JPWO2005056885A1 - Plated steel sheet for battery container, battery container using the plated steel sheet for battery container, and battery using the battery container - Google Patents

Abstract

It aims at providing the plated steel plate for battery containers which can be set as the battery which has the outstanding discharge characteristic, the battery container using the same, and the battery using the same. 10 to 200 nm, which is extremely fine in the plating layer of nickel, cobalt, nickel-cobalt alloy, nickel-cobalt-phosphorus alloy, nickel-boron alloy, nickel-phosphorus alloy, etc. A plated steel sheet for battery containers formed by forming a dispersed plating layer in which carbon black having a particle size of 5 is dispersed.

Description

  The present invention relates to a plated steel sheet for battery containers, a battery container using the plated steel sheet for battery containers, and a battery using the battery container.

  In recent years, portable devices such as audio devices and mobile phones have been used in various fields, and alkaline batteries that are primary batteries, nickel-hydrogen batteries that are secondary batteries, lithium ion batteries, and the like are frequently used as operating power sources. In these batteries, higher output such as higher output and longer life is always required, and battery containers filled with positive electrode and negative electrode active materials are also required to improve performance as important components of the battery. . For example, for the purpose of improving the adhesion between the negative electrode active material and the surface of the battery container and reducing the contact resistance, the surface is unevenly formed by dispersing and precipitating graphite in the nickel plating formed on the steel plate surface. And a surface-treated steel sheet having a dispersed plating layer in which graphite particles are dispersed in the plating layer, and the graphite particles having excellent conductivity are exposed on the surface of the plating layer to reduce the contact resistance between the negative electrode active material and the battery container surface. It has been proposed by the present inventors (see Patent Documents 1 and 2).

  When a surface-treated steel sheet in which these graphite particles are dispersed is molded into a battery container and filled with a positive electrode and a negative electrode active material to form a battery, the contact resistance with the negative electrode active material to be filled is reduced, resulting in discharge characteristics. However, there is a need for a plated steel sheet for battery containers that can provide even better discharge characteristics.

Prior art documents relating to the present invention include the following.
JP 2002-180296 A International Publication No. WO00 / 05437 Pamphlet

  An object of this invention is to provide the plated steel plate for battery containers which can be set as the battery which has the outstanding discharge characteristic, a battery container using the same, and a battery using the same.

In the plated steel sheet for battery containers of the present invention that solves the above problems, in the plated steel sheet for battery containers, carbon black having an average particle size of 10 to 200 nm is dispersed in the plating layer on at least the surface that becomes the inner surface of the battery container. A plated steel sheet for battery containers, wherein a dispersion plating layer is formed (Claim 1),
In the plated steel sheet for battery containers of the above (Claim 1), the carbon black is dispersed in an amount of 0.1 to 10% by weight in the dispersion plating layer (Claim 2) or the above (Claim). In the plated steel sheet for battery containers according to item 1 or 2), the plating is nickel plating or nickel alloy plating (claim 3), or in the plated steel sheet for battery containers according to the above (claims 1 to 3), A diffusion layer is formed below the plating layer (Claim 4).

Furthermore, the battery container of the present invention is a battery container (Claim 5) obtained by forming any one of the above (Claims 1 to 4) into a bottomed cylindrical shape.
And the battery of this invention is a battery (Claim 6) using the battery container as described in said (Claim 5).

  In the present invention, by forming a dispersion plating layer in which extremely fine carbon black having an average particle size of 10 to 200 nm is dispersed during plating on the surface that is the battery container inner surface of the plated steel sheet for battery containers, Battery performance is improved, for example, the contact resistance is small, the short-circuit current is large, and the continuous discharge time is long.

  Hereinafter, the present invention will be described in detail. First, a steel plate that is a substrate of the steel plate for battery containers according to the present invention will be described. As a steel plate to be used as a substrate, general-purpose low carbon aluminum killed steel (carbon content 0.01 to 0.15% by weight) or non-aging ultra low carbon aluminum killed steel to which niobium or titanium is added (carbon content 0.01 weight) %). These steel hot-rolled sheets are pickled to remove surface scales, then cold-rolled, and then subjected to electrolytic cleaning, annealing, and temper rolling as a substrate. After cold rolling and electrolytic cleaning, the substrate may be plated without annealing, and then annealed. A chromium steel sheet containing 3 to 20% by weight of chromium can also be used.

  A plated layer is formed on the steel plates which are these substrates to obtain the plated steel plate for battery containers of the present invention. The plated steel sheet for battery containers according to the present invention is characterized in that a dispersed plating layer in which fine carbon black having an average particle size of 10 to 200 nm is dispersed during plating is formed on at least the surface that is the inner surface of the battery container. And As the carbon black to be dispersed during plating, channel black, thermal black, furnace black, acetylene black, ketjen black, and the like can be used, but ketjen black having an average particle size of 10 to 60 nm and an average particle size of 50 to 50 can be used. It is preferable to use 200 nm acetylene black. These carbon blacks are preferably dispersed in an amount of 0.1 to 10% by weight during plating, and more preferably in an amount of 0.1 to 5% by weight. In addition to these extremely fine carbon blacks, graphite particles having an average particle diameter of 1 to 10 μm may be mixed and dispersed during plating. In this case, it is preferable that both carbon black and graphite are dispersed in an amount of 0.1 to 10% by weight.

  Examples of the plating layer for dispersing carbon black include a nickel plating layer, a cobalt plating layer, or a nickel alloy plating layer such as a nickel-cobalt alloy, a nickel-cobalt-phosphorus alloy, a nickel-boron alloy, and a nickel-phosphorus alloy. Moreover, it is preferable to provide a diffusion layer under the plating layer in which these carbon blacks are dispersed.

  Since these carbon black and graphite particles are hydrophobic, they are dispersed in the plating solution using a surfactant. By performing electrolytic treatment using a plating solution in which carbon black or graphite particles are further dispersed, dispersion plating in which carbon black or graphite particles are dispersed during plating can be obtained.

  Further, nickel-based base plating that does not disperse carbon black during plating may be performed on the steel sheet, and then the above-described dispersed plating layer may be formed thereon. Nickel base plating includes matte nickel plating, semi-bright nickel plating, cobalt plating, or nickel alloys such as the above nickel-cobalt alloy, nickel-cobalt-phosphorus alloy, nickel-boron alloy, nickel-phosphorus alloy Plating or the like can be used.

  These plating is made to adhere on a steel plate using an electroplating method using a well-known plating solution. The plating thickness is preferably 1 to 3 μm. When applying the base plating, after plating the base plating with a thickness of 0.5 to 2.5 μm, the dispersion plating is plated with a thickness of 0.1 to 1.5 μm, and the total plating thickness is set to 1 to 1. 3 μm.

  A plating layer similar to the surface on the battery container inner surface may be formed on the surface on the battery container outer surface, but the nickel-based base plating formed on the battery container inner surface side It is preferable to form the same plating as in a single layer. The thickness of the plating to be deposited is preferably 1 to 4 μm. Similarly to the inner surface side, it is preferable that after forming the plating layer, the diffusion layer is formed by heat treatment.

  The diffusion layer is provided on the steel sheet by plating the surface on the side that becomes the outer surface of the battery container as described above, and by applying the base plating on the surface that becomes the inner surface of the battery container and then performing heat treatment. In the case where the base plating is not applied, plating is performed on the surface on the outer surface of the battery container, and dispersion plating is performed on the surface on the inner surface of the battery container, followed by heat treatment. In addition, after the base plating is applied to the surface to be the inner surface of the battery container, and then the above dispersion plating layer is formed thereon, the diffusion layer may be formed by heat treatment. As the heat treatment for forming the diffusion layer, heating is performed at a temperature of 450 ° C. or higher in a non-oxidizing atmosphere or in a reducing manner. As a heating method, the heating method used in the box-type annealing method or the continuous annealing method can be used as it is. The heating time is preferably 6 to 15 hours in the box annealing method and 0.5 to 2 minutes in the continuous annealing method within the above temperature range.

  The plated steel sheet for battery containers of the present invention is obtained as described above. The battery container of the present invention combines the above-mentioned plated steel sheet for a battery container with a drawing process, a drawing and ironing process (DI process method), a drawing stretch process (DTR process method), or a drawing process and a stretching process. Using a processing method, it is obtained by molding into a bottomed cylindrical shape. 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 in which the height of the side wall is appropriately selected according to the application. The battery container thus obtained is filled with a positive electrode, 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.
[Preparation of plated steel sheet for battery containers]
Using a low carbon aluminum killed steel having the chemical composition shown below as the substrate, using the plating solution shown below, or using the dispersion plating solution shown below containing carbon black or graphite in the plating solution, After forming the plating layer on the surface that becomes the outer surface of the battery container and the base plating layer shown in Table 1 on the surface that becomes the inner surface of the battery container, heat treatment is performed under the conditions shown in Table 1 to A diffusion layer is formed below, and then the plating layer shown in Table 1 is formed on the base plating layer on the surface that becomes the inner surface of the battery container under the conditions shown in Table 1. A plated steel sheet was created.

<Chemical composition of steel sheet>
C: 0.04 wt%, Si: 0.01 wt%, Mn: 0.023 wt%, P: 0.006 wt%, S :: 0.01 wt%, Al: 0.046 wt%, N : 0.0023 wt%, Nb: 0.001 wt%, and the balance Fe

<Nickel plating conditions (indicated by “A” in Table 1)>
Bath composition Nickel sulfate 300g / L
Nickel chloride 40g / L
Boric acid 30g / L
pH 4 to 4.6
Bath temperature 55-60 ° C
Agitation Air agitation Current density 20A / dm ²

<Nickel-cobalt alloy plating conditions (indicated by “B” in Table 1)>
Bath composition Nickel sulfate 300g / L
Cobalt sulfate 25g / L
Nickel chloride 45g / L
Boric acid 45g / L
pH 4 to 4.6
Bath temperature 55-60 ° C
Agitation Air agitation Current density 5A / dm ²

<Carbon black dispersed nickel plating conditions (indicated by “C” in Table 1)>
Bath composition Nickel sulfate 300g / L
Nickel chloride 40g / L
Boric acid 30g / L
Acetylene black (average particle size 120 nm) 10 g / L
Sodium benzenesulfonate (dispersant) 20g / L
Pit inhibitor (sodium lauryl sulfate) 2mL / L
pH 4 to 4.6
Bath temperature 55-60 ° C
Agitation Air agitation Current density 5A / dm ²

<Carbon black dispersed nickel plating conditions (indicated by “D” in Table 1)>
Bath composition Nickel sulfate 300g / L
Nickel chloride 40g / L
Boric acid 30g / L
Ketjen black (average particle size 25nm) 10g / L
Sodium benzenesulfonate (dispersant) 20g / L
Pit inhibitor (sodium lauryl sulfate) 2mL / L
pH 4 to 4.6
Bath temperature 55-60 ° C
Agitation Air agitation Current density 5A / dm ²

<Graphite-dispersed nickel plating conditions (indicated by “E” in Table 1)>
Bath composition Nickel sulfate 300g / L
Nickel chloride 40g / L
Boric acid 30g / L
Graphite (average particle size 1.3μm) 10g / L
Sodium benzenesulfonate (dispersant) 20g / L
Pit inhibitor (sodium lauryl sulfate) 2mL / L
pH 4 to 4.6
Bath temperature 55-60 ° C
Agitation Air agitation Current density 5A / dm ²

<Carbon black and graphite-dispersed nickel-cobalt alloy plating conditions (indicated by “F” in Table 1)>
Bath composition Nickel sulfate 300g / L
Cobalt sulfate 25g / L
Nickel chloride 45g / L
Boric acid 45g / L
Graphite (average particle size 1.3μm) 10g / L
Ketjen black (average particle size 25nm) 5g / L
Sodium benzenesulfonate (dispersant) 30g / L
Pit inhibitor (sodium lauryl sulfate) 2mL / L
pH 4 to 4.6
Bath temperature 55-60 ° C
Agitation Air agitation Current density 5A / dm ²

  In Table 1, the content of dispersed particles such as carbon black and graphite during plating was measured by an infrared absorption method described in JIS-G-1211.

[Create battery container]
After blanking a 57 mm diameter blank from a sample of a plated steel sheet for battery containers shown in Table 1 with sample numbers 1 to 10, the side on which only the iron-nickel alloy layer and the nickel layer are provided is the outer surface of the container. Was formed into a cylindrical LR6 type battery (AA size battery) container having an outer diameter of 13.8 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, the positive electrode mixture was pressed in a mold to form a donut-shaped positive electrode mixture pellet having a predetermined size, and was press-inserted into the battery container. A mixture of graphite powder (80 parts by weight) and epoxy resin (20 parts by weight) was diluted with methyl ethyl ketone and applied to the inner surface of 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 cloth is inserted along the inner periphery 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 added to the battery. The container was filled. Further, an insulating gasket was attached to the negative electrode plate and inserted into the battery container, and then caulking was performed to produce an alkaline manganese battery.

[Characteristic evaluation]
The characteristics of the batteries prepared using the battery containers prepared from the samples Nos. 1 to 10 as described above were evaluated as follows.

<Internal resistance>
The battery was left at 80 ° C. for 3 days, and then the internal resistance (mΩ) was measured using the AC impedance method.

<Short-circuit current>
The battery was allowed to stand at 80 ° C. for 3 days, an ammeter was connected to the battery, a closed circuit was provided, and the current value was measured. 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 at 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.
These characteristic evaluation results are shown in Table 2.

  As shown in Table 2, in the battery using the plated steel sheet for battery containers of the present invention in which extremely fine carbon black is dispersed during plating to be formed on the surface to be the battery container inner surface, carbon black is dispersed. The internal resistance, short-circuit current, and discharge characteristics are superior to those of the battery using the plating without plating or the plated steel sheet for battery containers in which graphite particles having a relatively large particle size are dispersed.

  The battery using the plated steel sheet for battery containers according to the present invention in which carbon black having an extremely fine particle diameter of 10 to 200 nm is dispersed during plating to be formed on the surface to be the inner surface of the battery container. The internal resistance, short-circuit current, and discharge characteristics are superior to those of the battery using the plating without plating or the plated steel sheet for battery containers in which graphite particles having a relatively large particle size are dispersed. Therefore, a high-performance battery can be provided.

Claims (6)

In a plated steel sheet for a battery container, a battery container characterized in that a dispersed plating layer in which carbon black having an average particle size of 10 to 200 nm is dispersed in a plating layer is formed on at least the surface that is the inner surface of the battery container. Plated steel sheet. The plated steel sheet for battery containers according to claim 1, wherein the carbon black is dispersed in an amount of 0.1 to 10% by weight in the dispersion plating layer. The plated steel sheet for battery containers according to claim 1, wherein the plating is nickel plating or nickel alloy plating. The plated steel sheet for battery containers according to any one of claims 1 to 3, wherein a diffusion layer is formed in a lower layer of the plating layer. The battery container formed by shape | molding the plated steel plate for battery containers of any one of Claims 1-4 in a bottomed cylindrical shape. A battery comprising the battery container according to claim 5.