JPH0589873A - Negative electrode plate for lead-acid storage battery - Google Patents

Abstract

PURPOSE:To provide a lead acid storage battery excellent particularly in the high rate discharging performance and cycle life characteristic forming a neg. electrode plate with an active substance prepared by including metal tin in a metal lead active substance to which at least an organic expander is added. CONSTITUTION:A lattice of a Sn-based alloy containing 0.1% Pb and 0.7% Ca is filled with a paste 1 consisting of a kneaded mixture of lead oxide and sulphuric acid, pastes 2, 3 prepared by adding 0.1 and 0.5wt.% lignin respectively to the paste 1, and a paste 4 prepared by adding 5wt.% tin oxide to the paste 2, and thus a neg. electrode plate is formed. Current is fed while it is immersed in a diluted sulphuric acid, followed by rinse with water and drying, and the specific surface area is measured by the BET method and the high rate discharge capacity is measured in a good surplus of dilsulphuric acid, which gives the results that the active substance 4 has the greatest specific surface area and has the longest discharge duration. A cycle life test performed on a fully charged battery should reveal that the active substance 4 excels the most. Too little addition of lignin leads to a large drop of the specific surface area of the neg. electrode active substance while too much addition causes deterioration of the charging receiving characteristic.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative electrode plate for a lead storage battery, and an object thereof is to provide a lead storage battery having excellent high rate discharge performance and cycle life performance.

[0002]

2. Description of the Related Art In order to improve the high rate discharge performance of a lead storage battery, it is an effective means to increase the surface area of a negative electrode active material made of spongy metallic lead. For that purpose, the amount of active material is increased, and lignin, which is a kind of surfactant, is generally added as an organic expander to the negative electrode active material. However, if the amount of active material is increased, the weight of the battery becomes heavy and the weight efficiency becomes poor. Further, if the amount of lignin added is increased too much, charge acceptability will deteriorate.

[0003]

An object of the present invention is to improve the high rate discharge performance and the cycle life performance in a lead storage battery without lowering the weight efficiency and without deteriorating the charge acceptability.

[0004]

Means for Solving the Problems The present invention uses a negative electrode plate for a lead storage battery, which is characterized in that an active material contains metal tin together with an organic expander, so that high rate discharge performance and cycle life performance are excellent. It provides a lead acid battery.

[0005]

EXAMPLES The present invention will be described in detail below with reference to examples. (Experiment 1) Pb-0.1% Ca-0.7% Sn alloy lattice, 1) paste obtained by plastering lead oxide and sulfuric acid, 2) 1) further 0.1 wt% lignin. The added paste, 3) 1) was added with 0.5 wt% of lignin, and 4) 2) was added with 5 wt% of tin oxide, and each of the four types of negative electrode plates had a specific gravity of 1. The specific surface area of each metallic lead active material was measured by applying a BET method after applying an electric amount of 200% of the theoretical electric amount for 40 hours in 10 (20 ° C.) dilute sulfuric acid, washing with water and drying.

Then, using these plates, a high rate discharge capacity was measured by performing rate discharge for 5 minutes in a large excess of 1.30 (20 ° C.) dilute sulfuric acid. The discharge was performed until the cell voltage became 1.0V. A lead dioxide electrode having a capacity three times the capacity of the test electrode was used as the counter electrode. These measurement results are shown in Table 1.
Shown in.

[0007]

[Table 1] As described above, the active material according to the present invention obviously has a large specific surface area, and the effect of containing tin is recognized. In this experiment, tin oxide was added to the paste, and electricity was applied to the paste to reduce the metal tin, but it is considered that there is no problem if the metal tin is directly added to the paste. Further, it is speculated that the active material of the present invention is made of lead-tin alloy.

It was also confirmed that the product of the present invention has excellent efficiency discharge performance. (Experiment 2) Since it was found that the performance of the electrode plate was excellent as described above, a test was performed using a battery. The battery was composed of three positive electrode plates, four negative electrode plates, and a separator, and dilute sulfuric acid having a specific gravity of 1.30 (20 ° C.) was used as an electrolytic solution to manufacture a single cell battery having a nominal capacity of 28 AH.

Then, high rate discharge capacity was measured by performing rate discharge for 5 minutes. The discharge was performed at −15 ° C. and 150 A until the cell voltage became 1.0V. The results are shown in Table 2.

[0010]

[Table 2]

As described above, the product NO. It can be seen that No. 4 is excellent in high rate discharge performance even in an actual battery. Next, a cycle life test was performed using a fully charged battery.

The test conditions were a discharge current of 25 A for 4 minutes and a charging of 2.45 V for 10 minutes with a maximum current of 25 A. The battery was discharged at 270 A for 30 seconds every 500 cycles on the way, and the life was defined when the terminal voltage at that time was below 1.2 V.
The test temperature was 75 ° C. The results are shown in Figure 1. As described above, the product NO. It can be seen that 4 is the best. This is because the negative surface area of the negative electrode active material was greatly reduced in the battery to which lignin was not added or the battery in which the addition amount was small, and the charge acceptability was inferior in the battery in which the addition amount was large.

In addition, an additional experiment was conducted, and when metal tin was contained and lignin, which is an organic expander, was not added at the same time, a short circuit and short circuit occurred between the electrode plates during the cycle life test, and the life was short. .. Furthermore, the addition of carbon or barium compound to the active material did not impair the effects of the present invention.

[0014]

As is apparent from the above embodiments, the lead storage battery according to the present invention has a great industrial value in that the discharge capacity and life performance of the conventional lead storage battery can be greatly improved.

[Brief description of drawings]

FIG. 1 is a diagram showing a result of a battery life test.

Claims (1)

[Claims] 1. A negative electrode plate for a lead storage battery, comprising a negative electrode plate made of an active material containing metallic tin in a metallic lead active material containing at least an organic expander.