JP2002343359A - Sealed type lead storage battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealed type lead storage battery with excellent life performance. SOLUTION: With the sealed type lead storage battery provided with an electrode plate group consisting of a positive/negative electrode plate and a separator having electrolyte solution absorbed, and a battery case containing the electrode plate group, a negative electrode active material contains 0.3 to 2.0 weight percent of carbon particles, whose average size is preferably 0.01 to 0.20 micron. The sealed type lead storage battery may be a retainer type battery or a gel-retainer hybrid type battery.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a sealed lead-acid battery.

[0002]

2. Description of the Related Art In a sealed lead-acid battery, oxygen gas generated at a positive electrode is absorbed by a negative electrode, so that the amount of electrolyte does not decrease so much, and thus it is not necessary to refill water. The sealed lead-acid battery is position-free and can be placed horizontally. For this reason, sealed batteries have recently been used as automotive batteries.

As shown in FIG. 1, various types of sealed lead-acid batteries have been conventionally known. In the gel type battery shown in FIG. 1A, the positive and negative electrode plates 1 and 2 are housed in a battery case 3 together with a silica gel 4, and the silica gel 4 contains an electrolytic solution. Also, as a battery having an improved electrolyte diffusion performance than this battery, a retainer type battery (FIG. 1)
(B)) and a granular silica battery (FIG. 1 (C)).
In the case of a retainer type battery, a separator 5 made of glass fiber is used.
The positive / negative electrode plates 1 and 2 are laminated through the intermediary of the electrode plate, thereby forming an electrode plate group. Then, the electrolytic solution is absorbed by the separator 5. On the other hand, in the granular silica battery, the electrolytic solution is held in the granular silica gel 6.

Further, as a battery obtained by improving the retainer type battery, there is a gel-retainer hybrid type battery shown in FIG. In this battery, the contact area between the battery case and the electrolytic solution is increased by filling the silica gel 4 containing the electrolytic solution between the inner surface of the battery case 3 and the electrode plate group. Therefore, according to the gel-retainer hybrid battery, the temperature rise of the battery is suppressed.

[0005]

However, the conventional sealed lead-acid battery has a problem in that the capacity is greatly reduced with use and the life is short. Therefore, an object of the present invention is to provide a sealed lead-acid battery having excellent life performance.

[0006]

SUMMARY OF THE INVENTION The present invention has been completed as a result of intensive studies to solve the above-mentioned problems. The sealed lead-acid battery of the present invention is a sealed lead-acid battery including a positive / negative electrode plate and an electrode plate group including a separator absorbing an electrolytic solution, and a battery case accommodating the electrode plate group.
It is characterized by containing 0.3 to 2.0% by weight of carbon particles.

In the present invention, the average particle size of the carbon particles is
Desirably, 0.01 to 0.20 microns. Since the sealed lead-acid battery of the present invention includes the separator, it can be used as a retainer-type battery. However, it is more preferable to use a gel-retainer hybrid battery by filling a gel holding an electrolyte between the inner surface of the battery case and the electrode plate group. When used as a retainer type, Pb is used as a grid for the positive electrode.
A lattice comprising a Ca-based alloy and a Pb-Ca-based alloy containing Ca in a higher concentration than the alloy, or Pb-C
It is desirable to use a lattice composed of an a-based alloy and a Pb-Sb-based alloy, a Pb-Sn-based alloy, or a Pb-Sb-Sn-based alloy.

[0008]

EXAMPLES-Example 1-A sealed lead-acid battery was manufactured as follows. First,
A 10 mm thick lead alloy plate made of Pb-0.07 wt% Ca-1.3 wt% Sn was rolled to a thickness of 1.0 mm with a rolling roller.
After that, a mesh grid was formed using a rotary expanding machine. Next, dilute sulfuric acid having a specific gravity of 1.10 (20 ° C.) was added to 95 parts of the lead powder and 5 parts of the red lead in 0.13 kg / kg.
A paste-like positive electrode active material was prepared by adding L and kneading. A positive electrode plate was obtained by filling the grid with a positive electrode active material, aging and drying.

Subsequently, trace amounts of ligninsulfonic acid and barium sulfate were added to the lead powder, and acetylene black was further added as carbon particles. Furthermore, specific gravity 1.1
A paste-like negative electrode active material was prepared by adding 0.13 L of diluted sulfuric acid of 0 (20 ° C.) per 1 kg and kneading. The amount of the carbon particles was 0.2, 0.3, 1.0, 2.0, and 3.0% by weight based on the negative electrode active material. Then, the grid was filled with a negative electrode active material, which was aged and dried to obtain five types of negative electrode plates having different amounts of carbon.

Next, a group of electrode plates was prepared for various negative electrode plates. The production of the electrode plate group was performed by alternately stacking five positive electrode plates and six negative electrode plates via a glass fiber separator. Then, after putting the prepared electrode group in a battery case, dilute sulfuric acid is injected into the separator as an electrolytic solution,
Chemical formation. Further, a sol solution composed of dilute sulfuric acid and colloidal silica was injected between the electrode group and the battery case to gel. Thus, five types of gel-retainer hybrid batteries having different negative electrode plates were manufactured. The battery has a nominal voltage of 2V and a nominal capacity of 30Ah.

With respect to these batteries, the number of charge / discharge cycles until the discharge capacity was reduced to 80% or less of the nominal capacity was examined by appropriately measuring the discharge capacity while repeating charge / discharge in water at 40 ° C. Here, the discharge is 10A
(1/3 CA) constant current for 2.4 hours, charging 10
After performing 90% of the discharge amount at a constant current of A, 1.5 A
At a constant current of 20% of the discharge amount. The discharge capacity was measured by discharging at a constant current of 10 A (1/3 CA) for 2.4 hours. Further, the same test was performed on the retainer type battery and the gel type battery. The retainer type battery is manufactured in the same procedure as above except that the sol liquid is not injected around the electrode group, and the gel type battery is the same as above except that the gel is filled between the electrode plates instead of the separator. .
Table 1 shows the results.

[0012]

[Table 1]

As shown in Table 1, in the gel-retainer hybrid battery, the carbon content was 0.3 to 2.0% by weight.
In this case, the life performance was remarkably good. It is considered that the reason is that the oxygen gas absorption reaction in the negative electrode plate was promoted by optimizing the amount of carbon. The life performance of the retainer-type battery is inferior to that of the gel-retainer hybrid-type battery, which is considered to be due to the fact that the temperature inside the battery increases and the amount of the electrolyte decreases largely. In addition, in the gel type battery, the life performance was not improved even if the amount of carbon was changed. Is done.

Example 2 A sealed lead-acid battery was manufactured as follows. First,
One side of a 10 mm-thick lead alloy plate made of Pb-0.07% by weight Ca-1.3% by weight Sn
A 0.3 mm thick lead alloy sheet made of -1% by weight Sn was overlaid. Then, this is rolled to a thickness of 1.
After reducing the thickness to 0 mm, the mesh was formed using a rotary expanding machine. As a result, a grid having a 30 μm-thick lead alloy foil on one side was produced, and this grid was used as a grid for the positive electrode. Next, a positive electrode active material was prepared in the same manner as in Example 1, filled in a positive electrode grid, then aged and dried to obtain a positive electrode plate.

Subsequently, a grid having no lead alloy foil on the surface was prepared in the same manner as in Example 1, and this was used as a grid for the negative electrode. Further, a negative electrode active material was prepared in the same manner as in Example 1. However, the amount of carbon is 0.1, 0.3, 1.0,
2.0 and 3.0% by weight. Then, after filling the negative electrode grid with the negative electrode active material, aging and drying were performed to obtain five types of negative electrode plates having different amounts of carbon.

Next, an electrode plate group was prepared for various types of negative electrode plates. The production of the electrode plate group was performed by alternately stacking five positive electrode plates and six negative electrode plates via a glass fiber separator. Then, after putting the prepared electrode group in a battery case, dilute sulfuric acid is injected into the separator as an electrolytic solution,
Chemical formation. As a result, five types of retainer batteries having different negative electrode plates were manufactured. The battery has a nominal voltage of 2V and a nominal capacity of 30Ah.

In the same manner as in Example 1, the number of charge / discharge cycles until the discharge capacity was reduced to 80% or less of the nominal capacity was examined for these batteries. For comparison, a battery using a grid without lead alloy foil instead of the above-described grid for the positive electrode was manufactured and subjected to a test. The amount of carbon in the negative electrode active material of this battery was 0.1% by weight. Table 2 shows the results.

[0018]

[Table 2]

As shown in Table 2, as the grid for the positive electrode, C
In a battery using a grid composed of a lead alloy plate containing a and a lead alloy foil containing Ca at a higher concentration, the life performance is improved when the carbon amount is 0.3 to 2.0% by weight. It was remarkably good. It is considered that the reason for this is that by adjusting the amount of carbon appropriately, the current distribution during chemical formation was made uniform, and thus the adhesion between the positive electrode grid and the positive electrode active material was improved.

Example 3 A sealed lead-acid battery was manufactured as follows. First,
One side of a 10 mm thick lead alloy plate made of Pb-0.07% by weight Ca-1.3% by weight Sn was coated with Pb-5% by weight Sb.
A 0.3 mm thick lead alloy sheet made of -1% by weight Sn was overlaid. Then, this is rolled to a thickness of 1.
After reducing the thickness to 0 mm, the mesh was formed using a rotary expanding machine. As a result, 30 μm thick Sb and Sb
A grid having a lead alloy foil containing n on one side was produced, and this grid was used as a grid for the positive electrode. Next, a positive electrode active material was prepared in the same manner as in Examples 1 and 2, and after filling this in a positive electrode grid, aging and drying were performed to obtain a positive electrode plate.

Subsequently, in the same procedure as in Example 2, the preparation of the negative electrode plate, the preparation of the electrode plate group, the injection of the electrolyte, and the formation of a battery were performed. Thus, five types of retainer batteries having different amounts of carbon in the negative electrode active material were obtained. The battery has a nominal voltage of 2V and a nominal capacity of 30Ah. For these batteries, the number of charge / discharge cycles until the discharge capacity was reduced to 80% or less of the nominal capacity was examined in the same manner as in Example 2. Table 3 shows the results.

[0022]

[Table 3]

As shown in Table 3, as the grid for the positive electrode, C
In a battery using a grid composed of a lead alloy plate containing a and a lead alloy foil containing Sb and Sn, when the carbon amount in the negative electrode active material is 0.3 to 2.0% by weight, the life performance is improved. Was remarkably good. It is considered that the reason for this is that by adjusting the amount of carbon appropriately, the current distribution during chemical formation was made uniform, and thus the adhesion between the positive electrode grid and the positive electrode active material was improved.

[0024]

According to the present invention, it is possible to obtain a sealed lead-acid battery having excellent life performance.

[Brief description of the drawings]

FIG. 1 is a sectional view showing a sealed lead-acid battery.

[Explanation of symbols]

 1 positive electrode plate 2 negative electrode plate 3 battery case 4 silica gel 5 separator 6 granular silica gel

Continued on the front page F term (reference) 5H017 AA01 AS10 CC05 EE03 HH06 5H028 AA06 CC05 EE01 FF04 FF09 HH01 HH03 HH05 5H050 AA07 BA10 CA06 CB15 DA05 DA10 EA10 HA01 HA05

Claims (5)

[Claims] 1. A sealed lead-acid battery comprising an electrode group consisting of a positive / negative electrode plate and a separator absorbing an electrolytic solution, and a battery case accommodating the electrode group, wherein the negative electrode active material is 0.3 to A sealed lead-acid battery containing 2.0% by weight of carbon particles. 2. The carbon particles having an average particle size of 0.01 to 0.01.
2. The sealed lead-acid battery according to claim 1, which is 0.20 microns. 3. The sealed lead-acid battery according to claim 1, wherein a gel for holding an electrolytic solution is filled between the inner surface of the battery case and the electrode plate group. 4. The sealing mold according to claim 1, wherein the grid for the positive electrode comprises a Pb-Ca-based alloy and a Pb-Ca-based alloy containing Ca at a higher concentration than the alloy. Lead storage battery. 5. A grid for a positive electrode comprising a Pb-Ca alloy and P
b-Sb alloy, Pb-Sn alloy or Pb-Sb-S
The sealed lead-acid battery according to any one of claims 1 to 3, comprising an n-based alloy.