Fe can be diffused so as to be in a predetermined state. However, it can be formed by heat treatment in an inert gas or reducing gas atmosphere. The heat treatment may be either batch processing or continuous processing in a steel sheet production line, but continuous processing is preferable in view of productivity and uniformity. Specifically, the treatment is performed at a temperature of about 700 to 850 ° C. for a soaking time of about 20 to 60 seconds. At this time, if the Ni plating adhesion amount on the inner surface of the container is about 10 g / m ² or more, depending on the conditions, an Fe—Ni diffusion layer and a recrystallized and softened Ni plating layer are formed on the upper layer. Is done. Further, for the surface that becomes the outer surface of the container, after the adhesion amount of Ni specified in the present invention is adhered, the heat treatment for forming the Fe—Ni diffusion layer of the surface that becomes the inner surface of the container is performed at the same time. Adhering Ni diffuses inside, and the Ni / (Fe + Ni) mass ratio of the surface layer can be made 0.1 to 0.9. In addition, when the non-recrystallized steel plate is used as the base steel plate, the heat diffusion treatment and the recrystallization annealing of the steel plate can be simultaneously performed by setting the heat treatment here to the recrystallization temperature or higher of the steel plate.

  Further, the surface roughness may be adjusted by rolling after plating, and may be performed using a roll having an appropriate roughness required for the product. Roughness such as front and back surfaces or different roughness may be used, and rolling can be performed by adjusting the roughness of the roll according to the application.

  When the plated steel plate described so far is pressed into a can shape and plated on the outer surface of the can, the inner surface, the outer surface, and the end have uniform plating layers, and the adhesion of the inner plating layer is particularly high, and the battery contents After filling, a can in which the plating layer is not peeled off even if the lid is covered with caulking can be manufactured.

  The press molding method is not particularly limited, and is performed by a method such as a deep drawing method, a DI (Drawing and Ironing) method, or a DTR (Draw Thin and Redraw) method that has been conventionally used in the can manufacturing process. can do.

  If the inner and outer surfaces of the container after pressing do not have a certain Ni plating thickness or more, it may not be possible to prevent corrosion and even perforation under severe conditions in long-term use. A predetermined Ni plating thickness is required.

  The outer surface of the container does not have a Ni layer at the time of pressing, so Ni plating is performed by means such as barrel plating. It is necessary to apply Ni plating so that the Ni plating thickness of the outer surface of the container is 0.5 μm or more. However, when the Ni layer is thicker than 5 μm, the rate of improvement in corrosion resistance by increasing the thickness of the Ni layer is lower than when the Ni layer is 5 μm or less. Therefore, Ni plating may be performed so as to be 5 μm or less from the economical point of view. Therefore, the upper limit and the lower limit of the Ni plating layer on the outer surface of the container are 5 μm and 0.5 μm, respectively. As a more preferred range, if the lower limit of the thickness is 1 μm or more, high corrosion resistance can be stably exhibited, and if the upper limit is 3 μm, sufficient corrosion resistance can be exhibited in normal use.

  The Ni layer thickness on the inner surface of the container after pressing may be not less than 0.25 μm and not more than 4 μm, as before pressing. Here, for the inner surface of the container, from the Ni layer thickness before pressing, the thickness is slightly reduced after pressing along with press molding, and when the outer surface of the container is plated after pressing, the inner surface also has plating attached, This increases the Ni layer thickness. After the press and outer surface plating, the Ni layer thickness on the inner surface of the container may be 0.25 μm or more and 4 μm or less.

In the present invention, the surface to be the outer surface of the container has a pre-coating weight 0.05 g / m ² or more 1.5 g / m ² less than Ni before the press, the Ni has diffused into the surface layer of Ni / (Fe + Ni) mass ratio is 0.1 or more and 0.9 or less. The Ni plating after pressing is performed on the Ni diffused layer. As a result, the outer surface of the Ni-plated container has an Fe—Ni diffusion layer having a thickness of 0.1 μm to 0.5 μm below the Ni plating layer. By having such a Fe—Ni diffusion layer under the Ni layer on the outer surface of the container, the adhesion of the Ni layer can be enhanced.

  The plating thickness of the inner and outer surfaces here is a value measured by GDS as described above. For example, round cans can be centered at the bottom of the can as shown in FIG. Measured around a portion 5 mm from the opening and the central height portion of the can side wall, with the strength of Fe being the maximum as shown in FIG. 1, the Fe strength is less than 20% of the reference value. The range A is defined as the Ni layer thickness, and the region C in which the Fe strength is 20% or more and less than 80% of the reference value can be obtained as the Fe—Ni diffusion layer thickness.

  The plating after the press is not particularly limited as long as it is plating mainly composed of Ni. However, when the can is finally covered, since processing such as caulking may be performed, soft pure Ni Plating is preferred. However, when a can is allowed to flow through the battery production line, if it is required to have a high surface slidability in order to ensure the flow of the can, a hard gloss plating to which S or the like is added may be used. good.

  The plating method is not particularly limited as long as it can finally form a predetermined Ni layer and Fe—Ni diffusion layer. Even if electroless plating is performed, it can be electrolyzed by connecting it to a single can cathode electrode. Plating or barrel plating may be used, but electroless plating takes a long time to obtain a predetermined thickness, and there is relatively much plating on the inner surface of the can that does not require plating. The method of plating one can and one can takes time, and it is preferable to plate by barrel plating. With barrel plating, it is possible to plate a large number of cans at one time, and barrel plating has the disadvantage that almost no plating is attached inside, but in the case of the present invention, the cutting edge and the outer surface of the steel plate Since Ni plating is sufficient, it is more economical than uniformly plating the whole.

  The battery using the Ni-plated steel sheet of the present invention and the can made thereby has high durability because the productivity of the can is high and the battery is low in cost and economical, and there are no plating defects on the inner and outer surfaces of the can. Have sex.

The container of the present invention has a Fe—Ni diffusion layer having a thickness of 0.5 μm or more and 4 μm or less on the surface that becomes the inner surface of the container by press molding, and further a Ni layer having a thickness of 0.25 μm or more and 4 μm or less. And the outer surface of the container contains Ni having an adhesion amount of 0.05 g / m ² or more and less than 1.5 g / m ² , and the Ni diffuses inside, and Ni / (Fe + Ni in the surface layer) ) Using a Ni-plated steel sheet for containers, characterized in that the mass ratio is 0.1 or more and 0.9 or less, and pressing so that the surface having the Ni layer and Fe—Ni diffusion layer becomes the inner surface, barrel plating The outer surface of the container is subjected to Ni plating with a thickness of 0.5 μm or more and 5 μm or less. Accordingly, the container of the present invention can easily mass-produce cans having sufficient durability even when used as a container for a battery that is used for a long time like a secondary battery.

  The battery of the present invention is a battery in which the container of the present invention is filled with at least an electrolytic solution, an electrode, and a separator. Since the battery of the present invention has high can productivity, the battery is low in cost and economical, and has high durability because there are no plating defects on the inner and outer surfaces of the can.

  The invention will be further described on the basis of examples.

First, the evaluation method will be described.
・ Ni layer ・ Fe-Ni diffusion layer thickness (μm)
The thicknesses of the Ni layer and the Fe—Ni layer were evaluated using a GDS (Glow Discharge Optical Emission Spectrometer). In the evaluation method, depth analysis is performed from the surface toward the inside of the steel sheet, and the strength of Fe is 80% or more and 100% or less of the reference value with reference to the case where the strength of Fe is maximum as shown in FIG. The range d was determined as the ground layer, the Fe strength was 20% or more of the reference value, the range U was less than 80%, the Fe-Ni diffusion layer, and the range A in which the Fe strength was less than 20% of the reference value was determined as the Ni layer. .

-Ni adhesion amount (g / m ² )
The amount of Ni adhesion was determined using ICP. The surface to be evaluated was covered with a resin, the plating layer on the evaluation surface was dissolved with an acid, the amount of Ni contained therein was determined, and the amount of Ni and the area of the surface on which the plating layer was dissolved were calculated.

Ni / (Fe + Ni) mass ratio The Ni / (Fe + Ni) mass ratio of the surface layer was evaluated by AES (Auger Electron Spectrometer). The electron extraction angle was measured by tilting it at 45 ° from the normal direction of the sample, and the mass ratio FeX: NiX of Fe and Ni was obtained from the intensity of the spectrum, and Ni / (Fe + Ni) mass ratio = NiX / (FeX + NiX) was calculated. Asked. The evaluation was less than 0.1 as “below standard”, 0.1 or more and 0.9 or less as “within standard”, and over 0.9 as “over standard”.

(Performance evaluation method)
-External surface galling resistance As for external surface galling resistance, a steel plate was pressed, a normal LR06 type battery-shaped can was produced, the outer surface was observed with SEM (x1000), and the presence of hairline galling marks was examined. In the evaluation, “no galling” was evaluated as “◯”, extremely slight galling was “Δ”, galling was “×”, and the criteria were satisfied up to “Δ”.

  Moreover, the evaluation result of galling resistance has a correlation with continuous breathing property.

-Corrosion resistance Corrosion resistance manufactured the can for normal LR06 type | mold batteries, the positive electrode terminal part outer surface was faced down, the salt spray test (JIS-Z-2371) was performed for 3 hours, and the red rust generation | occurrence | production condition was observed visually. In the evaluation, “○” indicates that there is no rust, “Δ” indicates that there is very slight rust (up to 5 point-like rusts), “×” indicates that rust is present, and “Δ” indicates that the standard is satisfied.

  Next, a method for creating a sample will be described.

  As the original plate, NbTi-SULC steel having a thickness of 0.25 mm and not recrystallized after cold rolling was used. After pre-treatment of degreasing and pickling on the plate, a matte Watt bath is used as the plating bath, and the surface of the Ni layer is the thickness of each example and comparative example or the amount of adhesion on each side. Each time, electroplating was performed with the current density controlled. Next, in a non-oxidizing atmosphere at 800 ° C., the thickness of the Fe—Ni diffusion layer on the surface serving as the inner surface of the container is maintained for 40 to 60 seconds so as to be the thickness of each example and comparative example, and the recrystallization of the original plate proceeds. At the same time, the Ni plating layer was diffused on both sides of the steel plate. The temper rolling was dry rolled with a two-stand rolling mill.

  This plate was pressed into the shape of a normal LR06 battery can.

  Table 1 shows the Ni layer, Fe—Ni layer thickness, Ni adhesion amount, Ni adhesion amount and Ni / (Fe + Ni) mass ratio of the surface to be the can outer surface of the prepared plated steel sheet. Table 1 shows the galling state of the outer surface of the can when the can was formed by pressing. In both Tables 1 and 2, numerical values that are out of the scope of the present invention are underlined.

  Examples 1 to 14 in Table 1 are examples of the present invention, and Comparative Examples 1 to 6 are comparative examples. In the examples, the criteria were satisfied with Δ or ○ in the evaluation of the anti-galling property on the outer surface. On the other hand, in Comparative Examples, Comparative Examples 3 to 6 satisfied the standard with ○, but the amount of Ni adhesion on the outer surface was small and the Ni / (Fe + Ni) mass ratio was less than the standard and Comparative Example 1 with a large amount of Ni adhesion on the outer surface. In Comparative Example 2 in which the / (Fe + Ni) mass ratio was over the standard, the standard was not satisfied with x.

  Next, as shown in Table 2, using a steel plate selected from the examples and comparative examples in Table 1 as a working steel plate, Ni plating was performed mainly on the outer surface of the vessel by barrel plating. Table 2 shows the thicknesses of the Ni layer and the Fe—Ni diffusion layer on the outer surface of the container, and the thicknesses of the Ni layer and the Fe—Ni diffusion layer on the inner surface. Table 2 shows the results of evaluating the corrosion resistance using the prepared cans.

  Examples 15 to 30 in Table 2 are examples of the present invention. In each example, both the inner and outer surface corrosion resistance evaluations satisfied the criteria with Δ or ○.

  Comparative Example 7 prepared using the plate of Comparative Example 3 having a thin inner surface Fe—Ni diffusion layer, Comparative Example 8 using the plate of Comparative Example 4 having a thick inner surface Fe—Ni diffusion layer, In Comparative Example 9 prepared using the plate of Comparative Example 5 having a small Ni layer thickness, the corrosion resistance of the inner surface was x and did not satisfy the standard.

  Comparative Example 10 prepared by using Comparative Example 6 having a thick Ni layer on the inner surface satisfied the criteria for both the inner and outer surface corrosion resistance evaluations with Δ or ○, but the effect of increasing the inner plating thickness was positive. Therefore, it is not economical when considering the cost increase by increasing the plating thickness.

  In Comparative Example 11 prepared using the plate of Example 3, the Ni layer thickness on the outer surface was thin, and the corrosion resistance of the outer surface was x, which did not satisfy the standard.

  In Comparative Example 12 prepared using the plate of Example 3, the Ni layer thickness of the outer surface was thick and the evaluation of the corrosion resistance of the inner surface and the outer surface satisfied the standard with ○, but the effect of increasing the outer plating thickness was positive It is not economical because it does not come out, considering the cost increase by increasing the plating thickness.

As mentioned above, although preferred embodiment of this invention was described referring an accompanying drawing, it cannot be overemphasized that this invention is not limited to this example. It should be understood that various changes and modifications within the scope of the claims belong to the technical scope of the present invention.

It is a schematic diagram of the reference | standard which determines the thickness of a Ni layer and a Fe-Ni diffused layer from the measurement result of GDS. It is the schematic diagram which showed the plating thickness measurement site | part of the round can. It is the schematic diagram which showed the plating thickness measurement site | part of the square can.

Explanation of symbols

A) Fe layer with 100% strength b) Ni layer c) Fe-Ni diffusion layer d) Geotechnical layer c GDS measurement part Can bottom center key GDS measurement part Can side center center GDS measurement part 5mm from the can opening
S GDS measurement unit Can bottom center center GDS measurement unit Can side center center GDS measurement unit 5mm from can opening

Claims (5)

The outer surface of the container has a Fe-Ni diffusion layer with a thickness of 0.5 μm or more and 4 μm or less on the surface that becomes the inner surface of the container by press molding, and further has a Ni layer with a thickness of 0.25 μm or more and 4 μm or less on it. The surface has Ni with an adhesion amount of 0.05 g / m ² or more and less than 1.5 g / m ² , the Ni is diffused inside, and the Ni / (Fe + Ni) mass ratio of the surface layer is 0.1. As mentioned above, it is 0.9 or less, Ni-plated steel sheet for containers.   The base material is a steel plate, the inner surface has a Fe—Ni diffusion layer with a thickness of 0.5 μm or more and 4 μm or less, and further has a Ni layer with a thickness of 0.25 μm or more and 4 μm or less on the outer surface. A container having a Fe—Ni diffusion layer having a thickness of 0.1 μm or more and 0.5 μm or less, and further having a Ni layer having a thickness of 0.5 μm or more and 5 μm or less thereon.   The steel sheet according to claim 1 is pressed so that the surface having the Ni layer and the Fe-Ni diffusion layer becomes the inner surface, and Ni plating with a thickness of 0.5 μm or more and 5 μm or less is performed on the outer surface of the container by barrel plating. A method for producing a container.   The steel sheet according to claim 1 is pressed so that the surface having the Ni layer and the Fe-Ni diffusion layer becomes the inner surface, and Ni plating with a thickness of 0.5 μm or more and 5 μm or less is performed on the outer surface of the container by barrel plating. Container.   A battery in which the container according to claim 2 or 4 is filled with at least an electrolytic solution, an electrode, and a separator.

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