JP2007273407A - Alkaline battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alkaline battery superior in leakage resistance and discharge performance by suppressing generation of gas and without blocking reaction of a negative electrode. <P>SOLUTION: In the alkaline battery, the negative electrode contains zinc alloy powder and an anionic surfactant, and the surfactant is a compound having a structure expressed by general formula (1) or its alkaline metallic salt. In the formula, R<SB>1</SB>is hydrogen atom or a hydrocarbon group with carbon number 1-4, R<SB>2</SB>is -CH<SB>2</SB>CH<SB>2</SB>- or -CH(CH<SB>3</SB>)CH<SB>2</SB>-, m=0-1, and when R<SB>1</SB>is hydrogen atom, n=1-8, and when R<SB>1</SB>is hydrocarbon group, n=0-8. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an alkaline battery, and more particularly to an organic anticorrosive added to a negative electrode.

Generally, an alkaline battery has a cylindrical positive electrode mixture containing manganese dioxide powder as a positive electrode active material in close contact with a positive electrode case in a positive electrode case that also serves as a positive electrode terminal, and a negative electrode through a separator in the center. It has a structure in which a gelled negative electrode containing zinc powder as an active material is disposed.
And as an anticorrosive for the negative electrode, it is proposed to use an anionic surfactant containing a sulfonic group such as a sulfonic acid ester having 7 or more carbon atoms or a sulfonic acid having an alkyl group having 5 or more carbon atoms. (For example, Patent Documents 1 and 2).

The anionic surfactant forms an aggregate and is adsorbed on the surface of the zinc particles to form a protective coating layer. This protective coating layer prevents the hydroxide ions and water from approaching the zinc particles, and the reaction of the formulas (1) and (2) on the surface of the zinc particles is suppressed.
^{Zn + 4OH - → Zn (OH} ) 4 2- + 2e - (1)
^{_{2H 2 O + 2e - → 2OH}} - + H 2 (2)

The surfactant is dispersed from the surface of the zinc particles and dispersed in the electrolyte during the negative electrode reaction. However, since the surfactants of Patent Documents 1 and 2 have a large number of carbon atoms, they are strongly adsorbed on the surface of zinc particles and have a low diffusion rate, which hinders the progress of the electrode reaction shown in Formula (1). is there.
In recent years, the number of digital devices that require a heavy load instantaneously has increased, and it is necessary to use a battery with excellent high-current discharge performance as a power source for such devices. However, in an alkaline battery in which a conventional surfactant is added to the negative electrode, the closed circuit voltage is greatly reduced, and sufficient large current discharge performance may not be obtained.

The surfactant is easily foamed and has the property of being most easily foamed especially in the vicinity of 13 carbon atoms (for example, Non-Patent Document 1). Therefore, when such an anionic surfactant is added to the negative electrode, the density of the negative electrode is reduced, and the filling amount of the negative electrode active material is reduced, resulting in a problem that the discharge performance is lowered.
Further, when the surfactant has a large number of carbon atoms, it becomes difficult to dissolve in the alkaline electrolyte. Therefore, when zinc powder, gelling agent, alkaline electrolyte, and anionic surfactant are mixed during the preparation of the gelled negative electrode, the anionic surfactant is uniformly dispersed in the alkaline electrolyte. It may be difficult.
Japanese Unexamined Patent Publication No. 63-248063 JP 63-250061 A "Surfactant", Yoneda Publishing, p. 149

  Accordingly, an object of the present invention is to provide an alkaline battery excellent in leakage resistance and discharge performance in which gas generation is suppressed without inhibiting the negative electrode reaction even when a negative electrode containing an anticorrosive agent is used. .

The alkaline battery of the present invention includes a positive electrode including at least one of manganese dioxide powder and nickel oxyhydroxide powder, a negative electrode including a zinc alloy powder and an anionic surfactant, and a separator disposed between the positive electrode and the negative electrode And an alkaline electrolyte,
The surfactant is
General formula (1):

(In the formula, R ₁ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, R ₂ is —CH ₂ CH ₂ — or —CH (CH ₃ ) CH ₂ —, and m = 0 to 1. And when R ₁ is a hydrogen atom, n = 0 to 8, and when R ₁ is a hydrocarbon group, n = 1 to 8) or a alkali metal salt thereof It is.

In the general formula (1), when R ₁ is a hydrogen atom, n = 1 to 4, and when R ₁ is a hydrocarbon group, n = 0 to 4 is preferable.
The negative electrode preferably contains the surfactant in an amount of 0.005 to 1 part by weight per 100 parts by weight of the zinc alloy powder.
The zinc alloy powder preferably contains 30 to 250 ppm of bismuth.

The negative electrode further includes a gelling agent and the alkaline electrolyte, and preferably includes 170 to 220 parts by weight of the zinc alloy powder per 100 parts by weight of the electrolyte.
In the negative electrode, the zinc alloy powder preferably contains 5 to 45% by weight of particles having a particle size of 75 μm or less.

  According to the present invention, even when a negative electrode containing an anticorrosive agent is used, gas generation can be suppressed without inhibiting the negative electrode reaction, so that both excellent liquid leakage resistance and discharge performance can be achieved.

The present invention relates to a positive electrode including at least one of manganese dioxide powder and nickel oxyhydroxide powder as a positive electrode active material, a negative electrode including zinc powder and an anionic surfactant as a negative electrode active material, and between the positive electrode and the negative electrode The present invention relates to an alkaline battery comprising a separator and an alkaline electrolyte.
And as said surfactant, general formula (1):

(In the formula, R ₁ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, R ₂ is —CH ₂ CH ₂ — or —CH (CH ₃ ) CH ₂ —, and m = 0 to 1. And when R ₁ is a hydrogen atom, n = 0 to 8, and when R ₁ is a hydrocarbon group, n = 1 to 8) or a alkali metal salt thereof It is characterized in that

  Conventionally, it is known to use a sulfonic acid surfactant such as a sulfonic acid ester as an organic anticorrosive for a negative electrode. However, since most of the sulfonic acid surfactants form aggregates on the surface of the zinc particles and strongly adsorb, the negative electrode reaction may be hindered and the discharge performance may be reduced. Therefore, the present inventors have conducted various studies on the structure of a sulfonic acid surfactant that has an effect of suppressing corrosion of the negative electrode and has an adsorbing ability to zinc particles to such an extent that the discharge performance does not deteriorate. As a result, when the compound having the structure represented by the general formula (1) or the alkali metal salt thereof is added to the negative electrode, gas generation due to corrosion of the zinc particles can be suppressed, and the surface of the zinc particles can be suppressed. It has been found that the adsorbing power of is not so strong as to inhibit the negative electrode reaction, so that a reduction in discharge performance can be suppressed.

R ₁ which is a hydrophobic group is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. At this time, since the surfactant diffuses rapidly into the electrolyte during the negative electrode reaction, it does not inhibit the negative electrode reaction. Therefore, even when the surface of the zinc particles is sufficiently covered with the surfactant, a drop in the closed circuit voltage during a heavy load is suppressed, and an excellent large current discharge performance can be obtained. On the other hand, when the number of carbon atoms exceeds 4, the adsorptive power to the zinc alloy particles is increased and the discharge performance is deteriorated. When R ₁ is a hydrocarbon group, the hydrocarbon group may contain a double bond and may be linear or branched. For example, R ₁ may be CH ₃ CH ₂ CH (CH ₃ ) — or CH ₃ CH═CHCH ₂ —.
The degree of polymerization _{n of the} polyoxyalkylene group (— (R ₂ O) _n —) is 0-8. When n exceeds 8, the effect as an anticorrosive will become weak and liquid leakage resistance will fall. Preferably, n is 0-4, and most preferably n is 0.
Examples of the compound having the structure represented by the general formula (1) or the alkali metal salt thereof include, for example, the general formula (2):

(In the formula, R ₂ is —CH ₂ CH ₂ — or —CH (CH ₃ ) CH ₂ —, and l, m, and n are 1 = 0 to 4, m = 0 to 1, and n = 0 to 0. 8 and l + n ≠ 0, and X is H, Na, or K.).
It is preferable that the negative electrode contains 0.005 to 1 part by weight of the surfactant per 100 parts by weight of the zinc alloy powder in that excellent liquid leakage resistance and discharge performance can be obtained at the same time.
More preferably, the content of the surfactant in the negative electrode is 0.005 to 0.3 parts by weight per 100 parts by weight of the zinc alloy powder in that a better discharge performance can be obtained.

  The zinc alloy powder preferably contains 30 to 250 ppm of bismuth. Bismuth is added to a zinc alloy as an inorganic anticorrosive, and bismuth has the property of inhibiting the negative electrode reaction during discharge. However, since the surfactant is used as an organic anticorrosive, the amount of bismuth added can be reduced, and the corrosion resistance of the negative electrode can be sufficiently improved without impairing the discharge performance. If the bismuth content in the zinc alloy powder is less than 30 ppm, the effect of improving the corrosion resistance of the negative electrode by bismuth cannot be sufficiently obtained. If the bismuth content in the zinc alloy powder exceeds 250 ppm, the bismuth content increases, and the discharge performance tends to deteriorate.

For the negative electrode, for example, a gelled negative electrode made of a mixture of a zinc alloy powder, a gelling agent, an alkaline electrolyte, and a surfactant represented by the general formula (1) is used.
The zinc alloy includes, for example, at least one element selected from the group consisting of aluminum, bismuth, indium, calcium, and magnesium. The average particle diameter of the zinc alloy powder is, for example, 75 to 180 μm.
As the gelling agent, for example, sodium polyacrylate is used.
For the alkaline electrolyte, for example, a potassium hydroxide aqueous solution or a sodium hydroxide aqueous solution is used.

  As a method for adding the surfactant into the gelled negative electrode, the surfactant may be added to the gelled electrolyte which is a mixture of the alkaline electrolyte and the gelling agent when the gelled negative electrode is produced. The surfactant used in the alkaline battery of the present invention is soluble in the gel electrolyte and is uniformly dispersed in the gel negative electrode. Moreover, you may make a separator and a positive electrode impregnate a surfactant at the time of battery preparation. After the battery is produced, the surfactant is dispersed in the electrolytic solution and adsorbed on the surface of the zinc alloy particles in the gelled negative electrode.

In addition, since the surfactant used in the alkaline battery of the present invention has a lower foaming property than the surfactant used in conventional alkaline batteries, it is possible to suppress a decrease in the density of the gelled negative electrode.
In the gelled negative electrode, the zinc alloy powder is preferably contained in an amount of 170 to 220 parts by weight per 100 parts by weight of the electrolyte contained in the gel negative electrode. When the content of the zinc alloy powder in the gelled negative electrode is less than 170 parts by weight per 100 parts by weight of the electrolyte contained in the gelled negative electrode, the gelled negative electrode is liable to foam and discharge performance is deteriorated. On the other hand, when the content of the zinc alloy powder in the gelled negative electrode exceeds 220 parts by weight per 100 parts by weight of the electrolyte contained in the gel negative electrode, the amount of the electrolyte in the gel negative electrode is too small and the discharge performance is lowered. To do.

  In general, an aqueous solution to which a surfactant such as a sulfonic acid ester is added is known to increase foam stability. Therefore, when the negative electrode is produced, the gelled negative electrode is foamed to take in air, and the density of the gelled negative electrode is lowered. Therefore, the present inventors examined the relationship between the ratio of the amount of zinc alloy powder to the amount of electrolyte in the gelled negative electrode and the foamability of the gelled negative electrode. As a result, it was found that as the ratio of the amount of zinc alloy powder to the amount of electrolytic solution was larger, the decrease in negative electrode density due to foaming was suppressed. This is probably because the zinc alloy particles having a complicated shape have a greater effect of breaking bubbles.

In the negative electrode, the zinc alloy powder preferably contains 5 to 45% by weight of particles having a particle size of 75 μm or less. When the content of particles having a particle size of 75 μm or less in the zinc alloy powder is 5% by weight or more, the reaction efficiency of the negative electrode is improved and the discharge performance is improved. When the content of particles having a particle size of 75 μm or less in the zinc alloy powder exceeds 45% by weight, the productivity in the filling process of the gelled negative electrode is lowered.
For example, the zinc alloy powder is classified with a sieve having a mesh size of 75 μm and 425 μm, and a powder made of particles having a particle size of 75 μm or less is mixed with a powder having a particle size of 75 μm to 425 μm to a predetermined weight. A zinc alloy powder containing 5 to 45% by weight of particles having a diameter of 75 μm or less is obtained.
Moreover, it can confirm that zinc alloy powder contains 5-45 weight% of particles with a particle size of 75 micrometers or less by sieving and weighing zinc powder with a sieve of 75 micrometers of openings.

Conventionally, when the zinc alloy powder is pulverized in order to increase the reaction efficiency of the negative electrode, there is a problem that the viscosity of the gelled negative electrode is increased and the productivity is deteriorated.
However, the viscosity of the gelled negative electrode is reduced by adding the surfactant. This is because the interfacial tension between the electrolyte, the zinc alloy particles and the gelling agent decreases, the wettability of the zinc alloy particles and the gelling agent increases, and the lubricity increases. It is considered that this is because the friction caused by the collision of can be reduced. Due to the decrease in the viscosity of the gelled negative electrode, the productivity of the step of filling the gelled negative electrode into the battery case is improved. In particular, sulfonic acid esters having a short carbon chain are known to have a strong interfacial tension reducing ability (see JP-A-55-148277).
Therefore, since the surfactant is added to the gelled negative electrode as described above, an increase in the viscosity of the gelled negative electrode can be suppressed even if a zinc alloy fine powder is used, and the discharge can be performed without reducing the productivity. Performance can be improved.

For the positive electrode, for example, a positive electrode mixture made of a mixture of a positive electrode active material, graphite powder as a conductive agent, and an alkaline electrolyte is used. As the positive electrode active material, manganese dioxide powder, nickel oxyhydroxide powder, or a mixture thereof is used. The average particle diameter of the manganese dioxide powder or the nickel oxyhydroxide powder is, for example, 25 to 55 μm. The average particle diameter of the graphite powder is, for example, 8 to 20 μm.
For the separator, for example, a nonwoven fabric mainly composed of polyvinyl alcohol fiber and rayon fiber is used.

(1) Preparation of positive electrode mixture Manganese dioxide powder (average particle size: 40 μm) as a positive electrode active material, graphite powder (average particle size: 15 μm) as a conductive agent, and an electrolyte solution are 100: 6: 1. After being mixed at a weight ratio, the mixture was compression molded into flakes. Next, the flaky positive electrode mixture was pulverized into granules, which were classified with a sieve, and those having a 10 to 100 mesh shape were pressure-formed into a hollow cylinder to obtain a pellet-like positive electrode mixture. In addition, 40 weight% potassium hydroxide aqueous solution was used for electrolyte solution.

(2) Preparation of gel-like negative electrode Zinc is heated to about 500 ° C. to be in a molten state, a predetermined amount of Al, Bi and In is added and melted therein, this is dropped into a trickle, and compressed air is injected. By spraying, a zinc alloy powder containing 50 ppm Al, 200 ppm Bi, and 250 ppm In was obtained.
Then, the obtained zinc alloy powder is classified with a sieve having openings of 75 μm and 425 μm, and a predetermined weight of the powder made of particles of 75 μm or less is mixed with the powder made of particles sieved between 75 to 425 μm. Thus, a zinc alloy powder (average particle size: 120 μm) containing 25% by weight of fine powder having a particle size of 75 μm or less was obtained.

On the other hand, after adding a surfactant as an organic anticorrosive agent to 40% by weight potassium hydroxide aqueous solution as an electrolytic solution and stirring for 1 minute, sodium polyacrylate was added as a gelling agent and mixed for 45 minutes. Then, it was left to stand at room temperature for 10 minutes to obtain a gel electrolyte.
To this gel electrolyte, the above zinc alloy powder was added and mixed for 30 minutes to obtain a gelled negative electrode. At this time, the mixing weight ratio of the aqueous sodium hydroxide solution, the surfactant, the sodium polyacrylate, and the zinc alloy powder was 32.934: 0.066: 1: 66. At this time, the addition amount of the surfactant in the gelled negative electrode was 0.1 part by weight per 100 parts by weight of the zinc alloy powder.

(3) Assembly of alkaline battery The cylindrical AA alkaline battery shown in FIG. FIG. 1 is a front view with a cross section of a part of an alkaline battery.
Two pieces of the positive electrode mixture obtained above were inserted into the battery case 1, and the positive electrode mixture 2 was remolded with a pressure jig and brought into close contact with the inner wall of the battery case 1. And the bottomed cylindrical separator 4 was arrange | positioned in the center of the positive mix 2 arrange | positioned in the battery case 1, and predetermined amount electrolyte solution similar to the above was inject | poured into the separator 4. FIG. After a predetermined time had elapsed, the gelled negative electrode 3 obtained above was filled into the separator 4. In addition, the separator 4 used the nonwoven fabric which mixed and mixed mainly the polyvinyl alcohol fiber and the rayon fiber.

  Subsequently, the negative electrode current collector 6 was inserted into the center of the gelled negative electrode 3. The negative electrode current collector 6 was previously integrated with a gasket 5 and a bottom plate 7 that also served as a negative electrode terminal. And the opening edge part in the battery case 1 was crimped to the peripheral part of the baseplate 7 via the edge part of the gasket 5, and the opening part of the battery case 1 was sealed. Finally, the outer surface of the battery case 1 was covered with the exterior label 8 to obtain an alkaline battery.

<< Examples 1-9 and Comparative Examples 1-2 >>
By changing the number of carbon atoms of the alkyl group-derived precursor, which is a raw material of the surfactant, the degree of polymerization of the polyoxyethylene structure, and the type of salt that neutralizes the sulfonic acid group, when the alkaline battery is manufactured, In the general formula (2), R ₂ was —CH ₂ CH ₂ —, and l, m, n, and X were variously changed as shown in Table 1 to prepare compounds 1 to 11 as surfactants. Compounds 1 to 3 were obtained by sulfonation of a linear saturated hydrocarbon compound. Compounds 4 and 9 were obtained by esterification reaction of ethanol and sulfuric acid. Compounds 5 to 7 and 11 were obtained by an esterification reaction of sulfuric acid with a compound obtained by adding ethylene oxide to alkyl alcohol. Compounds 8 and 10 were obtained by esterification reaction of polyethylene oxide and sulfuric acid.
And the batteries 1-11 were produced using the compounds 1-11, respectively.

<< Comparative Example 3 >>
An alkaline battery was produced in the same manner as in Example 1 except that the surfactant was not added to the negative electrode.

[Battery evaluation]
(4) Evaluation of discharge performance About each battery, after discharging at 1.5 W for 2 seconds, pulse discharge which repeats the process of discharging at 0.65 W for 28 seconds was performed 10 cycles per hour. Then, the discharge duration until the closed circuit voltage reached 1.05 V was examined.

(5) Evaluation of leakage resistance 150 batteries were prepared and stored at 60 ° C. The number of batteries that leaked after storage for 4 months, 8 months, and 12 months was then examined.
These evaluation results are shown in Table 2. The discharge capacity in Table 2 was expressed as an index with the discharge capacity of the battery of Example 1 being 100, and it was determined that the discharge performance was good when the discharge capacity was 100 or more.

In Comparative Examples 2 and 3 in which no organic anticorrosive was added to the gelled negative electrode, batteries leaked due to gas generation accompanying corrosion of the zinc alloy were observed. In the battery of Comparative Example 1, the number of carbon atoms in the surfactant increased, and the adsorptive power to the zinc alloy powder increased, so the discharge performance decreased.
On the other hand, the batteries of Examples 1 to 9 of the present invention showed good discharge performance and none leaked.

<< Examples 10 to 15 >>
An alkaline battery was prepared in the same manner as in Example 2 except that the amount of the organic anticorrosive added to the gelled negative electrode per 100 parts by weight of the zinc alloy powder was changed as shown in Table 3. evaluated. The evaluation results are shown in Table 3 together with the results of Example 2. The discharge capacity in Table 3 was expressed as an index with the discharge capacity of the battery of Example 1 being 100, and it was determined that the discharge performance was good when the discharge capacity was 100 or more.

  In the batteries of Examples 10 to 15, good leakage resistance and discharge performance were obtained at the same time. In particular, in the batteries of Examples 2 and 11 to 14 in which the amount of the organic anticorrosive added in the negative electrode is 0.005 to 1 part by weight per 100 parts by weight of the zinc alloy powder, excellent leakage resistance and discharge performance are obtained. It was.

<< Examples 16 to 19 >>
An alkaline battery was prepared in the same manner as in Example 2 except that the composition of the zinc alloy (bismuth content) was variously changed as shown in Table 4, and was evaluated in the same manner as described above. The evaluation results are shown in Table 4 together with the results of Example 2. The discharge capacity in Table 4 was expressed as an index with the discharge capacity of the battery of Example 1 being 100, and it was determined that the discharge performance was good when the discharge capacity was 100 or more.

  In the batteries of Examples 16 to 19, good leakage resistance and discharge performance were obtained at the same time. In particular, in the batteries of Examples 2, 17, and 18 in which the bismuth content in the zinc alloy was 30 to 250 ppm, excellent liquid leakage resistance and discharge performance were obtained.

<< Examples 20 to 23 >>
An alkaline battery was prepared by the same method as in Example 2 except that the content of the zinc alloy powder per 100 parts by weight of the electrolyte used for preparing the gelled negative electrode was variously changed as shown in Table 5. The discharge performance was evaluated in the same manner. The evaluation results are shown in Table 5 together with the results of Example 2. The discharge capacity in Table 5 was expressed as an index with the discharge capacity of the battery of Example 1 being 100, and it was determined that the discharge performance was good when the discharge capacity was 100 or more. The value in parentheses of the density of the gelled negative electrode is a value when no organic anticorrosive is added.

  In the batteries of Examples 20 to 23, good discharge performance was obtained. In particular, in the batteries of Examples 2, 21, and 22 in which the addition amount of the zinc alloy powder in the gelled negative electrode is 170 to 220 parts by weight per 100 parts by weight of the electrolyte in the gelled negative electrode, the density of the gelled negative electrode is Since the electrolyte solution is high and a sufficient amount of the electrolytic solution is present in the gelled negative electrode, excellent discharge performance was obtained.

<< Examples 24 to 25 >>
An alkaline battery was prepared in the same manner as in Example 2 except that the content of particles having a particle size of 75 μm or less in the zinc alloy powder was changed as shown in Table 6, and the discharge performance was evaluated in the same manner as described above. The evaluation results are shown in Table 6 together with the results of Example 2. The discharge capacity in Table 6 is expressed as an index with the discharge capacity of the battery of Example 1 being 100, and it was determined that the discharge performance was good when the discharge capacity was 100 or more.

In the batteries of Examples 2, 24, and 25, good discharge performance was obtained. In particular, in the batteries of Examples 2 and 25 in which the content of particles having a particle diameter of 75 μm or less in the zinc alloy powder was 5% by weight or more, the reaction area of the zinc alloy was increased, and thus excellent discharge performance was obtained. .
However, when the content of particles having a particle size of 75 μm or less in the zinc alloy powder exceeds 45% by weight, the viscosity of the gelled negative electrode is increased, and the productivity in the filling process of the gelled negative electrode is deteriorated. Therefore, the content of particles having a particle size of 75 μm or less in the zinc alloy powder is preferably 5 to 45% by weight.

  The alkaline battery of the present invention is suitably used as a power source for electronic devices such as communication devices and portable devices.

It is the front view which made a part of one example of the alkaline battery of the present invention into the section.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Battery case 2 Positive electrode mixture 3 Gel-like negative electrode 4 Separator 5 Gasket 6 Negative electrode current collector 7 Bottom plate 8 Exterior label

Claims (6)

A positive electrode including at least one of manganese dioxide powder and nickel oxyhydroxide powder; a negative electrode including zinc alloy powder and an anionic surfactant; a separator disposed between the positive electrode and the negative electrode; and an alkaline electrolyte. Equipped,
The surfactant is
General formula (1):

(In the formula, R ₁ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, R ₂ is —CH ₂ CH ₂ — or —CH (CH ₃ ) CH ₂ —, and m = 0 to 1. And when R ₁ is a hydrogen atom, n = 1-8, and when R ₁ is a hydrocarbon group, n = 0-8) or a alkali metal salt thereof Is an alkaline battery. 2. The alkaline battery according to claim 1, wherein, in the general formula (1), n = 1 to 4 when R ₁ is a hydrogen atom, and n = 0 to 4 when R ₁ is a hydrocarbon group.   The alkaline battery according to claim 1, wherein the negative electrode contains 0.005 to 1 part by weight of the surfactant per 100 parts by weight of the zinc alloy powder.   The alkaline battery according to claim 1, wherein the zinc alloy powder contains 30 to 250 ppm of bismuth.   5. The alkaline battery according to claim 1, wherein the negative electrode further includes a gelling agent and the alkaline electrolyte, and the zinc alloy powder includes 170 to 220 parts by weight per 100 parts by weight of the electrolyte.   6. The alkaline battery according to claim 1, wherein in the negative electrode, the zinc alloy powder contains 5 to 45 wt% of particles having a particle size of 75 μm or less.

Images