JP2002216837A - Lead storage battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lead storage battery whose cycle life characteristics at high temperature is not deteriorated even when Pb-Ca system alloy is used as a cathode latticed body. SOLUTION: A cathode electrode plate 1 housed in a sack-shaped glass mat 3 made of glass fiber and an anode electrode plate 2 inserted between a porous synthetic resin separator are installed layered in a battery container.

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 In recent years, lead-acid batteries for automobiles have been required to be maintenance-free and require no management, and Pb-Ca-based alloys have been used as a material of a grid, which is a current collector of an electrode plate.
In recent years, the load on batteries has increased due to the remarkable development of car electronics, and the batteries have been used at high temperatures due to the densification of the engine room, and the opportunities for use under extremely severe conditions have been increasing.

[0003] Further, in this type of conventional lead-acid battery, one of the electrodes has a structure in which it is accommodated in a separator made of a porous synthetic resin such as polyethylene.

[0004]

However, the Ca-based positive electrode lattice body containing no Sb has a problem that its high-temperature durability is poor. That is, at a high temperature, the adhesion to the active material is deteriorated, the active material is easily peeled from the current collector, and the high-temperature durability is poor. Therefore, when used at a high temperature, there is a problem that the cycle life characteristics deteriorate.

Further, when the synthetic resin separator is in direct contact with the positive electrode plate, there is a problem that the synthetic resin separator is oxidized and deteriorated.

Furthermore, when the upper portion of the positive electrode plate is stretched, the stretched portion comes into contact with the ear portion of the negative electrode plate or the negative electrode strap, causing a short circuit accident.

An object of the present invention is to provide a positive electrode grid body comprising Pb-
An object of the present invention is to provide a lead-acid battery that does not deteriorate the cycle life characteristics at high temperatures even when a Ca-based alloy is used.

Another object of the present invention is to provide a lead-acid battery which can prevent oxidation deterioration of a member covering a positive electrode plate.

[0009] Another object of the present invention is to provide a positive electrode grid having P
Provided is a lead-acid battery that does not deteriorate cycle life characteristics at high temperatures even when a b-Ca alloy is used, and that can prevent oxidative deterioration of a member covering a positive electrode plate and can prevent a short circuit accident of an electrode plate. It is in.

[0010]

A lead-acid battery according to the present invention comprises a positive electrode plate housed in a bag-shaped glass mat made of glass fiber and a negative electrode plate sandwiched between porous synthetic resin separators. It is housed in a battery case.

When the positive electrode plate is accommodated in the bag-like glass mat made of glass fiber as described above, it is possible to prevent the active material from peeling off from the positive electrode grid at a high temperature and to improve the high-temperature durability.

Further, since the positive electrode plate is housed in a bag-shaped glass mat made of glass fiber instead of a bag-shaped separator made of a synthetic resin film or sheet, the glass mat does not deteriorate by oxidation.

In this case, if the synthetic resin separator covering the negative electrode plate is also formed in a bag shape, the position of the negative electrode plate is defined between both side seal portions of the bag-shaped synthetic resin separator. The positional relationship with the positive electrode plate whose position is defined between them can be correctly maintained even with respect to vibration.

When the upper portion of the bag-shaped glass mat is sealed at a portion corresponding to the ear portion of the negative electrode plate and in the vicinity thereof, it is possible to prevent the positive electrode plate from extending and coming into contact with the ear portion of the negative electrode plate and the negative electrode strap to cause a short circuit. Can be prevented.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an embodiment which is an example of an embodiment of a lead storage battery according to the present invention will be described together with a comparative example.

(Comparative Example 1) The lead storage battery of Comparative Example 1
It was manufactured as follows. First, a positive electrode plate was made. That is, first, lead powder and 13% by mass of dilute sulfuric acid (specific gravity
1.26: 20 ° C.) and 12% by mass of water with respect to the lead powder to prepare a positive electrode active material paste. Next, 102 g of this positive electrode active material paste was filled into a current collector comprising a lattice of a Ca-containing alloy containing 0.08% by mass of Pb-Ca and 0.8% by mass of Sn. After aging for 18 hours, the mixture was left to dry at 110 ° C. for 2 hours to produce an unformed positive electrode plate.

Next, a negative electrode plate was prepared. That is, first, lead powder and 13% by mass of dilute sulfuric acid with respect to the lead powder (specific gravity 1.26: 20 ° C)
And 12% by mass of water with respect to the lead powder were mixed to prepare a negative electrode active material paste. Next, this negative electrode active material paste 73
g of Pb-Ca 0.08% by mass-Sn0.8% by mass into a current collector consisting of a lattice of a Ca-containing alloy,
After aging for 18 hours at 95 ° C and 95% humidity, the temperature was 110
It was left to dry at 2 ° C. for 2 hours to produce an unformed negative electrode plate.

Next, seven unformed positive electrode plates and eight unformed negative electrode plates
Each of the sheets was alternately laminated with a negative electrode plate covered with a bag-shaped separator made of a porous synthetic resin to form each electrode plate group. After disposing these electrode plates in a battery case, an electrolytic solution was injected into the battery case to produce unformed lead-acid batteries. The electrolytic solution was diluted sulfuric acid having a specific gravity of 1.26 (20 ° C.).

Next, these unformed lead-acid batteries were formed at 9 A for 42 hours to complete the lead-acid batteries.

Comparative Example 2 The positive and negative electrode plates of Comparative Example 1 were laminated via a glass mat SSG MSL (manufactured by Nippon Inorganic Co., Ltd.) to make each electrode plate group. Using these electrode plates, an unformed lead storage battery was formed under the same conditions as in Comparative Example 1, and a lead storage battery was completed by formation.

(Embodiment) The lead storage battery of this embodiment was manufactured as follows. The present invention is not limited to the lead storage battery of this embodiment.

A positive electrode plate 1 and a negative electrode plate 2 shown in FIGS. 1 and 2 were prepared under the same conditions as in Comparative Example 1, and the positive electrode plate 1 was covered with a bag-like glass mat FM920N (manufactured by Nippon Inorganic Co., Ltd.) 3. 2 was covered with a bag-shaped separator 4 made of a porous synthetic resin. The ears 1 a of each positive electrode plate 1 are connected to each other by a positive electrode strap 5, and the ears 2 a of each negative electrode plate 2 are connected to each other by a negative electrode strap 6. The bag-shaped glass mat 3 is formed by folding a glass fiber non-woven fabric into two parts,
Is a bottom part, both sides are sealed with seal parts 3b, and the positive electrode plate 1 is accommodated from the upper opening part 3c, and the upper part is at least a part corresponding to the ear part 2a of the negative electrode plate 2 and a seal part 3b near the part. Sealed.

The electrode plate group 7 formed by alternately stacking the positive electrode plates 1 placed in the bag-shaped glass mat 3 and the negative electrode plates 2 placed in the bag-shaped separator 4 is housed in a battery case (not shown). An electrolytic solution was injected into the battery case to produce unformed lead-acid batteries. The electrolytic solution was diluted sulfuric acid having a specific gravity of 1.26 (20 ° C.).

Next, these unformed lead-acid batteries were formed at 9 A for 42 hours to complete the lead-acid batteries.

Using each of the lead storage batteries of Comparative Examples 1 and 2 and Example thus completed, each was discharged at 25 A for 4 minutes at an ambient temperature of 75 ° C., and then charged at 14.8 V for 10 minutes. Repeat charge and discharge with one cycle of charge and discharge, 48
0 Leave for 56 hours every cycle. Thereafter, the battery is discharged at 582 A for 30 seconds, its voltage is measured, and the same cycle is repeated. The cycle life number was the number of times that the voltage at 30 seconds at 582 A became 7.2 V.

FIG. 3 shows the average number of life cycles in Comparative Examples 1 and 2 and the embodiment. As a result, it was found that the lead storage batteries of Comparative Example 2 and Example using the glass mat had improved high-temperature life characteristics.

Next, the lead storage battery after the cycle deterioration was disassembled, and the cause of the life deterioration was examined.

FIG. 4 shows the number of the lead storage batteries of Comparative Examples 1 and 2 and the working example, which are caused by short-circuits due to cycle deterioration. As is clear from this figure, in the examples, the cause of the service life is not at all due to the short circuit, but in the comparative examples 1 and 2, more than half of them are deteriorated due to the short circuit.

As shown in FIG. 5, the bag-shaped glass mat 3 is placed on both sides 2 cm from the lower portion of the bag-shaped glass mat 3.
It is preferable to provide the opening 8 at a height of, for example, about 2 cm. In this case, the diffusion of the electrolyte is further improved, and the diffusion of the electrolyte is not impaired.

[0030]

According to the lead storage battery of the present invention, since the positive electrode plate is housed in the bag-shaped glass mat made of glass fiber, the active material can be prevented from peeling off from the positive electrode grid at a high temperature, and the high temperature durability can be prevented. Performance can be improved. Further, since the positive electrode plate is housed in a bag-shaped glass mat made of glass fiber instead of a bag-shaped separator made of a synthetic resin film or sheet, the glass mat does not deteriorate by oxidation.

In this case, if the synthetic resin separator covering the negative electrode plate is also formed in a bag shape, the position of the negative electrode plate is defined between both side seal portions of the bag-shaped synthetic resin separator. The positional relationship with the positive electrode plate whose position is defined between them can be correctly maintained even with respect to vibration.

When the upper portion of the bag-shaped glass mat is sealed at a portion corresponding to the ear portion of the negative electrode plate and in the vicinity thereof, it is possible to prevent the positive electrode plate from extending and coming into contact with the ear portion of the negative electrode plate and the negative electrode strap to cause a short circuit. Can be prevented.

[Brief description of the drawings]

FIG. 1 is a vertical sectional side view of a part of an electrode group in an example of an embodiment of a lead storage battery according to the present invention.

FIG. 2 is a vertical sectional front view of a part of an electrode group in an example of an embodiment of a lead storage battery according to the present invention.

FIG. 3 is a comparison diagram showing average life cycle numbers of Comparative Examples 1 and 2 and an example.

FIG. 4 is a comparison diagram showing the number of the lead storage batteries of Comparative Examples 1 and 2 and the example due to a short circuit caused by cycle deterioration.

FIG. 5 is a longitudinal sectional front view of a part of an electrode plate group in another example of the embodiment of the lead storage battery according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Positive electrode plate 1a Ear part 2 Negative electrode plate 2a Ear part 3 Bag-shaped glass mat 3a Folding part 3b Seal part 3c Opening 4 Bag-shaped separator 5 Positive strap 6 Negative strap 7 Electrode group 8 Opening

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Nobukazu Tanaka 2-8-7 Nihonbashi Honcho, Chuo-ku, Tokyo Inside Shin-Kobe Electric Machinery Co., Ltd. (72) Inventor Kazuya Sasaki 2-87 Nihonbashi Honcho, Chuo-ku, Tokyo Inside Shin-Kobe Electric Co., Ltd. (72) Inventor Ichiro Mukai 2-8-7 Nihonbashi Honcho, Chuo-ku, Tokyo F-term in Shin-Kobe Electric Co., Ltd. 5H021 BB11 CC18 EE04 5H028 AA05 BB05 CC05

Claims (3)

[Claims] A positive electrode plate housed in a bag-like glass mat made of glass fiber and a negative electrode plate sandwiched between porous synthetic resin separators are stacked and housed in a battery case. Lead-acid battery. 2. The lead-acid battery according to claim 1, wherein the synthetic resin separator has a bag shape and houses the negative electrode plate. 3. The lead-acid battery according to claim 1, wherein an upper portion of the bag-shaped glass mat is sealed at a portion corresponding to an ear of the negative electrode plate and in the vicinity thereof.