JPH0732015B2 - Alkaline battery - Google Patents

Description

TECHNICAL FIELD The present invention suppresses an increase in battery internal pressure due to hydrogen gas generated in a battery of a battery using zinc as a negative electrode main active material and an alkaline aqueous solution as an electrolytic solution, and preserves the battery. It provides a battery with excellent storage and storage properties.

Conventional technology Conventional alkaline batteries of this type have been found to generate hydrogen gas due to self-depletion and corrosion of zinc during storage of the battery or after partial discharge, so 1.5% by weight of alloy containing indium aluminum and lead in zinc. The above-mentioned mercury was added to form an amalgam, and the rise in the internal pressure of the battery was suppressed. As a result, the internal pressure of the battery is prevented from rising during storage, the storability is ensured, and the battery is widely used as a practical battery with little performance deterioration.

However, with the recent increasing social needs for low pollution, it is necessary to further reduce the amount of mercury used and to secure the above-mentioned practical performance without using mercury. Has been done since. But,
Even though it is possible to reduce the amount of mercury to some extent, it is the current situation that no means that can essentially solve the problem is found, and it is extremely difficult to secure sufficient corrosion resistance of the negative electrode zinc without using mercury. It is considered.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention By reducing the amount of mercury added to a zinc alloy containing indium, aluminum, and lead to zinc to less than 1.5% by weight, it is possible to reduce unremoved zinc or 0.05% by weight (500 ppm) to an extremely low level. When a battery is constructed using zinc hydride, hydrogen gas is generated from zinc due to the corrosion reaction during storage of the battery or after the battery is partially discharged, and the internal pressure of the battery is significantly increased.

It is considered that the cause of promoting the generation of hydrogen gas is that mercury originally has an action of increasing hydrogen overvoltage to zinc and suppressing a corrosion reaction, but that the absolute amount of mercury is reduced to the limit.

When such a significant increase in internal pressure occurs in the battery, there is a problem in that the electrolyte leaks, the storage property and storage property of the battery are significantly impaired, and practical performance cannot be ensured.

The present invention is to solve such a problem, hydrogen gas generated during gel battery storage of a battery using unremoved or ultra-low zinc content, or after partial discharge fluorine in the gel-like alkaline electrolyte solution. An object of the present invention is to provide a battery that suppresses an increase in battery internal pressure by mixing a system surfactant and a zinc alloy corrosion inhibitor and suppresses the increase in battery internal pressure, and that has good storability and storability.

Means for Solving the Problem In order to solve this problem, the present invention uses unreduced or low-graded zinc gold powder with a mercury content of up to 500 ppm as the main active material of the negative electrode, and mixes this with a gel-like alkaline electrolyte. In the alkaline battery provided with the gelled zinc negative electrode, the gelled alkaline electrolyte contains a fluorine-based surfactant and a zinc alloy corrosion inhibitor. The content of the fluorine-based surfactant here is 0.01 with respect to the gelled zinc negative electrode.
~ 1 part by weight, and the zinc alloy corrosion inhibitor is 0.01
It is preferably ˜10 parts by weight.

Function With this configuration, the hydrogen gas generated can be reduced by the fluorine-based surfactant and the zinc alloy corrosion inhibitor mixed in the gelled alkaline electrolyte, and as a result, the liquid leakage resistance of the battery is improved.

The action mechanism of the fluorine-based surfactant and the zinc alloy corrosion inhibitor used in the present invention is unclear, but it is presumed as follows.

When the corrosion reaction in the alkaline electrolyte of zinc is represented by the following formula, a fluorine-based surfactant to form adsorbed film on the surface of the negative electrode, the anode reaction ^{Zn + 40H - → Zn (OH} ) 4 -2 + 2e - cathodic reaction 2H ₂ O + 2e ⁻ → 2OH ⁻ + H _{2 The} hydroxide ions that cause the anodic reaction are prevented from approaching the zinc negative electrode, and the water molecules necessary for the cathode reaction cannot exist near the surface of the zinc negative electrode, and zinc corrosion is suppressed. To be On the other hand, it is known that the corrosion reaction of zinc is promoted by the coexistence of a discharge product of zinc such as zinc oxide or zinc hydroxide. Although the mechanism of action of the zinc alloy corrosion inhibitor used here is not clear, it is considered that this inhibitor acts on these zinc discharge products to suppress zinc corrosion. Further, such an effect of the zinc alloy corrosion inhibitor exerts a synergistic effect in the coexistence of the fluorosurfactant.

As described above, by using the constitution of the present invention, the synergistic effect of the anticorrosion effect of the combination of the fluorine-based surfactant and the zinc alloy corrosion inhibitor can reduce the increase in the internal pressure of the battery after storage or after partial discharge. It is possible to provide an alkaline battery having good storability.

Example An example in which a gelled zinc negative electrode containing a fluorine-based surfactant and a zinc alloy corrosion inhibitor is applied to an alkaline manganese dry battery will be described.

FIG. 1 shows the alkaline manganese battery, LR, used in this example.
6 is a structural cross-sectional view of FIG. In FIG. 1, 1 is a positive electrode mixture,
2 is a gel negative electrode using a anhydrous silver-zinc alloy containing a fluorine-based surfactant and a corrosion inhibitor described in Examples 1, 2, 3 and 4 below in a gel electrolyte solution, 3 is a separator, and 4 is a gel negative electrode. It is a current collector. Reference numeral 5 is a positive electrode cap, 6 is a metal case, 7 is a battery outer can, 8 is a resin sealing body, and 9 is a bottom plate.

Example 1 A case of a gelled zinc negative electrode containing a fluorine-based surfactant and a zinc alloy corrosion inhibitor containing a group IIIB element of the periodic table (hereinafter abbreviated as a group IIIB inhibitor) will be described.

The gelled zinc negative electrode was prepared as follows.

First, 3 wt% of polyacrylic acid leader and 1 wt% of carboxymethylcellulose are added to 40 wt% potassium hydroxide solution (including ZnO) for gelation. After this, a zinc alloy is added in a weight ratio twice that of the gelled electrolysis, but before the zinc alloy is added, the fluorine-based surfactant and the group IIIB inhibitor are added and mixed sufficiently. These amounts are adjusted to the specified ratio after the zinc alloy powder is added. The addition ratio of the fluorine-based surfactant and the group IIIB inhibitor is the ratio with respect to the entire gel zinc negative electrode. Further, as the zinc alloy, one containing 0.05% by weight of indium, lead and aluminum was used. As the fluorinated surfactant, one having both a perfluoroalkyl group and a polyoxyethylene group was used. Group IIIB inhibitors are In ₂ O ₃ · xH ₂ O (75% In ₂ O ₃ ) Ga
₂ O ₃ , Tl ₂ O and potassium borate were used. In the following, In
Indicates In ₂ O ₃ · xH ₂ O (75% In ₂ O ₃ ), and similarly Ga is Ga ₂ O ₃ , Tl
Represents Tl ₂ O and B represents potassium borate.

First, the corrosion inhibition effect on the zinc alloy of the present invention was investigated. As an experimental method, the alkaline manganese battery shown in FIG. 1 was prototyped and a constant resistance discharge of 1Ω was performed for 22 minutes. After that, the battery was disassembled, 2 g of the gelled zinc negative electrode was collected, and the temperature was maintained at 60 ° C for 10 days.
The amount of hydrogen gas generated under the temperature was measured. Table 1 shows the results obtained when the amount of the Group IIIB inhibitor added to the gelled zinc negative electrode was 1% by weight and the amount of the fluorine-based surfactant was 0.1% by weight or no addition. For comparison, the measurement was carried out for the case where only the fluorine-based surfactant was added and the case where neither was added. The gas generation amount shown in Table 1 is shown as an index when the case where neither the IIIB group inhibitor nor the fluorosurfactant is added is 100.

However, as is clear from Table 1, it is
Only when a Group IIIB inhibitor coexists, the gas generation index becomes 60 or less. In other words, the index will be
The coexistence of those of about 81 to 95 exerts a synergistic effect, and the index can be set to 60 or less.

Next, the amount of the fluorine-based surfactant added was examined. As the experimental method, the concentration of the fluorine-based surfactant was changed, and the gas generation amount and discharge performance at that time were examined. The alkaline manganese battery shown in FIG. 1 is manufactured as a prototype. Gas generation measurement is 1
Ω, 2 g of the gel negative electrode of the battery after 22 minutes of discharge was sampled for 10 days at 60
The amount of hydrogen gas generated under the temperature of ° C is measured. Regarding the discharge performance of the battery, continuous discharge of 10Ω was performed. The group IIIB inhibitor (In ₂ O ₃ · xH ₂ O (75% I
n ₂ O ₃ )) is 1.0% by weight, and the specified amount of fluorine-based surfactant is mixed. The obtained results are shown in FIG. Second
In the figure, the solid line shows the amount of gas generated, and the broken line shows the average voltage during 10Ω continuous discharge. The amount of gas generated is
The index is shown with 100 when no inhibitor was added.
As is clear from FIG. 2, the gas generation amount is suppressed when the addition amount of the fluorine-based surfactant is increased (up to the addition amount of about 0.05 wt%), and beyond that, it hardly changes. On the other hand, the average voltage gradually decreased with the increase of the addition amount, and was 1% by weight.
It can be seen that the value drops sharply after passing. Therefore, considering the relationship between these two factors, the addition amount of the fluorine-based surfactant is preferably 0.01 to 1.0% by weight. It was found from experiments that almost the same concentration range is preferable when Ga, Tl, and B are used as the group IIIB inhibitor.

Next, the gas generation amount and the discharge performance with the change of the addition amount of the group IIIB inhibitor were examined. As an experimental method, the alkaline manganese battery shown in FIG. 1 was prototyped and a constant resistance discharge of 1Ω was performed for 22 minutes. After that, the battery is electrolyzed to form a gel zinc negative electrode.
Collect 2g and measure the amount of hydrogen gas generated by heating at 60 ℃ for 10 days. Regarding the discharge performance of the battery, continuous discharge of 10Ω was performed. The gel-type zinc negative electrode contained 0.1% by weight of a fluorine-based surfactant and a group IIIB inhibitor (In ₂ O ₃ · xH ₂ O (75%
In ₂ O ₃ )) is mixed in the specified amount. The obtained results are shown in FIG. In FIG. 3, the solid line shows the gas generation amount, and the broken line shows the average voltage during 10Ω continuous discharge. The amount of gas generated is an index with 100 when neither surfactant nor inhibitor is added. As is clear from FIG. 3, 0.1% by weight
Until the addition amount of IIIB group inhibitor is increased, the gas generation amount is suppressed, and thereafter becomes almost constant. On the other hand, the average voltage gradually decreases as the amount of inhibitor added increases, and sharply decreases when it exceeds 10% by weight. Considering these two phenomena together, the addition amount of the group IIIB inhibitor is preferably 0.01 to 10% by weight. It was also found that the similar addition amount regions are preferable for Ga, Tl, and B.

Finally, the corrosion inhibition effect of the combination of In, Ga, Tl, B (IIIB group inhibitor) was investigated. As an experimental method, the alkaline battery shown in FIG. 1 was prototyped and a constant resistance discharge of 1Ω was performed for 22 minutes. After that, the battery is disassembled, 2 g of the gelled zinc negative electrode is sampled, and the amount of hydrogen gas generated at a temperature of 60 ° C. for 10 days is measured. The obtained results are shown in Table 2. The type and amount of the added Group IIIB inhibitor and the amount of the fluorine-containing surfactant are also shown in the table. In addition, the amount of gas generated is shown as an index when 100 is obtained when neither the surfactant nor the group IIIB inhibitor is added. As is clear from the table, the gas generation is suppressed by combining the inhibitors, and it may be further suppressed by subtly changing the combination and the addition amount. In Table 2, regarding the number of leaked liquids, 20 batteries of each type were made as prototypes and 1Ω constant resistance discharge was performed for 22 minutes. After discharging, the battery was stored at a temperature of 60 ° C. for 2 months, and then the leaked state of the battery was observed. It can be seen that when neither the fluorine-based surfactant nor the group IIIB inhibitor is contained, a considerable number of liquids are leaked, but those containing both according to the present invention do not leak.

As described above, by using a gelled zinc negative electrode containing a fluorine-based surfactant and a zinc alloy corrosion inhibitor containing a Group IIIB element, a battery of anhydrous silver or ultra-low zinc content can be used to reduce the internal pressure of the battery due to gas generation. It is possible to suppress the rise of the liquid crystal and improve the liquid leakage resistance.

Example 2 A case of a gelled zinc negative electrode containing a fluorine-based surfactant and a zinc alloy corrosion inhibitor containing a group IVB element of the periodic table (hereinafter abbreviated as a group IVB inhibitor) will be described.

The gelled zinc negative electrode was prepared as follows. First, 40
3 wt% in a wt% potassium hydroxide solution (including ZnO)
Gelation is carried out by adding the polyacrylic acid leader of 1. and 1% by weight of carboxymethyl cellulose. After that, a zinc alloy is added to the gel electrolyte in a weight ratio of 2 times, but before the zinc alloy is added, the fluorine-based surfactant and the IVB group inhibitor are added and thoroughly mixed. These amounts are adjusted to the specified ratio after the zinc alloy powder is added. The addition ratio of the fluorine-based surfactant and the group IVB inhibitor is the ratio with respect to the entire gel zinc negative electrode. The zinc alloy used was one containing 0.05% by weight of indium, lead and aluminum. As the fluorinated surfactant, one having both a perfluoroalkyl group and a polyoxyethylene group was used.
Pb (OH) ₂ , GeO ₂ , and SnO ₂ were used as the group IVB inhibitors. For the sake of convenience, Pb means Pb (OH) ₂ , and Ge is GeO ₂ and Sn is SnO _{2 as well.}
Represents

First, the corrosion inhibition effect on the zinc alloy of the present invention was investigated. As an experimental method, the alkaline manganese battery shown in FIG. 1 was prototyped and a constant resistance discharge of 1Ω was performed for 22 minutes. After that, the battery was disassembled, 2 g of the gelled zinc negative electrode was collected, and the temperature was maintained at 60 ° C for 10 days.
The amount of hydrogen gas generated under the temperature was measured. Table 3 shows the results obtained by adding 1% by weight of the group IVB inhibitor added to the gelled zinc negative electrode and 0.1% by weight of the fluorine-based surfactant or not adding it. For comparison, the measurement was carried out for the case where only the fluorine-based surfactant was added and the case where neither was added. The gas generation amount shown in Table 3 is an index when the case where neither the IVB group inhibitor nor the fluorine-based interfacial agent is added is 100.

When Pb is used as a Group IVB inhibitor, the amount of gas generated can be suppressed even when it is not mixed with a fluorine-based surfactant. However, as is clear from Table 3, the fluorosurfactant and IVB
The gas generation index is 60 only when a group inhibitor is present.
The gas generation index will be 60 or less if and only if: That is, the coexistence of the index values of about 80 to 96 with only one of them causes a synergistic effect, and the index value can be 60 or less.

Next, the amount of the fluorine-based surfactant added was examined. As the experimental method, the concentration of the fluorine-based surfactant was changed, and the gas generation amount and discharge performance at that time were examined. Similar to the one shown in Example 1, the alkaline manganese battery shown in FIG. 1 is prototyped. For gas generation measurement, 2 g of the gel negative electrode of the battery after discharging for 1 Ω for 22 minutes is sampled, and the amount of hydrogen gas generated at a temperature of 60 ° C. for 10 days is measured. Regarding the discharge performance of the battery, continuous discharge of 10Ω was performed. IV in the gelled zinc negative electrode
The group B inhibitor (Pb (OH) ₂ ) is 1.0% by weight, and the specified amount of fluorine-based surfactant is mixed. The obtained results are shown in FIG. In FIG. 4, the solid line shows the gas generation amount, and the broken line shows the average voltage during 10Ω continuous discharge. Regarding the amount of gas generated, 100 is obtained when neither surfactant nor inhibitor is added.
It was shown by the index. As is clear from FIG. 4, the gas generation amount is suppressed if the addition amount of the fluorine-based surfactant is increased (up to the addition amount of about 0.1 wt%), and beyond that, it hardly changes. On the other hand, it can be seen that the average voltage gradually decreases with an increase in the amount of addition, and sharply decreases after exceeding 1% by weight. Therefore, considering the relationship between these two, the addition amount of the fluorine-based surfactant is 0.01 to 1.0.
It is preferably in the weight%. It was found from experiments that almost the same concentration range is preferable when Ge or Sn is used as the group IVB inhibitor.

Next, the amount of gas generated and the discharge performance with changes in the amount of IVB group inhibitor added were investigated. As an experimental method, the alkaline manganese battery shown in FIG. 1 was prototyped and a constant resistance discharge of 1Ω was performed for 22 minutes. After that, the battery is disassembled and the gel zinc negative electrode is attached.
Collect 2g and measure the amount of hydrogen gas generated by heating at 60 ℃ for 10 days. Regarding the discharge performance of the battery, continuous discharge of 10Ω was performed. The gel-type zinc negative electrode contains 0.1% by weight of a fluorosurfactant and a specified amount of a group IVB inhibitor (Pb (OH ₂ )). The obtained results are shown in FIG. In FIG. 5, the solid line shows the gas generation amount, and the broken line shows the average voltage during 10Ω continuous discharge. The amount of gas generated is an index with 100 when neither surfactant nor inhibitor is added. As is clear from FIG. 5, when the addition amount of the IVB group inhibitor is increased to 0.1% by weight, the gas generation amount is suppressed, and thereafter it becomes almost constant. On the other hand, the average voltage gradually decreases as the amount of inhibitor added increases, and sharply decreases when it exceeds 10% by weight. Considering these two phenomena, the addition amount of the group IVB inhibitor is preferably 0.01 to 10% by weight. It was found that the addition amount regions of Ge and Sn are also preferably almost the same.

Finally, the corrosion inhibition effect by the combination of Pb, Ge, and Sn (IVB group inhibitor) was examined. As an experimental method, the alkaline battery shown in FIG. 1 was prototyped and a constant resistance discharge of 1Ω was performed for 22 minutes. After that, the battery was disassembled and 2g of gel zinc negative electrode was sampled.
Measure the amount of hydrogen gas generated at a temperature of 60 ° C for 10 days.
The obtained results are shown in Table 4. The type and amount of the added Group IVB inhibitor and the amount of the fluorinated surfactant are also shown in the table. In addition, regarding the gas generation amount, surfactant, IVB
The index is based on 100 when no group inhibitor is added.

As is clear from the table, the gas generation is suppressed by combining the inhibitors, and it may be further suppressed by subtly changing the combination and the addition amount. In Table 4, regarding the number of leaked liquids, 20 batteries of each type were made as prototypes and 1Ω constant resistance discharge was performed for 22 minutes. After discharging, the battery was stored at a temperature of 60 ° C. for 2 months, and then the leaked state of the battery was observed. It can be seen that, when neither the fluorine-based surfactant nor the IVB group inhibitor is contained, a considerable number of liquids are leaked, but those containing both according to the present invention do not leak.

Thus, by using a gelled zinc negative electrode containing a zinc alloy corrosion inhibitor containing a fluorine-based surfactant and a Group IVB element, a battery of anhydrous silver or polar zinc reduction is
It is possible to suppress an increase in battery internal pressure due to gas generation and improve liquid leakage resistance.

Example 3 A case of a gelled zinc negative electrode containing a fluorine-based surfactant and a zinc alloy corrosion inhibitor containing a group IIIA element of the periodic table (hereinafter abbreviated as a group IIIA inhibitor) will be described.

The gelled zinc negative electrode was prepared as follows. First, 40
3 wt% in a wt% potassium hydroxide solution (including ZnO)
Gelation is carried out by adding the polyacrylic acid leader of 1. and 1% by weight of carboxymethyl cellulose. After that, a zinc alloy is added to the gel electrolyte in a weight ratio of 2 times, but before the zinc alloy is added, the fluorine-based surfactant and the group IIIA inhibitor are added and thoroughly mixed. These amounts are adjusted to the specified ratio after the zinc alloy powder is added. The addition ratio of the fluorine-based surfactant and the group IIIA inhibitor is the ratio with respect to the entire gel zinc negative electrode. The zinc alloy used was one containing 0.05% by weight of indium, lead and aluminum. As the fluorinated surfactant, one having both a perfluoroalkyl group and a polyoxyethylene group was used. Group IIIA inhibitors are Sc ₂ O ₃ , Y ₂ O ₃ , La ₂ O ₃ , CeO ₂ , Nd
₂ O ₃ and Sm ₂ O ₃ were used. For convenience sake, SC is Sc ₂ O ₃ ,, Y is Y ₂ O ₃ , Ce
Represents CeO ₂ , Nd represents Nd ₂ O ₃ , and Sm represents Sm ₂ O ₃ .

First, the corrosion inhibition effect on the zinc alloy of the present invention was investigated. As an experimental method, the alkaline manganese battery shown in FIG. 1 was prototyped and a constant resistance discharge of 1Ω was performed for 22 minutes. After that, the battery was disassembled, 2 g of the gelled zinc negative electrode was sampled, and the amount of hydrogen gas generated at a temperature of 60 ° C. for 10 days was measured. Table 5 shows the results obtained when the amount of the Group IIIA inhibitor added to the gelled zinc negative electrode was 1% by weight and the amount of the fluorine-based surfactant added was 0.1% by weight or no addition. For comparison, the measurement was carried out for the case where only the fluorine-based surfactant was added and the case where neither was added. The gas generation amount shown in Table 5 is
The index is shown based on 100 when neither the group IIIA inhibitor nor the fluorosurfactant is added. When Y and Nb are used as the group IIIA inhibitor, the gas generation amount can be suppressed even when the fluorine-based surfactant is not mixed.

However, as is clear from Table 5, the index of gas generation amount becomes 60 or less only when the fluorosurfactant and the group IIIA inhibitor containing the lanthanoid system coexist. That is, the coexistence of the index values of about 80 to 95 with only one of them causes a synergistic effect, and the index value can be reduced to 60 or less.

Next, the amount of the fluorine-based surfactant added was examined. As the experimental method, the concentration of the fluorine-based surfactant was changed, and the gas generation amount and discharge performance at that time were examined. Similar to the one shown in Example 1, the alkaline manganese battery shown in FIG. 1 is prototyped. For gas generation measurement, 2 g of the gel negative electrode of the battery after discharging for 1 Ω for 22 minutes is sampled, and the amount of hydrogen gas generated at a temperature of 60 ° C. for 10 days is measured. Regarding the discharge performance of the battery, continuous discharge of 10Ω was performed. II during gel zinc loading
The group IA inhibitor (Y ₂ O ₃ ) is 1.0% by weight, and the specified amount of fluorine-based surfactant is mixed. The obtained results are shown in FIG. In FIG. 6, the solid line shows the gas generation amount, and the broken line shows
The average voltage during 10Ω continuous discharge is shown. The amount of gas generated is shown as an index with 100 when neither surfactant nor inhibitor is added. As is clear from FIG. 4, when the amount of the fluorine-based surfactant added is increased (up to the amount added of around 0.05 wt%), the gas generation amount is suppressed, and beyond that, it hardly changes. On the other hand, it can be seen that the average voltage gradually decreases with an increase in the amount of addition, and sharply decreases after exceeding 1% by weight. Therefore, considering the relationship between these two, the addition amount of the fluorine-based surfactant is 0.01 to 1.0.
It is preferably in the weight%. It was found from experiments that almost the same concentration range is preferable when Y, La, Ce, Nd, and Sm are used as the group IIIA inhibitor.

Next, the gas generation amount and the discharge performance with the change of the addition amount of the group IIIA inhibitor were examined. As an experimental method, the alkaline manganese battery shown in FIG. 1 was prototyped and a constant resistance discharge of 1Ω was performed for 22 minutes. After that, the battery is disassembled and 2 g of the gelled zinc negative electrode is sampled, and the amount of hydrogen gas generated at a temperature of 60 ° C. for 10 days is measured. Also, regarding the discharge performance of the battery, 10Ω
Was continuously discharged. The gelled zinc negative electrode contains 0.1% by weight of a fluorosurfactant and a specified amount of a group IIA inhibitor (Y ₂ O ₃ ). The obtained results are shown in FIG. 7. In FIG. 7, the solid line shows the gas generation amount, and the broken line shows the average voltage during 10Ω continuous discharge. The amount of gas generated is an index with 100 when neither surfactant nor inhibitor is added. As is clear from FIG. 7, when the addition amount of the group IIIA inhibitor is increased up to 0.05% by weight, the gas generation amount is suppressed, and thereafter it becomes almost constant. On the other hand, the average voltage gradually decreases as the amount of inhibitor added increases, and sharply decreases when it exceeds 10% by weight. Considering these two phenomena, the addition amount of the group IIIA inhibitor is preferably 0.01 to 10% by weight. In addition, Sc, La, C
For e, Nd, and Sm, it was found that similar addition amount regions are preferable.

Finally, the corrosion inhibiting effect of some combinations of Group IIIA inhibitors Sc, La, Nd, Sm, Y, Ce was investigated. As an experimental method, the alkaline battery shown in FIG. 1 was prototyped and a constant resistance discharge of 1Ω was performed for 22 minutes. After that, the battery is disassembled, 2 g of the gelled zinc negative electrode is sampled, and the amount of hydrogen gas generated at a temperature of 60 ° C. for 10 days is measured. The obtained results are shown in Table 6. The type and amount of the added Group IIIA inhibitor and the amount of the fluorinated surfactant are also shown in the table. Regarding the amount of gas generated, 100% is obtained when neither surfactant nor IIIA inhibitor is added.
It was shown by the index when.

As is clear from the table, the gas generation is suppressed by combining the inhibitors, and it may be further suppressed by subtly changing the combination and the addition amount. In Table 6, regarding the number of leaked liquids, 20 batteries of each type were made as prototypes and 1Ω constant resistance discharge was performed for 22 minutes. After discharging, the battery was stored at a temperature of 60 ° C. for 2 months, and then the leaked state of the battery was observed. It can be seen that, when neither the fluorosurfactant nor the group IIIA inhibitor is contained, a considerable number of liquids are leaked, but those containing both according to the present invention do not leak.

Thus, by using a gelled zinc negative electrode containing a zinc alloy corrosion inhibitor containing a fluorine-based surfactant and a Group IIIA element, a battery of anhydrous silver or ultra-low mercury zinc can be used to reduce the battery internal pressure due to gas generation. It is possible to suppress the rise and improve the liquid leakage resistance.

Example 4 A case of a gelled zinc negative electrode containing a fluorine-based surfactant and lithium hydroxide as a zinc alloy corrosion inhibitor will be described.

The gelled zinc negative electrode was prepared as follows. First, 40
3 wt% in a wt% potassium hydroxide solution (including ZnO)
Gelation is carried out by adding the polyacrylic acid leader of 1. and 1% by weight of carboxymethyl cellulose. After this, a zinc alloy is added to the gel electrolyte in a weight ratio of 2 times. Before the zinc alloy is added, the fluorine-based surfactant and lithium hydroxide are added and thoroughly mixed. These amounts are adjusted to the specified ratio after the zinc alloy powder is added. The addition ratio of the fluorine-based surfactant and lithium hydroxide is the ratio with respect to the whole gel zinc negative electrode. Further, as the zinc alloy, one containing 0.05% by weight of indium, lead and aluminum was used. As the fluorinated surfactant, one having both a perfluoroalkyl group and a polyoxyethylene group was used.

First, the corrosion inhibition effect on the zinc alloy of the present invention was investigated. As an experimental method, the alkaline manganese battery shown in FIG. 1 was prototyped and a constant resistance discharge of 1Ω was performed for 22 minutes. After that, the battery was disassembled, 2 g of the gelled zinc negative electrode was collected, and the temperature was maintained at 60 ° C for 10 days.
The amount of hydrogen gas generated under the temperature was measured. Table 7 shows the results obtained when the addition amount of thylium hydroxide added to the gelled zinc negative electrode was 0.5% by weight and the addition amount of the fluorosurfactant was 0.1% by weight or no addition.

For comparison, measurements were also carried out for the case where only the fluorine-based surfactant was added and the case where neither was added. The gas generation amount shown in Table 7 is shown as an index when 100 is assumed when neither thylium hydroxide nor a fluorine-containing surfactant is added. As is clear from Table 7, the index of gas generation amount is greatly reduced to 51 only when the fluorine-based surfactant and lithium hydroxide coexist. In other words, the coexistence of the index values of about 78 to 81 with only one of them causes a synergistic effect, and the gas generation amount can be significantly suppressed.

Next, the amount of the fluorine-based surfactant added was examined. As the experimental method, the concentration of the fluorine-based surfactant was changed, and the gas generation amount and discharge performance at that time were examined. Similar to the one shown in Example 1, the alkaline manganese battery shown in FIG. 1 is prototyped. For gas generation measurement, 2 g of the gel negative electrode of the battery after discharging for 1 Ω for 22 minutes is sampled, and the amount of hydrogen gas generated at a temperature of 60 ° C. for 10 days is measured. Regarding the discharge performance of the battery, continuous discharge of 10Ω was performed. During loading of gel-like zinc, 0.5% by weight of lithium hydroxide and a specified amount of fluorine-based surfactant were mixed. The obtained results are shown in FIG.
In FIG. 8, the solid line shows the gas generation amount, and the broken line shows the average voltage during 10Ω continuous discharge. Regarding the amount of gas generated,
100% when neither surfactant nor lithium hydroxide is added
It was shown by the index. As is clear from FIG. 8, the gas generation amount is suppressed when the addition amount of the fluorine-based surfactant is increased (up to the addition amount of around 0.05 wt%), and beyond that, it hardly changes. On the other hand, it can be seen that the average voltage gradually decreases with an increase in the amount of addition, and sharply decreases after exceeding 1% by weight. Therefore, considering the relationship between both, it is preferable that the addition amount of the fluorine-based surfactant is 0.01 to 1.0% by weight.

Next, the amount of gas generated and the discharge performance with changes in the amount of lithium hydroxide added were examined. As an experimental method, the alkaline manganese battery shown in FIG. 1 was prototyped and a constant resistance discharge of 1Ω was performed for 22 minutes. After that, the battery is disassembled and 2 g of a gelled zinc negative electrode is adopted, and the amount of hydrogen gas generated at a temperature of 60 ° C. for 10 days is measured. Also, regarding the discharge performance of the battery,
A continuous discharge of Ω was performed. The gelled zinc negative electrode contains 0.1% by weight of a fluorosurfactant and a specified amount of lithium hydroxide. The obtained results are shown in FIG. In FIG. 9, the solid line shows the gas generation amount, and the broken line shows the average voltage during 10Ω continuous discharge. The amount of gas generated is an index with 100 when neither surfactant nor lithium hydroxide is added. As is clear from FIG. 9, if the amount of lithium hydroxide added is increased up to 0.05% by weight, the amount of gas generation is suppressed, and thereafter it becomes constant. On the other hand, the average voltage gradually decreases as the amount of lithium hydroxide added increases, and sharply decreases when it exceeds 10% by weight. Considering these two phenomena, the addition amount of lithium hydroxide is preferably 0.01 to 10% by weight.

Thus, by using a gelled zinc negative electrode containing lithium hydroxide as a fluorine-based surfactant and a zinc alloy corrosion inhibitor, a battery of anhydrous silver or extremely low zinc halide,
It is possible to suppress the rise in the internal pressure of the battery due to the generation of gas and improve the liquid leakage resistance.

EFFECTS OF THE INVENTION As described above, according to the present invention, in a gelled zinc negative electrode in an alkaline battery, a fluorine-based surfactant and a zinc alloy corrosion inhibitor are contained, whereby zinc-free or extremely low-leveling is achieved. Even if zinc is used, it is possible to obtain the effect of suppressing the rise in internal pressure of the battery and improving the liquid leakage resistance.

[Brief description of drawings]

FIG. 1 is a sectional view of a battery according to an embodiment of the present invention,
2 to 9 are graphs showing the relationship between the amount of corrosion inhibitor added, the gas generation index, and the average voltage during discharge. 1 ... Positive electrode mixture, 2 ... Gel-like negative electrode using anhydrous silver-zinc alloy containing gel-electrolytic solution containing fluorochemical surfactant and zinc alloy corrosion inhibitor, 3 ... Separator.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Seiji Toge, 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Yoshiaki Nitta, 1006 Kadoma, Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd. (72) Inventor Suetsugu Sachiko 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.

Claims (15)

[Claims] 1. An alkaline battery provided with a gel-like zinc negative electrode obtained by using unreduced or low-definition zinc gold powder having a mercury content of up to 500 ppm as a main active material of a negative electrode and mixing this with a gel-like alkaline electrolyte. An alkaline battery, wherein the gelled alkaline electrolyte contains a fluorine-based surfactant and a zinc alloy corrosion inhibitor containing an element of Group IIIB of the periodic table. 2. The zinc alloy corrosion inhibitor is at least one oxide or hydroxide selected from the group of indium, gallium, thallium and boron, or an alkali metal salt thereof. The alkaline battery according to item 1. 3. The alkaline battery according to claim 1, wherein the content of the fluorine-based surfactant is 0.01 to 1% by weight with respect to the gelled zinc negative electrode. 4. The alkaline battery according to claim 1, wherein the total amount of the zinc alloy corrosion inhibitor is 0.01 to 10% by weight with respect to the gelled zinc negative electrode. 5. An alkaline battery provided with a gelled zinc negative electrode prepared by mixing a gelled alkaline electrolyte with unblended or low-graded zinc gold powder having a mercury content of up to 500 ppm as a living material for the negative electrode. An alkaline battery characterized in that the gelled alkaline battery liquid contains a fluorine-based surfactant and a zinc alloy corrosion inhibitor containing an element of Group IVB of the periodic table. 6. A zinc alloy corrosion inhibitor is at least one oxide or hydroxide from the group of lead, tin and germanium,
Alternatively, the alkaline battery according to claim 5, which is an alkali metal salt thereof. 7. The alkaline battery according to claim 5, wherein the content of the fluorine-based surfactant is 0.01 to 1% by weight with respect to the gelled zinc negative electrode. 8. The alkaline battery according to claim 5, wherein the total amount of the zinc alloy corrosion inhibitor is 0.01 to 10% by weight with respect to the gelled zinc negative electrode. 9. An alkaline battery provided with a gel-like zinc negative electrode obtained by using unreduced or low-definition zinc gold powder having a mercury content of up to 500 ppm as a main active material of the negative electrode and mixing this with a gel-like alkaline electrolyte. The periodic table II containing a fluorosurfactant and a lanthanoid system in the gelled alkaline electrolyte.
An alkaline battery comprising a zinc alloy corrosion inhibitor containing a Group IA element. 10. A zinc alloy corrosion inhibitor is scandium,
At least one oxide or hydroxide from the group of yttrium, lanthanum, cerium, neodymium, samarium,
The alkaline battery according to claim 9, which is also an alkali metal salt thereof. 11. The alkaline battery according to claim 9, wherein the content of the fluorine-based surfactant is 0.01 to 1% by weight with respect to the gelled zinc negative electrode. 12. The alkaline battery according to claim 9, wherein the total amount of the zinc alloy corrosion inhibitor is 0.01 to 10% by weight with respect to the gelled zinc negative electrode. 13. A method for producing a negative electrode as a living substance,
An alkaline battery comprising a gelled zinc negative electrode obtained by mixing low-grade zinc-gold powder with a mercury content of up to 500 ppm into a gelled alkaline electrolyte, wherein the gelled alkaline electrolyte contains a fluorine-based interface. An alkaline battery comprising an activator and lithium hydroxide as a zinc alloy corrosion inhibitor. 14. The alkaline battery according to claim 13, wherein the content of the fluorine-based surfactant is 0.01 to 1% by weight based on the gelled zinc negative electrode. 15. The alkaline battery according to claim 13, wherein the total amount of lithium hydroxide is 0.01 to 10% by weight with respect to the gelled zinc negative electrode.