JP2003277974A - Method for producing Ni-plated steel sheet for battery can - Google Patents

Abstract

(57) [Problem] To provide a method for producing a Ni-plated steel sheet for a battery can excellent in corrosion resistance, battery characteristics, and slidability. SOLUTION: This is a method for producing a plated steel sheet for a battery can, wherein the P content is 0.1 mass% or more without Ni plating or Ni plating on the surface to be the outer surface of the can.
mass-% Ni-P alloy plating, and then heat treatment is performed, so that Fe-Ni
It is characterized in that a diffusion layer is formed. In this case, Ni-
The adhesion amount of P alloy plating is 1 g / m ² or more as Ni, and the total N of Ni plating and Ni-P alloy plating is N
It is desirable that the i amount is 9 g / m ² or more. On the inner surface of the can, one or two types of Ni plating or Ni-P alloy plating having a P content of 0.1 mass% or more and less than 3 mass% are applied in an amount of Ni (in the case of a multi-layer, a total of two or more). After the application of 1 g / m ² or more (with the amount of Ni), the heat treatment is performed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a plated steel sheet material used for a battery can, and more specifically, a method for producing a plated steel sheet material capable of improving the corrosion resistance, battery characteristics and surface sliding property of the battery can. It is about the method.

[0002]

2. Description of the Related Art Generally, a Ni-plated steel plate is used as a material for battery cans. Conventionally, Ni plating has been performed by so-called barrel plating after processing into cans. However, since the adhesion of Ni plating to the inner surface of the can is not sufficient and there is a problem of instability in quality, the pre-plated steel plate can be It is being replaced by the method of processing. In the case of a pre-plated steel sheet, since the Ni plating layer is hard and the spreadability is poor, the press workability is inferior, and there is a problem that the plating peels off during processing and corrosion resistance easily deteriorates.

To address this problem, heat treatment after Ni plating forms a Fe-Ni diffusion layer at the interface between the plating and the base metal to improve adhesion, and at the same time recrystallizes and softens Ni to form a plated layer. A method for improving the spreadability is known, and press workability and corrosion resistance are significantly improved (for example, Japanese Patent Laid-Open No. 61-235594).

However, in the above-mentioned prior art, Ni
As a result of the recrystallization and softening of the plating layer, when the battery cans are transported at high speed during the battery manufacturing process, the slidability at the contact between the battery can outer surfaces is not always sufficient, and the flowability of the cans is inferior and the productivity is reduced. It may worsen.

In Japanese Patent Publication No. 5-25958, an Ni-P diffusion layer and a recrystallized and softened Ni are formed by Ni-P alloy plating and heat treatment after Ni plating.
A Ni-plated steel sheet having a harder Ni-P alloy plating layer on the plating layer and having excellent corrosion resistance and scratch resistance is shown. This steel sheet also has sufficient slidability on the outer surface of the battery can described above.

[0006]

[Problems to be Solved by the Invention]
The technique of Japanese Patent No. 958 maintains good corrosion resistance in simple forming such as overhanging, but the corrosion resistance when processed into an actual battery can is not necessarily sufficient. It is considered that this is because cracks in the upper hard plating layer spread to the lower layer, and the peeled hard plating layer adheres to the mold and scratches the battery can surface layer. Furthermore, although it is presumed that the similar causes, the battery can formed by using the above steel sheet has a problem that the contact resistance value after storage is high and the battery characteristics are easily deteriorated.

Therefore, an object of the present invention is to provide a method for producing a Ni-plated steel sheet for a battery can, which is excellent in corrosion resistance, battery characteristics and slidability.

[0008]

[Means for Solving the Problems] In order to improve the corrosion resistance, the battery characteristics, and the slidability as described in the problems, it is important to form an appropriate plated layer that is neither too hard nor too soft. The present invention has been completed and the present invention has been achieved.

That is, the gist of the present invention is a method for producing a plated steel sheet for a battery can, wherein the outer surface of the can is plated with a Ni-P alloy having a P content of 0.1 mass% or more and less than 3 mass%. After applying the heat treatment,
A method for manufacturing a Ni-plated steel sheet, which comprises forming an Fe-Ni diffusion layer at an interface between the plating layer and the base iron.
The amount of P alloy plating deposited is preferably 9 g / m ² or more as Ni.

Another aspect of the present invention is a method of manufacturing a plated steel sheet for a battery can, wherein the outer surface of the can is N-coated.
i plating, P content is 0.1 mass% or more and 3 mass
% Of Ni-P alloy plating, and then heat treatment to form an Fe-Ni diffusion layer at the interface between the plating layer and the base iron. In this case, the amount of Ni-P alloy plating deposited is Ni
Is 1 g / m ² or more, and Ni plating, Ni-
It is desirable that the total amount of Ni in the P alloy plating is 9 g / m ² or more.

In any of the above cases, the inner surface of the can is plated with Ni or has a P content of 0.1 mass.
Ni-P alloy plating of s% or more and less than 3 mass%, or Ni plating and P content of 0.1 mass% or more and 3 m
Ni-P alloy plating of less than ass% in multiple layers, in each case the amount of Ni (in the case of multiple layers, the total amount of Ni) 1 g /
It is desirable to perform heat treatment after applying m ² or more.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

First, the constituent features of the surface corresponding to the outer surface of the battery can in the present invention will be described.

On the outer surface, the P content is 0.1 ma.
After applying a Ni-P alloy plating of ss% or more and less than 3 mass%, heat treatment is performed, and Fe is added to the interface between the plating layer and the base iron.
-It is necessary to form a Ni diffusion layer. The reason for defining the P content to be 0.1 mass% or more and less than 3 mass% is less than the lower limit, the slidability of the battery can surface is insufficient,
If the amount exceeds the upper limit, the plating layer becomes too hard, and when the battery can is formed, the plating layer is largely damaged and corrosion resistance is insufficient. It is presumed that the same reason as above, but after storage, the contact resistance of the battery can increases and the battery characteristics deteriorate.

The P content is 0.1 mass% or more and 3 m
An example of a method for obtaining a Ni-P alloy plating of less than ass% is an electroplating method using a dull Watt bath to which an appropriate amount of phosphorous acid is added. At this time, the P concentration in the plating layer can be controlled by controlling the phosphorous acid concentration.
In order to set the P content to 0.1 mass% or more and less than 3 mass%, the phosphorous acid concentration is preferably about 0.01 to 10 g / l. The more preferable phosphorous acid concentration is determined by the ratio with the concentration of Ni sulfate which is the main component in the Watts bath,
A concentration of 1/300 to 1/30 of the Ni sulfate concentration is desirable.

The amount of plating is preferably 9 g / m ² or more in terms of the amount of Ni, and the greater the amount of deposition, the better the corrosion resistance. The upper limit may be determined in consideration of cost, and is usually about 40 g / m ² .

Needless to say, the usual pretreatment such as degreasing and pickling is performed prior to plating.

The reason why the Fe-Ni diffusion layer is formed at the interface between the plating layer and the base iron by heat treatment after plating is to enhance the adhesion of the plating layer and maintain the corrosion resistance after processing. The most efficient manufacturing method can be exemplified by using an unannealed plate as a plating original plate and performing the heat treatment after plating to form the Fe—Ni diffusion layer and anneal the steel sheet material at once. As a heating condition, it is desirable to perform a treatment in a non-oxidizing atmosphere at 800 ° C. for several tens of seconds.

Another aspect of the present invention is a method for manufacturing a plated steel sheet for a battery can, wherein the outer surface of the can is plated with Ni and the P content is 0.1 mass% or more and 3 mass or more.
After the Ni-P alloy plating of less than s% is sequentially applied, heat treatment is performed to form a Fe-Ni diffusion layer at the interface between the plating layer and the base iron. Ni plating prior to Ni-P alloy plating reduces the amount of Ni-P alloy plating that is more expensive to manufacture than Ni plating, and complements the corrosion resistance, which is reduced by that amount, with Ni plating. This is because you can enjoy the benefits.

In this case, the amount of Ni-P alloy plating on the upper layer is 1 g / m ² or more as Ni, and Ni plating and N
It is desirable that the total Ni content of the i-P alloy plating be 9 g / m ² or more. Ni-P alloy plating Ni content is 1g
If it is less than / m ² , the slidability of the surface of the battery can deteriorates. Also N
The total Ni content of i plating and Ni-P alloy plating is 9 g /
If it is less than m ² , the corrosion resistance of the battery can deteriorates. The upper limit of the total Ni content may be determined in consideration of the cost, and is usually about 40 g / m ² . The definition of the P content in the upper Ni-P alloy plating is the same as that in the case of the Ni-P alloy plating one-layer type already described.

The heat treatment after plating is also the same as that already described.

The inner surface of the can is not required to have a higher degree of corrosion resistance than the outer surface, and Ni plating or Ni-P having a P content of 0.1 mass% to less than 3 mass% is required.
Alloy plating or Ni plating and P content 0.1m
Ni-P alloy plating of not less than 3% by mass and less than 3% by mass may be applied in a multi-layer, and in any case, the heat treatment may be performed after applying 1 g / m ² or more with the Ni content (in the case of the multi-layer, the total Ni content). . The Ni plating and the Ni-P alloy plating may be carried out in the same manner as the above-mentioned outer surface. The P content of the Ni-P alloy plating is 0.1 mass% or more and less than 3 mass%. The reason is that different kinds of plating are performed on the outer surface and the inner surface because equipment load is large and the same kind of plating is more advantageous in terms of manufacturing cost. Therefore, it is defined from the required characteristics on the outer surface.

[0023]

EXAMPLES The present invention will be described in detail below with reference to examples.

(Examples 1 to 5 and Comparative Examples 1 to 3) In each of the following examples, Nb-Ti-S having a plate thickness of 0.3 mm is used.
The ulc steel (unrecrystallized steel plate) was used as a base plate (however, only the annealed recrystallized plate was used in Comparative Example 3), and samples were manufactured in the order of Ni plating → heat treatment → temper rolling. Ni plating was performed using one vertical plating tank having a Ni grain / Ti basket as a counter electrode.

Table 1 shows the respective conditions of Ni plating and heat treatment. The amount of Ni plating adhered is shown for each of the "outer surface" and "inner surface" of the battery can. Further, the plating layer P content rate (P / (Ni
Table 1 shows the results of actually measuring the outer surface side of + P)%).

[0026]

[Table 1]

(Examples 6 to 8 and Comparative Example 4) In all of the following examples, Nb-Ti-Sul having a plate thickness of 0.3 mm is used.
Using c steel (unrecrystallized steel plate) as a base plate, samples were manufactured in the order of Ni plating → heat treatment → temper rolling. Ni plating was performed using three vertical plating tanks having a Ni grain / Ti basket as a counter electrode. All heat treatments are non-oxidizing atmosphere, 7
It was carried out under the condition of 80 ° C. soaking for 40 seconds.

Table 2 shows the Ni plating conditions (respective conditions for the first, second and third baths). The amount of Ni plating adhered is shown for each of the "outer surface" and "inner surface" of the battery can. In the table of Ni content, "-"
"" Indicates that the plating current was not applied and the plate was immersed in the plating bath and passed. Further, the plating layer P content rate (P /
Table 2 shows the results of actually measuring the outer surface side of (Ni + P)%.

[0029]

[Table 2]

(Performance Evaluation Method) The above steel plate sample was pressed to manufacture a can for an ordinary LR06 type alkaline manganese battery, and the can was evaluated. Corrosion resistance: A salt spray test (JIS-Z-2371) was performed for 3 hours with the positive electrode terminal portion facing upward, and the occurrence of red rust was visually observed. No rust was evaluated as "○", slight rust (up to 10 spot rust) was evaluated as "△", and rust was evaluated as "x". Sliding property: Using a Heidon 14 type testing device, the side surface of the can body was slid with a load of 20 g on a 10 mmφ stainless steel ball to determine the dynamic friction coefficient. Less than 0.15 is "○", 0.
More than 15 and less than 0.2 was evaluated as “Δ”, and 0.2 or more was evaluated as “x”. Battery characteristics (contact resistance): Battery can at 60 ° C 90% RH
After leaving it for 20 days, the contact resistance was measured with an electric contact simulator CRS-1 manufactured by Yamazaki Seiki Kenkyusho under a load of 100 g. Less than 10 mΩ is "○", 10 mΩ or more 20
Less than mΩ was evaluated as “Δ”, and 20 mΩ or more was evaluated as “x”.

Table 3 shows the above evaluation results.

As shown in Table 3, good corrosion resistance, slidability, and battery characteristics (contact resistance after storage) were obtained in the examples of the present invention. On the other hand, in Comparative Example, good properties were not obtained in either corrosion resistance or slidable battery characteristics.

[0033]

[Table 3]

[0034]

The present invention is a method for producing a plated steel sheet for a battery can, wherein the P content is 0.1 ma on the outer surface of the can.
After applying a Ni-P alloy plating of ss% or more and less than 3 mass%, heat treatment is performed, and Fe is added to the interface between the plating layer and the base iron.
Forming a Ni diffusion layer, or Ni plating, Ni with P content of 0.1 mass% or more and less than 3 mass%
P alloy plating is sequentially applied and then heat treatment is performed to form a Fe-Ni diffusion layer at the interface between the plating layer and the base metal, thereby producing a plated steel sheet material having excellent corrosion resistance, battery characteristics, and slidability. I got a way.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI Theme Coat (reference) C25D 7/00 C25D 7/00 Y H01M 2/02 H01M 2/02 Z (72) Inventor Minohiro Tono Himeji 1Fujicho, Hirohata-ku, Japan New Nippon Steel Co., Ltd. F-term in Hirohata Works (reference) 4K024 AA03 AA15 AB02 AB03 AB04 AB06 AB07 BA03 BB09 BC01 DB01 GA04 GA16 5H011 AA02 AA04 CC06 DD18 KK01 KK02

Claims (5)

[Claims] 1. A method for producing a plated steel sheet for a battery can, which comprises subjecting the outer surface of the can to Ni—P alloy plating having a P content of 0.1 mass% or more and less than 3 mass% and then performing heat treatment. And a Fe-Ni diffusion layer is formed at the interface between the plating layer and the base metal. 2. The method for producing a Ni-plated steel sheet according to claim 1, wherein the amount of Ni-P alloy plating deposited is 9 g / m ² or more as Ni. 3. A method of manufacturing a plated steel sheet for a battery can, wherein the outer surface of the can is plated with Ni and the P content is 0.1 m.
A method for producing a Ni-plated steel sheet, which comprises applying Ni-P alloy plating in an amount of from ass% to less than 3 mass% in sequence and then performing heat treatment to form an Fe-Ni diffusion layer at the interface between the plating layer and the base iron. 4. The amount of Ni-P alloy plating adhered is 1 g / m ² or more as Ni, and Ni plating and Ni-P are used.
The method for producing a Ni-plated steel sheet according to claim 3, wherein the total amount of Ni in the alloy plating is 9 g / m ² or more. 5. A method of manufacturing a plated steel sheet for a battery can, wherein the inner surface of the can is plated with Ni or Ni-P having a P content of 0.1 mass% or more and less than 3 mass%.
Alloy plating or Ni plating and P content 0.1m
Ni-P alloy plating of not less than 3% by mass and less than 3% by mass is applied in multiple layers, and in each case, the heat treatment is performed after applying 1 g / m ² or more with the amount of Ni (in the case of multiple layers, the total amount of Ni). The method for producing a Ni-plated steel sheet according to any one of claims 1 to 4, which is characterized by the above-mentioned.