JPH065284A - Zinc alkaline battery - Google Patents

Abstract

PURPOSE:To provide a zinc alkaline battery of low pollution, with safety and high performance wherein non-amalgamated zinc alloy powder without additive lead is used. CONSTITUTION:In this zinc alkaline battery, a gel-like negative electrode is used, wherein non-amalgated zinc alloy powder without additive lead containing indium 0.01-0.1weight%, bismuth 0.001-0.01weight%, aluminum 0.001-0.01weight%, and at least one kind or more selected from a group of titanium, manganese, cobalt, nickel, and strontium 0.001-0.05weight% is adopted as a negative electrode active material. Accordingly, a zinc alkaline battery of low pollution, with safety, little gas generation and high performance can be provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a zinc-alkaline battery, and more particularly to a gelled negative electrode for zinc-alkaline batteries which is low-pollution, safe and high-performance, using a zinc alloy powder containing no lead and no lead. .

[0002]

2. Description of the Related Art Conventionally, zinc negative alloy powder has been used as a negative electrode active material of a zinc alkaline battery for the purpose of suppressing gas generation due to corrosion of zinc and improving electrical characteristics. Since environmental pollution due to batteries has come to be regarded as a problem, there has been a social demand for low pollution, and a zinc alloy composition and an anticorrosive agent (inhibitor) for making the zinc alloy powder unconstrained (silver-free). As a result of such research, finally, a gelled negative electrode for a mercury-free alkaline battery, which has no practical problems, was finally developed.

[0003]

However, in the unalloyed zinc alloy powder which has been put to practical use in a mercury-free alkaline battery, lead, which is a harmful substance like mercury, is contained in order to suppress generation of hydrogen gas. Since 100 ppm is added, the demand for a mercury-free alkaline battery using lead-free zinc alloy powder is increasing.

By the way, there are many patent publications of zinc alloys for zinc-alkaline batteries to which lead has not been added up to now, such as JP-A-63-133450 and JP-A-2-194103. Some of them can be expected to have some degree of corrosion resistance, but they are not sufficient. Also, although it may be usable for a battery having a structure for releasing generated gas, it is possible to improve the zinc alloy composition for a battery having a sealed structure such as a cylindrical alkaline manganese dry battery by simply improving the zinc alloy composition. Even if the generation of gas can be suppressed, the generation of gas after partial discharge cannot be suppressed and the gelled negative electrode cannot be practically used. Under such circumstances, there has been an urgent need to develop a zinc alloy composition with less gas generation and a gelled negative electrode applicable to an alkaline battery having a sealed structure.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a low-pollution, safe, and high-performance zinc-alkaline battery using a zinc alloy powder free of lead and containing no lead. is there.

[0006]

In order to solve the above-mentioned problems, the present invention provides 0.01-0.1% by weight of indium, 0.001-0.01% by weight of bismuth, and 0.0% of aluminum.
0.01 to 0.01% by weight and 0.001 to 0.05% by weight of at least one selected from the group consisting of titanium, manganese, cobalt, nickel and strontium, and lead-free and lead-free zinc The alloy powder was used as the negative electrode active material, and the indium compound was used as an anticorrosive for the zinc alloy powder, and the amount of indium was 0.005 as compared with the zinc alloy powder.
-0.5 wt% and / or tetrabutylammonium hydroxide based on zinc alloy powder 0.0001-0.05
By using the gelled negative electrode added by weight%, a low-pollution, safe and high-performance zinc alkaline battery was realized.

[0007]

In the zinc alloy of the present invention, by adding indium, bismuth, aluminum, titanium, manganese, etc. as an alternative element of lead, the corrosion resistance at the time of non-discharge is improved as compared with the unleaded and leaded zinc alloy. You can Although the details of the mechanism of action of each additive element in this case have not been fully clarified, it has been confirmed that hydrogen gas generation cannot be suppressed to a practical level when each element is added alone. It is considered that, due to the synergistic effect of the addition of a plurality of elements, the hydrogen overvoltage on the surface of the zinc alloy is increased, or the surface is smoothed and the surface area is reduced, so that the corrosion resistance is improved. In addition, what is expressed here as lead-free is
In the current general zinc smelting technology, it is unavoidable that even if it is called pure zinc, lead is mixed in as an impurity of about 30 ppm, and it is technically possible to set it to 30 ppm or less, but it is costly. This is because it is considered to be a disadvantage.

Further, the zinc alloy powder of the present invention produces less gas than leaded zinc alloy powder and can be used as it is for a battery having a structure for releasing the generated gas. In a manganese battery or the like, merely improving the zinc alloy composition as in the present invention cannot suppress the generation of gas at a practical level that does not cause liquid leakage. Therefore, by adding an indium compound and / or tetrabutylammonium hydroxide as an anticorrosive agent (inhibitor), it is possible to obtain a gelled negative electrode that can be used even in a battery having a sealed structure. Of these, the details of the gas generation suppressing mechanism of indium compounds are not clear, but they have a great effect on gas generation when the battery is partially discharged, while tetrabutylammonium hydroxide adheres to the surface of the zinc alloy powder. The self-discharge is suppressed to further suppress the generation of gas in the undischarged state, and when impurities are mixed in the gelled negative electrode, the chance of contact between zinc powder and impurities is reduced, and the risk of gas generation due to impurities is reduced. It can be lowered.

[0009]

EXAMPLES Examples of the present invention and comparative examples will be described in detail below. (Example 1) First, 0.0494 parts by weight of indium hydroxide (In (OH) ₃ ) equivalent to a reagent grade or higher was added to 0.4 parts by weight of polyacrylic acid as a gelling agent (a zinc alloy powder was calculated as In conversion). 0.05% by weight), and uniformly mixed with a pot mill for 10 minutes.
01% by weight, Bi: 0.003% by weight, Al: 0.00
3% by weight and Ti: 0.01% by weight, particle size 100-
It was added to 63.55 parts by weight of 300 μm zinc alloy powder and stirred for 5 minutes with a general-purpose mixer to uniformly mix. Next, 0.0006 parts by weight of tetrabutylammonium hydroxide was added to 35 parts by weight of a 35% by weight caustic potash aqueous solution in which 3.5% by weight of zinc oxide was dissolved, and mixed and stirred for 10 minutes to sufficiently disperse, The zinc alloy powder mixture was gradually added over 4 minutes, stirred and mixed under a reduced pressure of 150 mmHg or less, and further stirred under a reduced pressure of 10 mmHg or less for 5 minutes to produce a uniform gelled negative electrode. did. A JIS standard LR6 type (AA) alkaline battery shown in FIG. 1 was assembled using the obtained gelled negative electrode.

In FIG. 1, reference numeral 1 denotes a bottomed cylindrical metal can that also serves as a positive electrode terminal. The metal can 1 is filled with a positive electrode mixture 2 which is pressed into a cylindrical shape. Positive electrode mixture 2
Is a mixture of manganese dioxide powder and carbon powder, which is housed in a metal can 1 and pressure molded into a hollow cylinder at a predetermined pressure. In addition, the hollow portion of the positive electrode mixture 2 is filled with the gelled negative electrode 4 manufactured by the above method via the bottomed cylindrical separator 3 made of a nonwoven fabric of acetalized polyvinyl alcohol fiber. In the gelled negative electrode 4, a brass negative electrode current collector rod 5 is inserted so that the upper end portion thereof protrudes from the gelled negative electrode 4. An insulating gasket 6 made of a double annular polyamide resin is disposed on the outer peripheral surface of the protruding portion of the negative electrode current collector rod 5 and the upper inner peripheral surface of the metal can 1.
A ring-shaped metal plate 7 is arranged between the double annular portions of the gasket 6, and a cap-shaped metal sealing plate 8 also serving as a negative electrode terminal is placed on the metal plate 7 so as to contact the head of the collector rod 5. It is arranged so as to contact. The opening edge of the metal can 1 is bent inward to seal the inside of the metal can 1 with the gasket 6 and the metal sealing plate 8.

Example 2 The alloy composition of zinc powder is In:
0.05% by weight, Bi: 0.003% by weight, Al: 0.
003% by weight, Ti: 0.01% by weight, except
A JIS standard LR6 type (AA) alkaline battery was assembled in the same manner as in Example 1.

Example 3 The alloy composition of zinc powder is In:
0.1 wt%, Bi: 0.003 wt%, Al: 0.0
A JIS standard LR6 type (AA) alkaline battery was assembled in the same manner as in Example 1 except that the content was 03% by weight and Ti: 0.01% by weight.

Example 4 The alloy composition of zinc powder was In:
0.05% by weight, Bi: 0.001% by weight, Al: 0.
003% by weight, Ti: 0.01% by weight, except
A JIS standard LR6 type (AA) alkaline battery was assembled in the same manner as in Example 1.

(Example 5) The alloy composition of zinc powder is In:
0.05% by weight, Bi: 0.005% by weight, Al: 0.
003% by weight, Ti: 0.01% by weight, except
A JIS standard LR6 type (AA) alkaline battery was assembled in the same manner as in Example 1.

Example 6 The alloy composition of zinc powder is In:
0.05% by weight, Bi: 0.01% by weight, Al: 0.0
A JIS standard LR6 type (AA) alkaline battery was assembled in the same manner as in Example 1 except that the content was 03% by weight and Ti: 0.01% by weight.

Example 7 The alloy composition of zinc powder was In:
0.05% by weight, Bi: 0.003% by weight, Al: 0.
001% by weight, Ti: 0.01% by weight, except that
A JIS standard LR6 type (AA) alkaline battery was assembled in the same manner as in Example 1.

(Embodiment 8) The alloy composition of zinc powder is In:
0.1 wt%, Bi: 0.003 wt%, Al: 0.0
A JIS standard LR6 type (AA) alkaline battery was assembled in the same manner as in Example 1 except that the amounts were 05% by weight and Ti: 0.01% by weight.

(Example 9) The alloy composition of zinc powder was In:
0.05% by weight, Bi: 0.001% by weight, Al: 0.
A JIS standard LR6 type (AA) alkaline battery was assembled in the same manner as in Example 1 except that the amounts were 01% by weight and Ti: 0.01% by weight.

(Example 10) The alloy composition of zinc powder was I
n: 0.05% by weight, Bi: 0.003% by weight, Al:
JIS standard LR6 type (AA) in the same manner as in Example 1 except that 0.003% by weight and Ti: 0.001% by weight.
Shape) Assembled alkaline battery.

(Example 11) The alloy composition of zinc powder was I
n: 0.05% by weight, Bi: 0.003% by weight, Al:
JIS standard LR6 type (AA) in the same manner as in Example 1 except that 0.003% by weight and Ti: 0.05% by weight.
Shape) Assembled alkaline battery.

Example 12 The alloy composition of zinc powder was I
n: 0.05% by weight, Bi: 0.003% by weight, Al:
JIS standard LR6 type (AA) in the same manner as in Example 1 except that 0.003% by weight and Mn: 0.01% by weight.
Shape) Assembled alkaline battery.

(Example 13) The alloy composition of zinc powder was I
n: 0.05% by weight, Bi: 0.003% by weight, Al:
JIS standard LR6 type (AA) in the same manner as in Example 1 except that 0.003% by weight and Co: 0.01% by weight.
Shape) Assembled alkaline battery.

(Example 14) The alloy composition of zinc powder was I
n: 0.05% by weight, Bi: 0.003% by weight, Al:
JIS standard LR6 type (AA) in the same manner as in Example 1 except that the content is 0.003% by weight and Ni: 0.01% by weight.
Shape) Assembled alkaline battery.

(Example 15) The alloy composition of zinc powder was I
n: 0.05% by weight, Bi: 0.003% by weight, Al:
JIS standard LR6 type (AA) in the same manner as in Example 1 except that 0.003% by weight and Sr: 0.01% by weight.
Shape) Assembled alkaline battery.

(Example 16) JIS standard LR6 was carried out in the same manner as in Example 2 except that the added amount of indium hydroxide was 0.005% by weight in terms of In based on the zinc alloy powder.
Type (AA) alkaline batteries were assembled.

(Example 17) JIS standard LR6 type (AA type) was used in the same manner as in Example 2 except that the added amount of indium hydroxide was 0.5% by weight in terms of In based on the zinc alloy powder. I assembled an alkaline battery.

(Example 18) A JIS standard LR6 type (AA) alkali was used in the same manner as in Example 2 except that the amount of tetrabutylammonium hydroxide added was 0.0001% by weight based on the zinc alloy powder. I assembled the batteries.

(Example 19) The amount of tetrabutylammonium hydroxide added was 0.05% by weight based on the zinc alloy powder.
JIS standard LR in the same manner as in Example 2 except that
A 6-type (AA) alkaline battery was assembled.

Comparative Example 1 The alloy composition of zinc powder is Pb:
0.05% by weight, Bi: 0.01% by weight, In: 0.0
JIS in the same manner as in Example 1 except that the amount is 2% by weight.
Standard LR6 type (AA) alkaline batteries were assembled.

(Comparative Example 2) The alloy composition of zinc powder is Bi:
0.003% by weight, Al: 0.003% by weight, Ti:
A JIS standard LR6 type (AA) alkaline battery was assembled in the same manner as in Example 1 except that the content was 0.01% by weight.

Comparative Example 3 The zinc powder alloy composition was In:
0.3% by weight, Bi: 0.003% by weight, Al: 0.0
A JIS standard LR6 type (AA) alkaline battery was assembled in the same manner as in Example 1 except that the content was 03% by weight and Ti: 0.01% by weight.

(Comparative Example 4) The alloy composition of zinc powder was In:
A JIS standard LR6 type (AA) alkaline battery was assembled in the same manner as in Example 1 except that the amount was 0.05% by weight.

(Comparative Example 5) The alloy composition of zinc powder was In:
0.05% by weight, Al: 0.003% by weight, Ti: 0.
JI in the same manner as in Example 1 except that the amount is 01% by weight.
An S standard LR6 type (AA) alkaline battery was assembled.

(Comparative Example 6) The alloy composition of zinc powder was In:
0.05% by weight, Bi: 0.05% by weight, Al: 0.0
A JIS standard LR6 type (AA) alkaline battery was assembled in the same manner as in Example 1 except that the content was 03% by weight and Ti: 0.01% by weight.

Comparative Example 7 The alloy composition of zinc powder is Bi:
A JIS standard LR6 type (AA) alkaline battery was assembled in the same manner as in Example 1 except that the amount was 0.05% by weight.

(Comparative Example 8) The alloy composition of zinc powder was In:
0.05% by weight, Bi: 0.003% by weight, Ti: 0.
JI in the same manner as in Example 1 except that the amount is 01% by weight.
An S standard LR6 type (AA) alkaline battery was assembled.

(Comparative Example 9) The zinc powder alloy composition was In:
0.05% by weight, Bi: 0.003% by weight, Al: 0.
A JIS standard LR6 type (AA) alkaline battery was assembled in the same manner as in Example 1 except that the amounts were 05% by weight and Ti: 0.01% by weight.

Comparative Example 10 The alloy composition of zinc powder is A
A JIS standard LR6 type (AA) alkaline battery was assembled in the same manner as in Example 1 except that l: 0.05% by weight.

Comparative Example 11 The alloy composition of zinc powder is I
n: 0.05% by weight, Bi: 0.003% by weight, Al:
A JIS standard LR6 type (AA) alkaline battery was assembled in the same manner as in Example 1 except that the amount was 0.003% by weight.

Comparative Example 12 The alloy composition of zinc powder is I
n: 0.05% by weight, Bi: 0.003% by weight, Al:
JIS standard LR6 type (AA) in the same manner as in Example 1 except that 0.003% by weight and Ti: 0.1% by weight.
Shape) Assembled alkaline battery.

Comparative Example 13 A JIS standard LR6 type (AA) alkaline battery was assembled in the same manner as in Example 2 except that indium hydroxide and tetrabutylammonium hydroxide were not added.

(Comparative Example 14) JIS Standard LR6 was prepared in the same manner as in Example 2 except that indium hydroxide was not added.
Type (AA) alkaline batteries were assembled.

(Comparative Example 15) JIS standard LR6 type (AA type) was carried out in the same manner as in Example 2 except that the added amount of indium hydroxide was 1.0% by weight based on the zinc alloy powder in terms of In. I assembled an alkaline battery.

COMPARATIVE EXAMPLE 16 J was prepared in the same manner as in Example 2 except that tetrabutylammonium hydroxide was not added.
An IS standard LR6 type (AA) alkaline battery was assembled.

(Comparative Example 17) JIS standard LR6 was carried out in the same manner as in Example 2 except that the amount of tetrabutylammonium hydroxide added was 0.1% by weight based on the zinc alloy powder.
Type (AA) alkaline batteries were assembled.

For each of the LR6 batteries assembled as described above, the undischarged and partially discharged (2Ω, 30 minutes discharged) batteries were stored at 60 ° C. for 40 days and then decomposed in water to decompose the gas inside the batteries. The result of collecting (n = 10 average values),
2Ω continuous discharge duration (up to 0.9v, average value of n = 6) and short life occurrence rate at 1.2kΩ continuous discharge (n = 5
0) was investigated. Tables 1 and 2 show the test results of these batteries.

[0047]

[Table 1]

[0048]

[Table 2]

As is clear from Tables 1 and 2, according to Comparative Examples 4, 7 and 10, even if indium, bismuth and aluminum were added alone, both undischarged and partially discharged were 6
It can be seen that liquid is leaked at 0 ° C. for 40 days, and there is no effect in suppressing gas generation. However, when a multi-element system is used as in Examples 1 to 19, the lead-containing zinc of Comparative Example 1 is synergistically effective. Gas generation is suppressed more than alloys.

According to Examples 1 to 3 and Comparative Examples 2 and 3,
Indium as an additive element in the zinc alloy is very effective in suppressing gas generation when lead is not added, and when indium is not added (Comparative Example 2), even if bismuth, aluminum, etc. are added, it becomes a practical level. Don't Even if indium is added in an amount of more than 0.1% by weight (Comparative Example 3), there is no remarkable effect, and in terms of cost, indium is preferably 0.1% by weight or less.

According to Examples 2, 4 to 6 and Comparative Examples 5 and 6, it is considered that bismuth suppresses gas generation by smoothing the surface and reducing the surface area, but on the other hand, when the addition amount is large, Since it seems to have an adverse effect on the load discharge characteristics, considering the balance between the gas generation suppression and the heavy load discharge characteristics, it is desirable to add in the range of 0.003 to 0.005% by weight.

According to Examples 2, 7 to 9 and Comparative Examples 8 and 9, although aluminum has a great effect of suppressing gas generation, it is feared that a large amount of aluminum tends to cause a short life at light load discharge. Considering the balance between gas generation suppression and light load discharge characteristics, 0.003 to 0.005% by weight
It is desirable to add in the range of.

Examples 2, 10 to 15 and Comparative Examples 11 and 1
According to 2, the addition of an element such as titanium can provide a safer alkaline battery with less gas generation after partial discharge than the case of adding the three elements of indium, bismuth and aluminum. However, if the addition amount of titanium or the like is too large, the amount of gas generated tends to increase, and therefore the addition amount is preferably 0.05% by weight or less. Although not shown in this example, even if two or more kinds of titanium, manganese, cobalt, nickel, and strontium are added in appropriate amounts, good results can be obtained as in this example.

Examples 2, 16-19 and Comparative Examples 13-1
7, it is clear that the addition of indium hydroxide is necessary to suppress the gas generation after partial discharge to a level practical for an alkaline battery having a sealed structure. However, adding more than 0.5% by weight has no remarkable effect, and from the viewpoint of cost, the addition amount of 0.5% by weight or less is sufficient.

Although not shown in this embodiment, the same good results as in this embodiment can be obtained by adding other indium compounds such as indium chloride, indium sulfate and indium oxide. Also, it can be seen that the addition of tetrabutylammonium hydroxide is effective in suppressing gas generation in the undischarged state, but if added in an amount of more than 0.05% by weight, the impedance of the gelled negative electrode rises, resulting in heavy load discharge Since it seems to have an adverse effect, the amount added may be 0.05% by weight or less.

[0056]

As described above, the zinc-alkaline battery having the gelled negative electrode using the zinc alloy powder and the anticorrosive of the present invention achieves further pollution reduction of the battery which is free of lead and containing no lead. In addition, it has less gas generation and is safe and high-performance superior to the unalloyed / existing zinc alloy powder.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of an alkaline dry battery incorporating a gelled negative electrode manufactured by the method of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Metal can, 2 ... Positive electrode mixture, 3 ... Separator, 4 ... Gel negative electrode, 5 ... Negative electrode collector rod, 6 ... Insulating gasket, 7 ... Ring-shaped metal plate, 8 ... Metal sealing plate.

Claims (3)

[Claims] 1. Indium 0.01 to 0.1% by weight, bismuth 0.001 to 0.01% by weight, aluminum 0.
0.001-0.05% by weight and 0.001-0.05% by weight of at least one selected from the group consisting of titanium, manganese, cobalt, nickel and strontium. A zinc alkaline battery having a gelled negative electrode using an alloy powder as a negative electrode active material. 2. The zinc according to claim 1, wherein an indium compound is added to the gelled negative electrode as an anticorrosive agent for the zinc alloy powder in an amount of 0.005 to 0.5% by weight in terms of indium with respect to the zinc alloy powder. Alkaline battery. 3. A gel negative electrode containing tetrabutylammonium hydroxide in an amount of 0.0001 to 0.05% by weight based on the zinc alloy powder as an anticorrosive agent for the zinc alloy powder. The zinc alkaline battery according to item 2.