JPH09231981A - Lead storage battery - Google Patents

Abstract

(57) 【Abstract】 PROBLEM TO BE SOLVED: To reduce the amount of antimony added in a positive electrode grid alloy or to adopt a lead alloy positive electrode grid containing no antimony, in order to improve the maintenance characteristics of a lead storage battery, so-called low antimony or antimony. With the progress of becoming free, a new problem of stratification of the electrolytic solution has arisen. SOLUTION: Antimony is 0.8% by weight or more and 3% by weight.
Hereinafter, arsenic is 0.1% by weight or more and 0.4% by weight or less, copper is 0.0005% by weight or more and 0.03% or less, bismuth is 0.001% by weight or more and 0.03% by weight or less, and silver is 0. 0
005 wt% or more and 0.25 wt% or less, tin 0.000
5% by weight or more and 0.1% by weight, and nickel 0.00
A lead-acid battery using a lead alloy containing 02 wt% or more and 0.003 wt% or less for a positive electrode grid.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an improvement of a lead storage battery.

[0002]

2. Description of the Related Art Lead-acid batteries are used in many applications including starting and lighting of automobiles, as well as small capacity consumers and large capacity stationary applications. In recent years, various improvements have been made to lead-acid batteries in order to suppress self-discharge during standing and to reduce water replenishment due to decomposition of electrolyte (dilute sulfuric acid) during use. Typical examples thereof include a reduction in the amount of antimony added to the positive electrode lattice alloy or the use of a positive electrode lattice made of a lead alloy (lead-calcium-tin-based alloy) containing no antimony. With the progress of so-called antimony reduction or antimony-free as described above, the above problem has been reduced, but a new problem of stratification of the electrolytic solution has arisen.

Sulfuric acid in the electrolytic solution of a lead-acid battery is deposited as lead sulfate in the positive and negative electrode active materials by the discharge reaction and is released from the active material into the electrolytic solution by the charging reaction. The sulfuric acid released during charging moves to the lower part of the battery because it has a higher specific gravity than the surrounding electrolytic solution, and as a result, the stratification phenomenon that the specific gravity of the electrolytic solution in the upper part of the battery is lower than that in the lower part Known to cause. Such electrolyte layering has been a problem in the past when the depth of discharge is large, that is, when used under heavy load, but with the recent low antimony or antimony-free use, even under light load use. It has become a problem.

As described above, when the electrolytic solution is stratified, it is difficult to charge the lower part of the battery, which has a high specific gravity, so that the discharge capacity is lowered early.

[0005]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the above-mentioned problem of early capacity reduction of lead acid batteries.
As a positive electrode grid alloy, antimony is 0.8% by weight or more and 3% by weight or less, arsenic is 0.1% by weight or more and 0.4% by weight or less, copper is 0.0005% by weight or more and 0.03% by weight or less, 0.0005 wt% or more and 0.25 wt% or less of silver, 0.0005 wt% or more and 0.1 wt% of tin
Hereinafter, a lead alloy containing 0.001% by weight or more and 0.03% by weight or less of bismuth and 0.0002% by weight or more and 0.003% by weight or less of nickel is used. .

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The lead-acid battery according to the present invention comprises, as a positive electrode grid alloy, antimony of 0.8% by weight or more and 3% by weight or less, arsenic of 0.1% by weight or more and 0.4% by weight or less, and copper. 0.0005 wt% or more and 0.03 wt% or less, silver 0.0005 wt% or more and 0.25 wt% or less, tin 0.0005 wt% or more and 0.1 wt% or less bismuth 0.001 % By weight and 0.03% by weight or less, and nickel by 0.0002% by weight and 0.
A lead storage battery is produced using a lead alloy containing 003% by weight or less.

As the lead alloy, a lead alloy recovered from scraps of lead storage batteries and a lead compound prepared by reducing impurities in a reducing furnace and removing impurities by a dry refining method are prepared. You may use.

By doing so, a lead storage battery having excellent life performance can be realized.

[0009]

EXAMPLES The details of the present invention will be described below with reference to examples.

First, a lead-antimony alloy obtained by reducing lead impurities and lead compounds recovered from scraps of lead-acid batteries and the like in a reducing furnace and then removing impurities by a dry refining method (referred to as lead or recycled lead). As antimony, 1.7% by weight of antimony and 0.25% by weight of arsenic
A conventional positive electrode grid made of lead-antimony alloy containing (N
O.1).

Next, the JIS manufactured by electrolytic refining
A special lead (described in JISH2105) containing 1.7% by weight of antimony and 0.25% by weight of arsenic was added to the conventional lead-
An antimony alloy positive electrode grid was prepared (NO. 2).

To the lead-antimony-arsenic alloy prepared from the above electrolytically refined lead, 0.0005% by weight of copper and 0.0% of silver are added.
A lead-antimony alloy positive electrode grid according to the present invention containing 005 wt%, 0.0005 wt% tin, 0.001 wt% bismuth, and 0.0002 wt% nickel was prepared (NO. 3). .

Further, 0.03% by weight of copper and 0.2% of silver are added to a lead-antimony-arsenic alloy prepared from electrolytically refined lead.
A lead-antimony alloy positive electrode grid according to the present invention containing 5% by weight, 0.1% by weight of tin, 0.03% by weight of bismuth, and 0.003% by weight or less of nickel was prepared (NO. 4). ).

For comparison, a lead-antimony-arsenic alloy prepared from electrolytically refined lead was added with 0.04% by weight of copper, 0.3% by weight of silver, 0.15% by weight of tin and 0.1% by weight of bismuth.
A lead-antimony alloy positive electrode grid according to the present invention containing 04% by weight and 0.004% by weight or less of nickel was prepared (NO. 5).

Table 1 shows the composition of these five types of lattice alloys.

[0016]

[Table 1] A paste-type positive electrode plate was produced by a conventional method using the above-mentioned five types of grids. Five kinds of lead acid batteries 55D23 for automobiles (described in JIS D5301) were produced by combining these positive electrode plates and a normal paste type negative electrode plate using a lead-calcium-tin based grid.

These batteries were subjected to the light load life test described in JIS D5301. The transition of the voltage at the 30th second of 356 A discharge during the life test is shown in FIG. 1, the transition of the specific gravity of the electrolytic solution is shown in FIG. 2, and the liquid reduction amount of the battery is shown in FIG.

The following facts were found from FIGS. 1 and 2. That is, both the conventional lead-containing NO.1 and the electrolytically refined lead-containing NO.2 caused a stratification of the electrolyte during the test and reached a relatively short life, but the battery according to the present invention (NO. 3 and 4) showed superior life performance compared with these.

According to the present invention, the life performance is improved because the stratification of the electrolytic solution which occurs during the life test is copper, as shown in FIG.
It is considered that this is because the addition of silver, tin, bismuth, and nickel could suppress it. It was possible to suppress stratification by these additional elements, because the positive electrode lattice surface was corroded during the test, these additional elements were eluted in the electrolytic solution, and then deposited on the negative electrode, so these additional elements deposited on the negative electrode This is because the amount of hydrogen gas generated by decomposition of the electrolytic solution during charging is slightly increased, and the generated gas is released into the atmosphere while stirring the electrolytic solution.

However, if these are added too much, the hydrogen overvoltage of the negative electrode is remarkably lowered, the electrolytic solution is decomposed during overcharge violently, the amount of liquid reduction is increased, and the specific gravity of the electrolytic solution is further increased. It has reached the end of its life (Battery No. 5).

In this example, 1.7% by weight of antimony and 0.25% by weight of arsenic were used as the positive electrode lattice alloy, but the effect of other additive elements becomes smaller when the amount of antimony is relatively small. Is large and preferably 0.8% by weight or more and 3% by weight or less. Arsenic having a content of 0.1% by weight or more and 0.4% by weight or less can be used. Further, selenium, sulfur and the like which are generally used in lead-antimony alloys may be added.

Further, in this embodiment, the positive electrode grid alloy of the lead storage battery according to the present invention was prepared from electrolytically refined lead. However, the lead alloy and the lead compound recovered from the scrap of the lead storage battery are reduced in the reduction furnace and then the dry type is used. It goes without saying that there is no problem even if it is prepared from a lead-antimony alloy (so-called lead) obtained by removing impurities by the refining method. Rather, it is advantageous to prepare the lead from unnecessary purification of the lead, and the amount of additive element is smaller than that to prepare from the electrolytic lead.

[0023]

As described above, according to the present invention, antimony is 0.8% by weight or more and 3% by weight or less, arsenic is 0.1% by weight or more and 0.4% by weight or less, and copper is 0.0005% by weight. Or more and 0.03% or less, silver 0.0005% by weight or more and 0.25% by weight or less, tin 0.0005% by weight or more and 0.1% by weight or less, and bismuth 0.001% by weight
More than or equal to 0.03 wt% and less than 0.0
A lead storage battery using a lead alloy containing 002% by weight or more and 0.003% by weight or less in the positive electrode grid has a great industrial value such as excellent life performance.

Further, when the lead alloy having the composition according to the present invention is prepared by using the lead, the refining cost can be minimized and the industrial value is further increased.

[Brief description of drawings]

FIG. 1 is a diagram showing the results of a JIS light load life test.

FIG. 2 is a diagram showing changes in the specific gravity of the electrolyte during the JIS light load life test.

FIG. 3 is a diagram showing the amount of liquid reduction during the JIS light load life test.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Haruhiko Mizuta No. 1 Babacho, Inosho Nishinosho, Kichijoin, Minami-ku, Kyoto

Claims (2)

[Claims] 1. Antimony 0.8% by weight or more and 3% by weight
Hereinafter, arsenic is 0.1% by weight or more and 0.4% by weight or less, copper is 0.0005% by weight or more and 0.03% by weight or less, bismuth is 0.001% by weight or more and 0.03% by weight or less, and silver is 0. 0
005 wt% or more and 0.25 wt% or less, tin 0.000
5% by weight or more and 0.1% by weight, and nickel 0.00
A lead storage battery, wherein a lead alloy containing 02 wt% or more and 0.003 wt% or less is used for a positive electrode grid. 2. A lead alloy obtained by reducing impurities in a lead furnace and a lead compound recovered from scraps of lead-acid batteries in a reducing furnace, and then removing impurities by a dry refining method.
The lead acid battery according to claim 1, which is prepared from an antimony-based alloy.