JP3035177B2 - Lead storage battery - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lead storage battery.

[0002]

2. Description of the Related Art Conventionally, as a lead storage battery, Ca0.05-
A positive electrode plate formed by filling a paste positive electrode active material into a grid substrate cast with an alloy consisting of 0.14% by weight, Sn 0.75 to 1.00% by weight, and the balance of lead is accommodated in a bag-shaped separator, and the bag is formed. A lead-acid battery in which an electrode plate group formed by laminating a negative electrode plate on the outer surface of a separator in a battery case is known.

[0003]

At present, a long life is required in the market. However, in the above-mentioned conventional lead-acid battery, the positive electrode plate has poor corrosion resistance, and the bag-like separator is broken by its elongation. As a result, a short circuit occurs between the positive and negative electrode plates, thereby shortening the battery life. Therefore, it is desired to extend the life by the improvement.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and provides a lead-acid battery having a longer life than conventional ones.
A positive electrode plate obtained by filling a paste positive electrode active material into a grid substrate cast with an alloy consisting of 1.50% by weight, with the balance being lead,
It is characterized in that an electrode plate group formed by laminating on the outer surface of a bag-like separator accommodating a negative electrode plate is incorporated in a battery case.

[0005]

According to the present invention, the composition of the alloy is from 0.03 to 0.03 Ca.
A grid substrate composed of 0.09% by weight, Sn 1.05 to 1.50% by weight, and the balance of lead is filled with a positive electrode active material to form a positive electrode plate. When this is used as a battery, the amount of corrosion of the grid substrate is 20%. % Or less. Furthermore, when the negative electrode plate is housed in a bag-shaped separator and the electrode plate group assembled by laminating the positive electrode plate on its outer surface is used in a battery case, the bag-shaped separator is not broken by the elongation of the electrode plate. A short circuit with the positive electrode is reliably prevented, and a long-life battery is provided in combination with the corrosion resistance of the grid substrate of the positive electrode plate. When the content of Ca in the lattice substrate alloy of the positive electrode plate is less than 0.03% by weight, the mechanical strength becomes weak. On the other hand, when the content of Ca is 0.1.
When the content exceeds 09% by weight, the amount of corrosion of the lattice substrate exceeds 20%, which is not preferable. If the Sn content is less than 1.05% by weight, the corrosion amount exceeds 20%. On the other hand, if the content exceeds 1.50% by weight, the molten metal flow during casting becomes poor, the cast grid substrate is cut off, and a high-quality grid substrate cannot be obtained reliably, resulting in loss of product. Not preferred.

[0006]

Next, embodiments of the present invention will be described. Ca0.
03 to 0.14% by weight, Sn 0.7 to 1.50% by weight,
With respect to the remaining lead, various alloys were produced by changing the alloy composition in various ways, and each of them was used as a material to produce each cast lattice substrate. Each of the lattice substrates thus produced was filled with a paste-like positive electrode active material, and each of the positive electrode plates was produced by a conventional method. A JIS overcharge test was performed at 75 ° C. for each positive electrode plate having a different alloy composition of the lattice substrate thus manufactured. That is, the battery is continuously charged at 4.5 A for 110 hours, and is charged for 48 hours.
After leaving for a period of time, discharging at 150 A for 30 seconds was performed for 3 cycles. Thereafter, the corrosion amount (%) of each grid substrate of the positive electrode plate was measured. As a result, the relationship between the change of the compounding amount of each of the composition components Ca and Sn in the alloy of the alloy lattice substrate of the positive electrode plate and the corrosion amount (%) of each alloy lattice substrate was examined. As is apparent from FIG.
In order to reduce the content to 0% or less, Ca is 0.09% by weight.
In the following, it was found that it was necessary to add Sn to a content of 1.05% by weight or more. However, when Ca is 0.02% by weight, the mechanical strength of the lattice substrate is weakened, which makes the lattice substrate unsuitable for practical use. Lattice defects such as cuts occur. Therefore, by using an alloy consisting of Ca in the range of 0.03 to 0.09% by weight, Sn in the range of 1.05 to 1.50% by weight, and the balance of lead, it is ensured that a good grid having low corrosivity is obtained. The substrate can be cast smoothly without loss, and a positive electrode plate having a corrosion amount of 20% or less can be obtained.

However, the above specified ranges of Ca and S
Using a compounding amount with n, a lead alloy lattice substrate is prepared, and a positive electrode plate is manufactured by filling it with a positive electrode active material. As long as the positive electrode plate is accommodated in the bag-shaped separator and used, a remarkably long life lead-acid battery cannot be obtained, and the positive electrode plate is used as it is without being accommodated in the bag-shaped separator, and the bag-shaped separator is used. It has been found that, by housing the negative electrode plate, laminating the positive electrode plate on the outer surface of the bag-shaped separator to form an electrode plate group, and incorporating the same in a battery case, a lead-acid battery having an extremely long life can be obtained for the first time. Was.

Hereinafter, the above facts will be clarified by a comparative test. As an example of the present invention, an alloy lattice substrate composed of 0.07 % by weight of Ca, 1.05% by weight of Sn, and the balance of lead was filled with a paste-like positive electrode active material . A large number of cathode plates B were prepared by filling a paste-like cathode active material into an alloy lattice substrate composed of 07 % by weight, Sn 1.20% by weight, and the balance being lead.
On the other hand, a large number of separately prepared ordinary negative electrode plates accommodated in a polyethylene bag-like separator were prepared. As a first embodiment, the above-mentioned two positive electrode plates A and the negative electrode plate 3 accommodated in the bag were prepared.
The electrode groups are assembled alternately by stacking the electrode groups, and the electrode groups are respectively housed in six cell chambers separated by partition walls in a polypropylene battery case. Then, a predetermined amount of the electrolytic solution was accommodated in each cell chamber, and a battery case lid of the same material was provided, thereby producing a lead-acid battery of the present invention composed of 6 cells.
Similarly, as a second embodiment, two positive electrode plates B were used, and three negative electrode plates housed in the bag were alternately laminated to form an electrode plate group. Thus, the lead storage battery of the present invention was manufactured.

For comparison, instead of accommodating the negative electrode plate in the bag-like separator, a number of sheets each containing the positive electrode plate A and the positive electrode plate B in the bag-like separator were prepared. Thus, two positive electrode plates A accommodated in the bag-shaped separator and three negative electrode plates not accommodated in the bag-shaped separator are alternately laminated to assemble an electrode plate group. Then, a comparative lead storage battery was manufactured in the same manner as described above. In addition, two positive electrode plates B accommodated in a bag and the three negative electrode plates described above are alternately laminated to assemble an electrode plate group, which is then assembled in a battery container including six cell chambers in the same manner as described above. Similarly, a lead storage battery for comparison was manufactured.

For further comparison, a conventionally known Ca content of 0.0
A grid substrate of a conventional alloy consisting of 7% by weight, Sn amount of 1.0% by weight, and the balance of lead was filled with the same paste-like positive electrode active material as described above to produce a number of conventional positive electrode plates C. Are assembled in the same bag-shaped separator as in the above-mentioned embodiment, and two negative electrode plates not accommodated in the bag-shaped separator are alternately laminated to assemble an electrode plate group. Each of the batteries was housed in a battery case comprising a chamber to produce a comparative lead storage battery. Instead of accommodating the positive electrode plate C in the bag-shaped separator, a large number of the negative electrode plates accommodated in the same bag-shaped separator as described above were prepared. Two positive electrode plates C were alternately laminated to form an electrode plate group, which was housed in a battery case in the same manner as described above, and a comparative lead storage battery was manufactured in the same manner.

Further, for comparison, a grid substrate of a conventional alloy consisting of 0.1% by weight of Ca, 1.0% by weight of Sn and the balance of lead was filled with the same paste-like positive electrode active material as in the above embodiment. A large number of positive electrode plates D
Are stacked in the same bag-shaped separator as described above, and three negative electrode plates as described above are alternately laminated to assemble an electrode plate group. To manufacture a lead storage battery for comparison. Instead of accommodating the positive electrode plate D in the bag-shaped separator, the negative electrode plate is accommodated in the bag-shaped separator, and three negative electrode plates accommodated in the bag-shaped separator and two positive electrode plates not accommodated in the bag-shaped separator are used. The electrode group was assembled by alternately stacking, and this was housed in a battery case in the same manner as described above, and a comparative lead storage battery was manufactured in the same manner.

The battery of the present invention and the comparative battery thus prepared were subjected to a discharge at 75 ° C. and a discharge of 200 A × 10.
A cycle life test was performed in which 1 cycle of 14.5 V constant voltage charging × 59 minutes and 50 seconds was one cycle. In this case, the life was defined as when the battery voltage became 7.5 V or less.

The results are shown in Table 1 below.

[0014]

[Table 1]

As is clear from Table 1, the cycle life of the lead storage battery of the present invention is 120 when the cycle life of the conventionally known comparative lead storage battery is 100.
% And 130% were found to significantly extend their life. Incidentally, of course in the case of the positive electrode plate using the alloy lattice substrate of the conventional alloy composition used lead electric storage batteries, in even a positive electrode plate using the grating substrate alloy composition of the present invention, a bag-shaped positive electrode plate When used in a separator, most of the bag-like separators were torn and short-circuited to the negative electrode plate. On the other hand, in the case where the negative electrode plate was accommodated in the bag-like separator, no break of the bag-like separator due to elongation of the electrode plate, and no short circuit with the positive electrode was observed. As a result of other general tests, the alloy lattice substrate of the positive electrode plate of the present invention was found to have a Ca content of 0.03 to 0.09% by weight and a Sn content of 1.05 to 1.05%.
1. An electrode plate composed of an alloy composition range of 1.50% by weight with the balance being lead, and having the positive electrode plate alternately stacked with the negative electrode plate accommodated in the bag-like separator without being accommodated in the bag-like separator. When a group of lead-acid batteries is used, the corrosion of the positive electrode plate is significantly reduced, and there is no breakage due to the elongation of the electrode plate of the bag-shaped separator.
It was found to extend to 0-135%. In the above-described embodiment, the number of the positive plates is equal to the number of the negative plates-1. However, the number of the positive plates may be the same or the number of the positive plates may be large.

[0016]

As described above, according to the present invention, Ca0.0
3 to 0.09% by weight, 1.05 to 1.50% by weight of Sn,
A grid substrate can be smoothly and satisfactorily cast by the alloy consisting of the balance of lead, and the positive electrode plate filled with the positive electrode active material in the grid substrate is not stored in the bag-like separator, and the negative electrode plate is stored in the bag. The electrode group was assembled by laminating on the outer surface of the separator, and this was housed in a battery case to make a lead-acid battery. And the service life of the battery can be significantly extended as compared with the conventional lead-acid battery.

[Brief description of the drawings]

FIG. 1 is a graph showing a relationship between a change in a Ca—Sn—Pb alloy composition of a lattice substrate of a positive electrode plate and an amount of corrosion.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-343070 (JP, A) JP-A-63-152882 (JP, A) JP-A-63-108675 (JP, A) JP-A-59-1985 209281 (JP, A) Japanese Utility Model Showa 56-24065 (JP, U) Japanese Utility Model Showa 59-152566 (JP, U) (58) Fields investigated (Int. Cl. ⁷ , DB name) H01M 4/14 H01M 4 / 68

Claims (1)

(57) [Claims] 1. 0.03 to 0.09% by weight of Ca, Sn
A positive electrode plate obtained by filling a paste positive electrode active material on a grid substrate cast with an alloy consisting of 1.05 to 1.50% by weight, with the balance being lead, is laminated on the outer surface of a bag-like separator accommodating the negative electrode plate. A lead-acid battery characterized by incorporating the electrode plate group in a battery case.