JP2002175794A - Lead-acid battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly reliable and long-life lead-acid battery with a strap excellent in the corrosion resistance. SOLUTION: In the lead-acid battery, a lead (Pb)-Sb-As-Se alloy comprising 1.7-3.5 mass % of antimony (Sb), 0.1-0.3 mass % of arsenic(As), 0.007-0.03 mass % of selenium(Se) is used as the added lead for forming the strap to connect lug parts of electrode plates by the cast-on-strap method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a lead storage battery.

[0002]

2. Description of the Related Art Conventionally, a Pb-Sb-based alloy has been used as a current collector (grid) in a so-called open-type lead-acid battery in which a fluid exists around an electrode group. However, a battery using this alloy has a large self-discharge and a large decrease in electrolyte, and it has been difficult to use it in a maintenance-free type battery. Therefore, we suppress self-discharge and decrease of electrolyte solution,
Pb-
Ca-based alloys have come to be used.

[0003] However, when a Pb-Ca alloy is used for the positive electrode grid, the life may be shortened at an early stage when exposed to deep discharge or used at a high temperature. Therefore, the positive electrode should be made of Pb so that it can withstand deep discharge and use at high temperatures while minimizing self-discharge and decrease in electrolyte.
A so-called hybrid battery using an -Sb-based alloy lattice and a Pb-Ca-based alloy lattice as a negative electrode has been manufactured.

[0004] As described above, both the positive and negative grids are composed of Pb-Ca.
A battery using a system alloy and a hybrid battery are used so as to bring out their respective performances according to the application.

[0005] The lead for forming a strap connecting the ears of the grid of these lead-acid batteries is usually Pb-S
A b-based alloy is used.

[0006] There are mainly two methods for welding the lugs of the lattice and the lead for forming the strap.

One is a cast-on-strap (C)
In a method called as on strap (COS), this involves pouring molten lead alloy into a mold engraving the shape of the strap, placing an ear there,
By cooling and solidifying the additional lead alloy, the ear portion and the additional lead are welded to each other and a strap is formed at the same time.

The other is to fit the lugs into a comb-shaped jig for forming a strap, and then pour the lead of a Pb-Sb-based alloy into a recess formed by the jig while melting it with a gas burner or the like. And welding the ears and the lead while melting, while simultaneously forming a strap.

[0009]

When welding the lugs of the lattice made of the Pb-Sb alloy and the lead made of the Pb-Sb alloy, the alloy compositions of the lugs and the lead are similar. Had no particular problems. However, when attempting to weld a lattice lug made of a Pb-Ca alloy and a lead made of a Pb-Sb-based alloy, Ca is very easily oxidized, and the vicinity of a welding interface between the lug and the lead is increased. In some cases, the strap is corroded at an early stage due to the fact that the compound is easily corroded, a compound of Ca and Sb is generated, and the battery reaches its end of life.

Regarding the problem that the positive electrode strap is corroded at an early stage due to the formation of a compound of Ca and Sb, the inventors of the present application disclose in Japanese Patent Publication Nos. 3-73985 and 3-73986. In order to suppress the formation of a compound of Sb and Ca, the amount of Ca
It has been proposed to suppress the amount of b to a certain amount or less. Japanese Patent Application Laid-Open No. 6-52845 proposes to further reduce the amount of Ca in a Pb-Ca based alloy lattice.

By these methods, the amount of Ca was reduced, and the amount of the compound of Ca and Sb which was easily corroded was reduced. However, the main alloy composition in the strap was a Pb-Sb-As alloy, although a part of the ear was melted and Sn contained in the ear was mixed in to some extent. Since this alloy has large crystal grains, there is a problem that when the strap starts to corrode, the corrosion progresses deeply along the crystal grain boundaries, thereby shortening the battery life.

An object of the present invention is to solve such a corrosion.
When a strap is formed by welding an additional lead using a b-Sb alloy, not only the corrosion of the strap due to the compound of Ca and Sb is suppressed, but also a large crystal grain of the Pb-Sb-As alloy. Accordingly, it is an object of the present invention to provide a strap excellent in corrosion resistance by suppressing the progress of deep corrosion along grain boundaries.

In recent years, for example, in the case of automobile batteries, the output of the alternator for charging the engine and the lead storage battery has been increased, the variety of electrical components has been increased, and the use of slant nose for reducing aerodynamic drag has led to an increase in the engine room. The temperature is getting higher. Under a severe use environment at such a high temperature, not only the strap is easily corroded, but also the positive electrode grid is easily corroded. This may be a problem particularly when a Pb-Ca alloy is used for the positive electrode. However, a Pb-Ca alloy having excellent corrosion resistance at high temperatures is used for the positive electrode grid, and a strap having excellent corrosion resistance is used. When used together, a more reliable and long-life lead-acid battery can be provided.

Incidentally, strap corrosion occurs not only in the positive electrode strap but also in the negative electrode strap. Generally, in a lead-acid battery, the negative electrode becomes metallic lead when charged, and should not be corroded, but for some reason, the electrolyte level drops,
If the negative electrode strap is exposed from the electrolytic solution, or if the electrolytic solution is not sufficiently replenished, such as in a small gap even in the electrolytic solution, it will not be reduced to metallic lead even when charged, and corrosion will proceed. It is.

[0015]

In order to solve the above-mentioned problems, a lead-acid storage battery according to the first aspect of the present invention uses a cast battery.
As an additional lead for forming a strap for connecting the electrode plate ears by the on-strap method, Sb is 1.7 to 1.7.
Pb-Sb-As-S containing 3.5% by mass, 0.1 to 0.3% by mass of As, and 0.007 to 0.03% by mass of Se
It is characterized by using an e-based alloy.

According to a second aspect of the present invention, in the lead-acid battery according to the first aspect, the Pb-Sb-As-Se alloy contains 0.02 to 0.1% by mass of Sn.

According to a third aspect of the present invention, in the lead-acid battery according to the first or second aspect, the positive electrode grid contains Ca in an amount of 0.
025 to 0.065% by mass, 0.75 to 2.0% by mass of Sn, the balance being Pb, and the negative electrode lattice containing Ca in an amount of 0.25% by mass.
It contains 0.25 to 0.065% by mass of Sn and 0.25 to 2.0% by mass of Sn, with the balance being Pb.

According to a fourth aspect of the present invention, in the lead-acid battery according to the third aspect, at least one of the positive electrode grid and the negative electrode grid contains 0.003 to 0.03% by mass of Al.

According to a fifth aspect of the present invention, in the lead-acid battery according to the third or fourth aspect, the positive electrode grid contains 0.02 to 0.09% by mass of Ag.

According to the invention described in claim 6, in the lead-acid battery according to claim 1 or 2, at least S
Pb-Sb containing 0.5 to 3.0% by mass of b, 0.1 to 0.3% by mass of As, and 0.007 to 0.03% by mass of Se
A Pb-Ca-Sn-based alloy lattice containing at least 0.025 to 0.065% by mass of Ca and 0.25 to 2.0% by mass of Sn is used for the negative electrode plate using a lattice made of an -As-Se-based alloy. Things.

In the invention according to claim 7, in the lead-acid battery according to claim 6, Pb-Sb-A for the positive electrode grid is provided.
The s-Se-based alloy contains 0.02 to 0.1% by mass of Sn.

According to the invention described in claim 8, in the lead-acid battery according to claim 6 or 7, the Pb-
Ca—Sn based alloy 0.003 to 0.03 mass% Al
Including.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a Pb-Sb-As based alloy for a lead which forms a strap by the COS method.
Since e is added, the crystal grains of the strap can be made finer, and the corrosion (grain boundary corrosion) along the crystal grain boundaries can be suppressed from deeply progressing not only in the positive electrode strap but also in the negative electrode strap. Since the amount of Ca used in the Pb-Ca-based alloy lattice is made smaller than before, the amount of the compound of Ca and Sb which is easily corroded in the strap can be suppressed, and the strap can be made more corrosion resistant. The present invention provides a lead-acid battery having a long life.

Further, when a Pb-Ca alloy lattice is used for the positive electrode, the positive electrode lattice having excellent corrosion resistance is used together even under a severe use environment at a high temperature.
An object of the present invention is to provide a reliable and long-life lead-acid battery.

Sb in Pb-Sb-As alloy for lead
When the amount is less than 1.7% by mass, welding workability and strength of the strap are inferior. When the amount is more than 3.5% by mass, in the case of the positive electrode, Sb is eluted from the strap during use of the battery and precipitates on the negative electrode plate. Therefore, the hydrogen overvoltage is reduced, and the decomposition of water is promoted.

As in Pb-Sb-As alloy for lead
If the amount is less than 0.1% by mass, the corrosion resistance is poor,
If the amount is more than the mass%, the effect is not so changed and it is uneconomical, so that 0.1 to 0.3 mass% is preferable.

If the amount of Se added to the Pb-Sb-As alloy for lead is less than 0.007% by mass, the effect of refining the crystal grains is inferior. The effect of miniaturization does not change much and is not only uneconomical, but also because of the temperature dependence of the solubility of Se in Pb alloys, it is difficult to dissolve at the normal welding operation temperature (about 500 ° C. or less). 007 to 0.03% by mass is preferred.

In order to improve the fluidity of the molten lead alloy during welding, Sn may be added to the Pb-Sb-As alloy for lead in an amount of 0.02 to 0.1% by mass.

The amount of Ca in the positive electrode lattice alloy is desirably 0.065% by mass or less in order to suppress the amount of the compound of Ca and Sb, but from the viewpoint of lattice strength, 0.025% by mass is preferred.
The above is desirable.

The amount of Sn in the positive electrode lattice alloy is desirably 0.75% by mass or more from the viewpoint of the corrosion resistance and strength of the positive electrode lattice during use of the battery. However, even if it exceeds 2.0% by mass, the corrosion resistance is rather poor. In addition, it is uneconomical in terms of cost, and 0.75 to 2.0% by mass is appropriate.

The amount of Ca in the negative electrode grid alloy is desirably 0.025 to 0.065% by mass, as in the case of the positive electrode grid.

On the other hand, the negative electrode grid does not require as much corrosion resistance as the positive electrode grid during use of the battery, and therefore does not require as much Sn content as the positive electrode grid does. Since the handleability deteriorates, the amount of Sn in the negative electrode lattice is desirably 0.25% by mass or more. The upper limit is desirably as small as possible from the economical point of view as long as there is no problem in handling. However, it is possible to add up to 2.0% by mass, which is almost the same as that of the positive electrode grid in relation to the production quantity and production equipment. .

The Pb-Ca-Sn based alloy lattice is not limited to the lattice produced by the gravity casting method which has been conventionally used, but the Pb-C alloy whose production amount is increasing in recent years.
It is also possible to use a grid manufactured by expanding or punching a rolled a-Sn alloy sheet or a cast sheet. In these methods, the production speed is higher than in the conventional gravity casting method, and the grid can be manufactured economically.

Further, the grid shape is engraved on the rotating roll, a shoe is pressed against the rotating roll from the outside, and the molten lead alloy is press-fitted between the engraved grid-shaped groove and the pressed shoe to solidify while rotating. The lattice can also be obtained by a method of performing continuous casting. Further, at this time, it is also possible to manufacture a grid by continuously casting a slightly thicker grid and then rolling.

When a Pb-Ca-Sn alloy grid is manufactured by gravity casting or continuous casting, or when a grid is manufactured by an expanding method or a punching method, a slab (flat plate) for a rolled sheet is cast or cast. When manufacturing a sheet, 0.003 to 0.03 mass% of Al is added to prevent oxidation of Ca and stabilize the Ca amount. If this method is used, it is not necessary to use an inert gas such as an argon gas to prevent the oxidation of Ca, and the workability is good and economical.

Here, the cast sheet is also called a DM sheet, and is obtained by slightly immersing a rotating roll in a molten lead alloy to form a sheet directly on the roll surface.

In recent years, the temperature of the environment in which lead-acid batteries are used has been increasing, and in order to improve the durability of the Pb—Ca-based alloy grid for the positive electrode under such high temperatures, it is necessary to use a positive grid. It is effective to add 0.02 to 0.09% by mass of Ag, and a more reliable and long-life lead-acid battery can be obtained by using Ag together with the above-described strap.

S in the Pb-Sb-As alloy for the positive electrode lattice
The amount b is determined based on a balance between deep discharge performance / high temperature characteristics and maintenance-free characteristics. If less than 0.5% by mass, maintenance-free characteristics are excellent but deep discharge performance / high-temperature characteristics are inferior. If the content is more than 3.0% by mass, although the deep discharge performance and the high-temperature characteristics are excellent, Sb elutes from the positive electrode grid during use of the battery, deposits on the negative electrode plate, reduces the hydrogen overvoltage, and the maintenance-free characteristics deteriorate. , 0.5 to 3.0% by mass.

A in the Pb-Sb-As alloy for the positive electrode lattice
If the amount of s is less than 0.1% by mass, the corrosion resistance is inferior.
If the amount is more than 30% by mass, the effect is not so different and it is uneconomical, so that 0.1 to 0.3% by mass is desirable.

When the amount of Se added to the Pb-Sb-As alloy for the positive electrode lattice is less than 0.007% by mass, the effect of refining the crystal grains is inferior. The effect of miniaturization does not change much and is not only uneconomical, but also because of the temperature dependence of the solubility of Se in the Pb alloy, it is difficult to dissolve at a normal casting working temperature (about 520 ° C. or less). 007 to 0.03% by mass is desirable.

In order to improve the fluidity of the molten lead alloy at the time of casting, the Pb-Sb-As-Se-based alloy for the positive grid was
n can be added in an amount of 0.02 to 0.1% by mass. P
In the case of the b-Sb-As alloy, the lattice can be obtained by the continuous casting method as in the case of the Pb-Ca-Sn alloy.

[0042]

Embodiments of the present invention will be described below. (Example 1) A rolled sheet using a Pb-Ca-Sn-based alloy in which the amounts of Ca and Sn were changed as shown in Table 1 was prepared and expanded to obtain a positive electrode grid for an automobile battery. Was. In each case, 0.01% by mass of Al was added in order to prevent oxidation during casting of the slab for rolling.

[0043]

[Table 1]

Next, these grids are filled with a positive electrode paste according to a conventional method, aged and dried.
Sheets, 6 negative plates and a separator, COS
A strap was formed by a method to obtain a 12 V, 30 Ah automotive battery. Pb-Sb-A for strap alloy
An s-Se alloy was used, the amounts of Sb and Se were as shown in Table 1, and the As was 0.25% by mass in each case.

The negative electrodes of these batteries were provided with No. Using a grid of 10, a negative electrode paste was filled according to a conventional method, and aged and dried.

When the cross sections of the positive electrode straps of these batteries were observed with a metallographic microscope, as shown in Table 2, column B,
When Se was contained in an amount of 0.007% by mass or more, the crystal grain size was extremely fine, about 1/5 to 1/6, irrespective of the lattice alloy composition, as compared with the case where Se was not contained.

Next, these batteries of the same lot were placed at 60 ° C.
In a gas tank, a continuous overcharge test was performed at a constant voltage of 14.4 V for 5 weeks, and the corrosion state of the positive electrode strap and the state of the positive electrode grid after the test were observed.

The corrosion states of the positive electrode strap and the positive electrode grid after the overcharge test are shown in Table 2, columns C and D, respectively.

[0049]

[Table 2]

In a lead-acid battery, corrosion of the positive electrode member is unavoidable.
When the amount of a is 0.020 to 0.065% by mass,
Even after the overcharge test, corrosion of the positive electrode strap portion was slight.

As described above, in the strap obtained by adding 0.007% by mass or more of Se to the Pb-Sb-As alloy for lead, the crystal grain size is about 1/5 to 1/1 compared to the case where Se is not added. 6, which is very small,
Progress of intergranular corrosion in the positive electrode strap after the overcharge test was hardly observed.

However, when the amount of Sn in the positive electrode grid was 0.4% by mass, corrosion of the positive electrode grid after the overcharge test was severe.

When the amount of Ca in the positive electrode grid was 0.02% by mass, the grid strength was low and the handling property in battery production was poor. (Example 2) A rolled sheet using a Pb-Ca-Sn-based alloy in which the amounts of Ca and Sn were changed as shown in Table 3 was prepared and expanded to obtain a negative electrode grid for an automobile battery. Was.

[0054]

[Table 3]

Next, these grids are filled with a negative electrode paste according to a conventional method, aged and dried.
Sheets, 6 negative plates and a separator, COS
A strap was formed by a method to obtain a 12 V, 30 Ah automotive battery. Pb-Sb-A for strap alloy
An s-Se alloy was used, the amounts of Sb and Se were as shown in Table 3, and As was 0.20% by mass in each case.

The positive electrode plates of these batteries were provided with No. 1 described in Example 1 and Table 1. Using 14 grids, a positive electrode paste was filled according to a conventional method, and aged and dried.

When the cross sections of the negative electrode straps of these batteries were observed with a metallurgical microscope, as shown in Table 4, column B,
When Se was contained in an amount of 0.007% by mass or more, the crystal grain size was extremely fine, about 1/5 to 1/6, irrespective of the lattice alloy composition, as compared with the case where Se was not contained.

Next, these batteries of the same lot were placed at 60 ° C.
A continuous overcharge test was performed at a constant voltage of 14.4 V in an air tank for 5 weeks, and the corrosion state of the negative electrode strap after the test was observed.

Prior to the overcharge test, the test was performed with the negative electrode strap exposed from the electrolyte surface by intentionally lowering the electrolyte surface of each battery. This is to evaluate the corrosion state of the strap in a short period of time because the corrosion of the positive electrode strap occurs in the electrolytic solution, but the corrosion of the negative electrode strap is more likely to be corroded when the strap is exposed from the electrolytic solution surface.

The corrosion state of the negative electrode strap after the overcharge test is shown in Table 4, column C.

[0061]

[Table 4]

As is apparent from Table 4, the amount of Ca was set to 0.0
In the case of 2 to 0.065% by mass, the corrosion of the negative electrode strap portion was slight even after the overcharge test. In addition, 0.007 Se was added to the Pb-Sb-As alloy for additional lead.
As described above, the crystal grain size of the strap added with not less than 5% by mass is about 1/5 to 1 /
As a result, the progress of intergranular corrosion in the negative electrode strap after the overcharge test was hardly recognized.

However, when the amount of Sn in the negative electrode lattice was 0.2% by mass, the lattice strength was low, and the handleability in battery production was poor.

When the amount of Ca in the negative electrode lattice was 0.02% by mass, the lattice strength was low and the handling property in battery production was poor. (Example 3) A positive electrode grid for an automobile battery was obtained by a gravity casting method using a Pb-Ca-Sn-Ag-based alloy in which the amount of Ag was changed as shown in column A of Table 5. The Ca content and the Sn content were 0.03% by mass and 1.0% by mass, respectively.
In each case, Al was added in an amount of 0.01% by mass to prevent oxidation during lattice casting.

Next, these grids are filled with a positive electrode paste according to a conventional method, aged and dried.
Sheets, 6 negative plates and a separator, COS
A strap was formed by a method to obtain a 12 V, 30 Ah automotive battery. Pb-Sb-A for strap alloy
An s-Se-Sn alloy was used, and the amounts of Sb, As, Se, and Sn were 2.8% by mass, 0.25% by mass, 0.02% by mass, and 0.02% by mass, respectively.

Incidentally, the negative electrode plates of these batteries were provided with Pb-
0.060 mass% Ca-0.75 mass% Sn-0.01
A gravity cast grid made of a mass% Al alloy was used, and a negative electrode paste was filled according to a conventional method, and aged and dried.

These batteries were placed in an air bath at 60 ° C. for 14.4 hours.
A continuous overcharge life test was performed at a constant voltage of V, and a discharge at 150 A was performed for 30 seconds every week, and the time when the battery voltage at the 30th second became 7.2 V or less was defined as the life. After the test, the deterioration state of the positive electrode plate and the corrosion state of the positive and negative electrode straps were observed. In this test, the electrolyte surface was adjusted to a normal upper level, and both the positive and negative electrode straps were located in the electrolyte.

The test results are shown in Table 5, columns B to D.

[0069]

[Table 5]

As is clear from Table 5, Ag was 0.02
In the case of containing not less than mass%, Ag was not contained, or even if containing Ag, it had a high temperature life performance 1.5 to 2 times that of the case of containing 0.01 mass%. This is considered to be due to the fact that the corrosion resistance of the positive electrode grid was improved by adding Ag. Even if Ag is added in an amount of more than 0.09% by mass, the corrosion resistance of the positive electrode grid is not so different from the case where 0.09% by mass is added, and it is uneconomical because silver is expensive. In addition, the positive and negative electrode straps were hardly corroded in any of the batteries, or were very little corroded, and did not affect the battery performance. (Example 4) Pb-0.7 mass% Sb-0.25 for the positive electrode
Mass% As-0.02 mass% Se-0.02 mass% Sn
Using a continuous casting grid made of an alloy, the negative electrode was made of Pb-0.
A continuous casting grid made of 065 mass% Ca-0.50 mass% Sn-0.01 mass% Al alloy was used. These positive / negative electrode grids are filled with positive / negative electrode pastes according to a conventional method, aged and dried, and then combined with five positive electrode plates, six negative electrode plates and a separator to form a strap by the COS method and forming a 12V strap. , 30 Ah for an automobile. Pb-Sb-As-Se for strap alloy
-Sn alloy is used, and the amount of Sb is 1.0, 1.7, 2.
The amounts of As, Se and Sn were 0.25% by mass and 0.02% by mass, respectively.
And 0.06% by mass.

The same test as in Example 1 was performed on these batteries.

When the amount of Sb in the lead-forming alloy for forming the strap was 1.0 to 3.5% by mass, almost no corrosion of the strap was observed, but when the amount of Sb was 4.0% by mass,
A little strap corrosion was observed. Further, when the amount of Sb is 1.
In the case of 0% by mass, the strength of the strap was weak. From these results, Pb-Sb-As-Se- for strap
The Sb content of the Sn-based alloy is desirably 1.7 to 3.5% by mass.

In Examples 1-4, welding with a gas burner was also attempted in place of the COS method.
The portion where the effect of crystal grain refinement by e was not observed was observed, and small lumpy particles were scattered around the strap surface.

This can be considered as follows.

In the case of the COS method, immediately before welding, approximately 45
In a Pb-Sb-As-Se alloy melt at 0 ° C., each element is uniformly dissolved and solidifies in a strap-shaped mold without further heating, so that Se It seems that the effect of was sufficiently obtained.

On the other hand, it is not clear why the effect of Se was not sufficiently observed due to partial refinement of crystal grains by the gas burner method. The molten Pb-Sb-As-Se alloy is heated by a gas burner, so that Se in the molten metal is oxidized and becomes particulate, and these particles rise upward in a strap still molten due to a difference in specific gravity. , And as a result, S inside the strap, which is effective for refining crystal grains,
This is considered to be due to the occurrence of a portion where e is greatly reduced. In addition, particles of Se or the like, which are considered to be oxidized or moved upward in the strap, are trapped in the strap surface when the strap surface solidifies, and as a result, small massive particles are trapped in the strap surface. It is probable that they were found nearby.

From the above description, it is desirable to form the strap by the COS method in order to ensure the effect of the refinement of the crystal grain by adding Se.

[0078]

As described above, according to the present invention, Se is added to the Pb-Sb-As alloy for lead which forms a strap by the COS method. Not only in the negative electrode strap but also in the negative electrode strap, corrosion along the crystal grain boundary (grain boundary corrosion) can be suppressed from progressing deeply, and at the same time, the amount of Ca used in the Pb-Ca-based alloy lattice is reduced. Ca and S in the strap are easily corroded.
The amount of the compound with b can be suppressed, and the strap can be made even more excellent in corrosion resistance. As a result, a long-life lead-acid battery can be provided.

Further, when a Pb-Ca based alloy lattice is used for the positive electrode, the positive electrode lattice having excellent corrosion resistance can be employed even under a severe use environment at a high temperature.
An object of the present invention is to provide a reliable and long-life lead-acid battery.

Claims (8)

[Claims] 1. An antimony (Sb) content of 1.7 to 3.5% by mass as an additional lead for forming a strap for connecting electrode plate ears by a cast-on-strap method.
0.1 to 0.3% by mass of arsenic (As), selenium (Se)
(Pb) -Sb- containing 0.007 to 0.03% by mass of
A lead-acid battery using an As-Se alloy. 2. The Pb—Sb—As—Se-based alloy,
The lead-acid battery according to claim 1, wherein the lead-acid battery contains 0.02 to 0.1% by mass of tin (Sn). 3. The positive electrode grid contains calcium (Ca) of 0.0
It is made of a Pb-Ca-Sn-based alloy containing 25 to 0.065% by mass and 0.75 to 2.0% by mass of Sn.
a is 0.025 to 0.065% by mass, Sn is 0.25 to
The lead-acid battery according to claim 1, comprising a Pb—Ca—Sn-based alloy containing 2.0% by mass. 4. The lead-acid battery according to claim 3, wherein at least one of the positive electrode grid and the negative electrode grid contains 0.003 to 0.03% by mass of aluminum (Al). 5. The positive electrode grid contains silver (Ag) in an amount of 0.02-0.
The lead-acid battery according to claim 3, wherein the lead-acid storage battery contains 09% by mass. 6. The positive electrode grid contains 0.5% to 3.0% by mass of Sb, 0.1% to 0.3% by mass of As, and 0.007% by mass of Se.
Pb-Ca-S made of a Pb-Sb-As-Se-based alloy containing 0.03% by mass, wherein the negative electrode lattice contains 0.025 to 0.065% by mass of Ca and 0.25 to 2.0% by mass of Sn.
The lead-acid battery according to claim 1, comprising an n-based alloy. 7. The positive electrode lattice Pb-Sb-As-Se.
The lead storage battery according to claim 6, wherein the system alloy contains 0.02 to 0.1% by mass of Sn. 8. The lead-acid battery according to claim 6, wherein the Pb—Ca—Sn-based alloy for a negative electrode grid contains 0.003 to 0.03% by mass of Al.