JP3293977B2 - Method of manufacturing negative electrode can for button type battery - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a negative electrode can for a button type battery such as an alkaline manganese battery, a silver oxide battery, a silver peroxide battery and an air battery.
no adverse effects contamination during press working n plated surface, and there is no adhesion of metal powders, H ₂ gas generation suppression relates to a method of manufacturing a negative electrode can for excellent button cells of corrosion effects.

[0002]

2. Description of the Related Art Generally, in alkaline batteries and air batteries, the former uses silver oxide as a positive electrode active material, the latter uses oxygen in the air as a positive electrode active material, zinc is used as a negative electrode active material, and the electrolyte is alkaline. This battery is composed of a saturated solution of metal salts, hydroxides and zinc oxide. It is characterized by a high discharge voltage and stability, a large energy density and a wide operating temperature range. It is widely used for various small precision electronic devices as an electronic device power supply.

In a button type alkaline battery, as shown in FIG. 1, a positive electrode 1 and a negative electrode 2 are arranged via a separator 3, a positive electrode can 4 is made of a Ni-plated steel plate or stainless steel, and a negative electrode can 5 is made of stainless steel. C on one main surface of steel
u is pressed and punched from the Cu surface side so that the Cu surface is disposed on the inner surface and the Ni surface is disposed on the outer surface, with a three-layer clad negative electrode plate having Ni applied to the other main surface by pressure welding or plating. Then, it is formed in a button shape. In the figure, reference numeral 6 denotes a gasket. As the negative electrode active material, granular zinc of 50 to 100 mesh is used. In an alkaline battery, a foaming phenomenon occurs on the negative electrode side during storage due to the reaction of the following formulas (1) and (2) due to generation of H ₂ gas. Therefore, in order to suppress the foaming phenomenon due to the generation of H ₂ gas, several percent of Hg is added to granular zinc as the negative electrode active material to form amalgam, and the hydrogen overpotential of zinc is increased. Restrained.
However, when the alkaline battery is discarded, Hg added to the negative electrode active material causes pollution of the global environment, and adding Hg to the negative electrode active material has become a problem.

[0004]

Embedded image

[0005]

Therefore, recently, H
As a negative electrode can of an alkaline battery to which g is not added, a copper-stainless-nickel three-layer clad negative electrode plate is manufactured by a pressure welding method or a plating method, and then electrolytic plating or chemical reduction plating (so-called electroless plating method) is performed on the Cu surface. , Below
Dissolution plating method), Sn or In
After pressing, a button-shaped negative electrode can was manufactured by pressing and punching into the required shape and dimensions from the Sn surface or In surface side. However, in the Sn-plated or In-plated surface of the inner surface of the negative electrode can, metal powder is pressed and adhered during press working, and further, microcracks are generated on the plated surface, which becomes a nucleus of H ₂ gas generation. ₂ gas generation suppression,
Furthermore, the effect of corrosion resistance is significantly reduced, and contamination of press oil is inevitable. Further, when the thickness of the Sn and In platings is increased, the Sn and In platings are soft and there is a drawback in that press molding at the time of forming the negative electrode can causes problems such as shape deformation and liquid leakage.

[0006] This invention is an alkaline manganese battery, a silver oxide battery, in the production of the negative electrode can for button-type battery such as a peroxide silver oxide battery and an air battery, in particular, contamination during press working Sn plated surface of the negative electrode can inner surface It is an object of the present invention to provide a production method capable of easily producing a negative electrode can for a button-type battery excellent in corrosion resistance and capable of suppressing the generation of H ₂ gas without causing adverse effects or adhesion of metal powder.

[0007]

According to the present invention, a three-layer clad plate comprising a stainless steel plate having one main surface coated with Cu and another main surface coated with Ni is pressed and punched from the Cu side. After forming the negative electrode can for a button-type battery, the Cu surface on the inner surface of the negative electrode can is cleaned and alkanol sulfo is removed.
Stannous acid 30-50 g / l, alkanesulfonic acid 65
１１０110 g / l, tartaric acid 10-20 g / l, thiourea 4
0-120 g / l, sodium citrate 10-20 g /
1, nonionic surfactant 1-30 g / l, organic sulfurization
0.5 to 1.0 g / l, pH 0.5 to 1.0
While stirring the plating solution with the replacement Sn plating solution of
A method for manufacturing a negative electrode can for a button-type battery, comprising applying a substituted Sn plating film to the Cu surface.

[0008] The displacement tin plating method, which is a feature of the present invention, comprises:
The basic plating bath composition shown in Table 1 is preferable, and the plating conditions are preferably a temperature of 50 ° C. and a pH of 1.0 or less. In the present invention, the plating thickness of Sn is 0.02 μm.
If it is less than m, the effect of suppressing the generation of H ₂ gas is poor, and 5.0
If it exceeds μm, liquid leakage may occur.
It is preferably from 02 μm to 5.0 μm, and more preferably the plating thickness is from 0.1 μm to 0.5 μm.

[0009]

[Table 1]

Formulas (A) to (C) are shown between Cu and Sn.
As shown, the standard oxidation-reduction potential of Cu is higher than that of Sn.
Therefore, the phenomenon of substitution on Cu usually occurs.
Absent. However, as shown in equation (D), the presence of S causes C
When u forms a thio complex, the standard oxidation-reduction
Position shifts in the base direction, so that substitutional precipitation of Sn occurs.
You. Cu⁺+ E → Cu E₀= 0.521 (A) Cu²⁺+ 2e → Cu E₀= 0.153 ... (B) Sn²⁺+ 2e → Sn E₀= −0.136 (C) Cu_TwoS + 2e → 2Cu + S^2-  E₀= -0.54 (D)

[0011] In carrying out displacement Sn plating, thiourea is added to an aqueous solution containing 30 g / l to 50 g / l of stannous alkanolsulfonate, 65 g / l to 110 g / l of alkanesulfonic acid, and 10 g / l to 20 g / l of tartaric acid. 4
0 g / l to 120 g / l, and in the present invention, as a nonionic surfactant, an alkyl polyoxyethylene ether type or polyoxyalkylene block copolymer type nonionic surfactant of HLB 5 to 16 1 g / l to
30 g / l, and organic sulfur compound 0.5 g / l or more
A substituted Sn plating solution containing 10 g / l is used. The substituted Sn plating solution is effective especially in a medium temperature range of about 60 to 70 ° C. and further in a low temperature range of 50 ° C. or less, and is extremely useful in practical use .

In the substituted Sn plating solution, the concentration of stannous alkanolsulfonate must be in the range of 30 g / l to 50 g / l, and the concentration of alkanesulfonic acid must be in the range of 65 g / l to 110 g / l. If it is outside the above range, a uniform and good plating layer cannot be obtained. The amount of the complexing agent added is 10% for sodium citrate.
g / l to 20 g / l, thiourea 40 g / l to 120 g
/ L is required, and Cu forms a thio complex due to the presence of S, so that the standard oxidation-reduction potential of Cu shifts in the base direction, and is an essential component for precipitating Sn. If the amount is too small, a stable bath cannot be obtained,
On the other hand, if the amount is too large, it is unfavorable because it inhibits the formation of a good plating layer. In order to stabilize the bath composition in addition to the above components, a foaming agent having a low cloud point is used as a wetting agent, and an alkyl polyoxyethylene ether type or polyoxyalkylene block copolymer type nonionic surfactant having an HLB of 5 to 16 is used. 1 g / l to 30 g / l are added. As an example, 1) polyoxyethylene-polyoxypropylene alkyl ether

[0013]

Embedded image A [(CmH ₂ mO) p (CuH ₂ nO) gB] r

Wherein A is a compound residue having an oxygen atom or an active hydrogen atom, B is a hydrogen atom, an alkyl group or an acyl group, m and n are 2 to 4, V is 1 to 6,
Among r, p, r, and g, those exhibiting the degree of polymerization of the hydrophobic polyoxyalkylene chain are 7 to 100, and the others are 1 to 1100.
It is.

For example, Pluronics type HO (C ₂ H
_{2 O) p (C 3 H} 6 O) q (C 2 H 4 O) rH ( wherein, q is 15 to 50, p and r are 1 to 150) and Tetoronikkusu type

[0016]

Embedded image

(Wherein q is 2 to 20 and r is 1 to 20) 2) Polyoxypropylene alkyl ether R—O (CH ₂ CH ₂ O) nH (where R is C _{5 to} C ₃₀₎ Alkyl group of n = 3 to 60) For example, polyoxypropylene alkyl ether, polyoxyethyrene setelether, polycaxethylenystearyl ether and the like. 3) Polyoxyalkylene asole ether 4) Alkyl ester type 5) Polyoxyethylene alkylamine 6) Polyoxyethylene alkylamide 7) Polyoxyethylene sorbitan fatty acid ester.

[0018] Of these low cloud point and low foaming, further in view of low-temperature detergency, polyoxyethylene down over polyoxypropylene alkyl ethers are most preferred. Special
, The content of the polyoxyalkylene ether type nonionic surface active agent is preferably 1g / l ~10g / l,
If it is less than 1 g / l , the wetting effect is poor, and if it exceeds 10 g / l, the wetting effect is saturated, which is not preferable in terms of cost.

As the gloss-imparting agent, the following general formula (a) and
0.5% of the water-soluble organic sulfur compound represented by
g / l to 10 g / l, but the amount added is 0.5 g / l
If less than 10 g / l, gloss and smoothness are poor.
Exceeding this is not preferred because the stability of the bath deteriorates. (B) R₇-(S) n-R₈  R₇, R₈Is-(CH_Two) M-R₉Even if they are the same,
May be different. R₉ : -OH, -NH_Two, -COOH, m = 1
~ 4, n = 1 ~ 2 R₉Is -COOH, C₆Up to alkanolami
Salt or R₉Is -NH_TwoIn the case of the above, the inorganic acid salt or C
₁~ C_ThreeMay be used. R₇: H or alkali
Metal salt, R₈:-(CH_Two) M-R_TenAnd R_Ten: -COOH, -OH, -NH_Two, M = 1
~ 3, n = 1 R_TenIs -COOH, C₆Up to alkanolua
Min salt, or -NH_TwoIn the case of the above, the inorganic acid salt or C₁
~ C_ThreeMay be used.

[0020]

Embedded image

In the above formula (B), R ₁₁ and R ₁₂ may be the same or different and each has an alkyl group having 1 to 8 carbon atoms, an alkenyl group, an allyl group, an alkyl allyl group,
Aralkyl group, alkanol group or _{- (CH 2 CH 2 O)} u - H n: 1~20 R 13 is represented by the following formulas and alkyl group having 1 to 18 carbon atoms,
An alkenyl group, an allyl group, an alkyl allyl group, an aralkyl group, or a mixture of two or more selected from the group consisting of alkanol groups, wherein the water-soluble organic ionic compound is thioglycol, thiolenamine, thiojetanol, And cysteine thiodiglycolate, thioacetamide, ethanolamine acid of dithiodipropionic acid and the like. R ₁₄ and R ₁₅ are the same as R ₁₁ and R ₁₂ .

[0022]

Embedded image

In the present invention, in the displacement plating method, an object to be plated is subjected to a usual plating treatment using the plating solution. That is, the plating tank or its method can be used as it is, such as a conventionally known barrel type, immersion type, or belt conveyor type,
First, an object to be plated is placed in a tank containing the plating solution,
Next, as the plating conditions, a pH of 0.5 to 1.0 and a temperature of 30 ° C. to 70 ° C. are appropriate, and the stirring of the solution in the plating process brings good results to the plating finish.

[0024]

According to the present invention, a three-layer clad plate in which one side of a stainless steel plate is coated with Cu and the other side is coated with Ni is pressed from the Cu side and punched to form a negative electrode can for a button type battery. It is characterized in that Sn is applied to the Cu surface by displacement plating, and displacement plating is performed after punching, so that the Sn plating surface has the adverse effect of contamination during press working and metal powder as in a conventional negative electrode can. No indentation, no adhesion, H ₂
The effect of suppressing gas generation is extremely high, and the Sn plating thickness deposited on the Cu surface is 0.02 μm to 5.0 μm,
For Sn plating the film thickness is thin, even no possibility of smooth leakage plated surface.

[0025]

【Example】

Example 1 After pressing a Cu plate and a stainless steel (SUS304) Ni plate so as to have a thickness ratio of 16: 76: 8, the width was cut with a slitter, and the dimensions were a thickness of 0.2 mm, a width of 12 mm, and a length. After obtaining a Cu-stainless steel-Ni three-layer clad strip of 100 m, the three-layer clad plate is pressed and punched from the Cu surface side using a 40-ton press, and the inner surface is C-shaped.
u, 10,000 pieces of button-shaped negative electrode cans having an outer surface of Ni dimensions of outer diameter 10 mm × height 2 mm were prepared. The weight of the obtained negative electrode can was 0.2143 g, and the surface area was 13.1 g.
mm ² , the negative electrode can was pre-degreased and washed with trichlorethane to remove press oil and metal powder during pressing.
Next, put in a barrel and use an alkaline electrolytic degreasing jet cleaner (manufactured by Fukuno Chemical Co., Ltd.) at 50 g / l and a temperature of 50 g / l.
C. and a current density of 5 A / dm ² for 3 minutes.
After rinsing with running water, the plate was further washed with water, then immersed in a 10% H ₂ SO ₄ solution at 40 ° C. for 30 seconds as an acid activation treatment, and further washed with water.

Next, a substituted Sn plating solution having the composition shown in Table 2 was prepared, and the resulting substituted plating solution having a pH of 0.59 was stirred and immersed in the bath by rotating the barrel at a bath temperature of 50 ° C. for 3 minutes. Then, the substrate was subjected to displacement Sn plating, washed twice with water, centrifugally dehydrated, and then dried to obtain 1,000 negative electrode cans having a Sn plating thickness of 0.1 μm and a metallic luster. Next, heat treatment was performed at a temperature of 125 ° C. for 3 hours to reduce the generation of Sn whiskers.
Table 8 shows the contamination status, corrosion resistance, and the height of the overflow of the electrolytic solution on the plating surface of the obtained negative electrode can.

The contamination on the plating surface was analyzed and measured by XMA, and the number of foreign substances was determined by an optical microscope using an area of 0.1 mm ^2.
The foreign matter of 0.001 mm or more in the inside was measured. The corrosion resistance is determined by soldering to the button-shaped negative electrode can and connecting the lead.
The i-plane was insulated, and the spontaneous potential and pitting potential (100 μA / cm ² ) were measured with a potentiostat. Further, the rising height of the electrolytic solution was determined by degreasing and cleaning an oxygen-free Cu plate having a thickness of 0.4 mm, a width of 10 mm, and a length of 100 mm as a rising height test piece. 0.1 μm, and placed in a container containing zinc powder and an electrolytic solution, and the height of wetting above the liquid level was measured.

[0028]

[Table 2]

REFERENCE EXAMPLE 2 Into 1,000 button-shaped negative electrode cans having an outer diameter of 10 mm and a height of 2 mm prepared in Example 1 and subjected to preliminary degreasing cleaning, electrolytic degreasing cleaning, water washing and acid activation treatment, and having the composition shown in Table 3 In a plating bath, under a plating condition of pH 9 (28% NH ₄ OH water addition) and a temperature of 80 ° C., the plating solution is stirred, the barrel is rotated for 5 minutes, immersed in the bath, displacement In plating is performed, and water washing 2 is performed. After that, drying was performed after centrifugal dehydration. Obtained plating thickness
The contamination status, corrosion resistance, and rising height of the electrolytic solution on the plated surface of the negative electrode can plated with In with a 1 μm metallic luster were measured in the same manner as in Example 1 and shown in Table 8.

[0030]

[Table 3]

Examples 3, 4, 5 Using the bath compositions shown in Table 2, the button-shaped negative electrode can obtained in Example 1 was plated in the same manner as in Example 1, and the plating time was variously changed to change the plating thickness. Negative electrode cans (Sample No. 3)
To 5), and then heat-treated at a temperature of 125 ° C. for 3 hours in order to reduce the generation of Sn whiskers. The height was measured and is shown in Table 8.

Comparative Example 6 Using the Cu-stainless steel-Ni three-layer clad strip obtained in Example 1, the same preliminary degreasing cleaning, electrolytic degreasing cleaning, and water washing as in Example 1 were carried out, followed by acid activation treatment. PH 9 (28% NH _{4) with} an electroless In plating solution having the composition shown in
OH water addition), under the conditions of electroless plating at a temperature of 80 ° C.,
Plating thickness 0.5μm strip thickness 0.2mm x width 12mm
× A material having a length of 20 m was prepared. The In-plated strip material was pressed and stamped out in the same manner as in Example 1, and the inner surface was In-plated and the outer surface was Ni.
Thus, 1000 mm button-shaped negative electrode cans were obtained. Further, in order to remove press oil and metal powder at the time of pressing, the material was degreased and washed with trichlorethane, washed with water, centrifugally dehydrated, and dried. After that, the contamination state, corrosion resistance, and rising height of the electrolytic solution of the plated surface of the negative electrode can obtained in the same manner as in Example 1 were measured. As shown as No. 6, the contaminant foreign matter of the metal powder remained without being removed.

[0033]

[Table 4]

Comparative Example 7 Using the Cu-stainless steel-Ni three-layer clad strip obtained in Example 1, preliminarily degreased and washed as in Example 1,
Scotch electrical insulation tape No. 56 (manufactured by Sumitomo 3M), and then subjected to the same electrolytic degreasing and water washing as in Example 1, followed by an acid activation treatment.
H13, temperature 50 ° C., current density 2 A / dm ² under electroplating conditions, In plating thickness 1.0 μm, strip thickness 0.2 m
A material of mx 12 mm wide x 20 m long was prepared. Scotch electrical insulation tape no. When 56 (manufactured by Sumitomo 3M) was peeled off, a defect of In plating occurred on both sides of the edge. This In-plated strip material was pressed and punched in the same manner as in Example 1 so that the inner surface was In.
Plating was performed to obtain 1000 button-shaped negative electrode cans having a Ni outer dimension of 10 mm in outer diameter × 2 mm in height. Further, in order to remove press oil and metal powder at the time of pressing, the material was degreased and washed with trichlorethane, washed with water, centrifugally dehydrated, and dried. After that, the contamination state, corrosion resistance, and rising height of the electrolytic solution of the plated surface of the negative electrode can obtained in the same manner as in Example 1 were measured. As shown by 7, the contaminant foreign matter of the metal powder remained without being removed. Further, microcracks were generated at the corners of the cap inner plating coating.

[0035]

[Table 5]

COMPARATIVE EXAMPLE 8 Using the Cu-stainless steel-Ni three-layer clad strip obtained in Example 1, the same preliminary degreasing and washing as in Example 1 was performed.
Scotch electrical insulation tape No. 56 (manufactured by Sumitomo 3M), followed by electrolytic degreasing and water washing as in Example 1, followed by acid activation treatment, followed by a Sn plating solution having the composition shown in Table 6 to obtain a pH of 1
3. Under electroplating conditions of a temperature of 50 ° C. and a current density of 2 A / dm ² , a Sn plating thickness of 1.0 μm and a strip thickness of 0.2 mm ×
A material having a width of 12 mm and a length of 20 m was prepared. Scotch electrical insulation tape no. When 56 (manufactured by Sumitomo 3M) was peeled off, Sn plating defects occurred on both sides of the edge. This Sn-plated strip material was used in Example 1.
Pressing and punching were performed in the same manner as in the above to obtain 1,000 button-shaped negative electrode cans having an inner surface of Sn plating and an outer surface of Ni having an outer diameter of 10 mm and a height of 2 mm. Further, in order to remove press oil and metal powder at the time of pressing, the material was degreased and washed with trichlorethane, washed with water, centrifugally dehydrated, and dried. After that, the contamination state, corrosion resistance, and rising height of the electrolytic solution of the plated surface of the negative electrode can obtained in the same manner as in Example 1 were measured. As shown by 8, the contaminant foreign matter of the metal powder remained without being removed. Furthermore, microcracks were generated at the corners of the Sn plating coating on the inner surface of the cap. Two months later, Sn whiskers occurred.

[0037]

[Table 6]

[0038]

[0039]

[0040]

[Table 8]

[0041]

According to the present invention, one of the stainless steel plates
Is pressed and punched from the Cu side to form a three-layer clad plate on which Ni is adhered on the other side to form a button-type battery negative electrode can. Then, Sn is adhered to the Cu surface by displacement plating. It is characterized by the fact that displacement plating is performed after punching, so there is no adverse effect of contamination at the time of press working, metal powder indentation, adhesion as in the conventional negative electrode can, as in the conventional negative electrode can,
Suppression of H ₂ gas generated is very high, also Sn plating thickness to be deposited on the Cu surface is 0.02Myuemu～5.0Myuemu, since Sn plated film is thin, the plated surface may smooth a leakage Nor.

[Brief description of the drawings]

FIG. 1 is a vertical sectional view showing a configuration of a button-type alkaline battery.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Negative electrode 3 Separator 4 Positive electrode can 5 Negative electrode can 6 Gasket

Claims (1)

(57) [Claims] 1. A three-layer clad plate comprising a stainless steel plate having one main surface coated with Cu and another main surface coated with Ni is pressed and punched from the Cu side to form a button-type battery negative electrode can. After the formation, the Cu surface on the inner surface of the negative electrode can piece was subjected to cleaning treatment, and stannous alkanolsulfonate was 30 to 50 g / l,
Alkanesulfonic acid 65-110 g / l, tartaric acid 10
20 g / l, thiourea 40-120 g / l, sodium citrate
Thorium 10-20 g / l, nonionic surfactants 1-3
0 g / l, containing organic sulfur compounds 0.5 to 10 g / l
Then, while stirring the plating solution with a substitution Sn plating solution having a pH of 0.5 to 1.0 , a substitution Sn plating film is formed on the Cu surface.
Anode can manufacturing method for a button-type battery, characterized by depositing.