JP3028578B2 - Battery storage method for lead-acid batteries - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a battery case of a lead-acid battery, and more particularly to a method of forming a battery case for a lead-acid battery in which lead is mixed in a paste used for a positive electrode plate active material. Things.

Prior art The battery formation method for lead-acid batteries requires a specific gravity of 1.18 before battery formation.
Inject 0 or more diluted sulfuric acid, consider the concentration of electrolyte by electrolysis during chemical formation and the amount of sulfuric acid generated from the electrode plate, determine the amount of solution to be injected, perform battery forming, and complete battery forming. There is a method in which the specific gravity of the subsequent electrolytic solution becomes an arbitrary specific gravity. Also, in order to rationalize the amount of electricity in the battery case formation, dilute sulfuric acid with a low specific gravity of 1.150 or less is injected before the formation of the battery case, and after the formation of the battery case, the chemical electrolyte is drained. Of sulfuric acid, and recharging with a large current of 100 to 400 A, stirring the electrolyte inside the battery within a short time to adjust the specific gravity of the electrolyte to an arbitrary value. At the present time, the latter method is mainly used.

Problems to be Solved by the Invention In a lead storage battery in which lead paste is mixed into a paste used for a positive electrode active material, the amount of electricity during battery formation can be reduced theoretically by the action of lead lead. In order to maximize the effect, the specific gravity of the diluted sulfuric acid injected before the formation of the above-mentioned battery tank was set to a low specific gravity. The method of stirring with water is effective.
However, since the positive electrode plate in which the lead material is mixed in the active material has a weak binding force between the grid and the active material, the active material peels off from the grid due to gas generation during electrolysis when charged with a large current, and the battery life is shortened. There was a major problem that it was significantly reduced. Therefore, in a lead-acid battery in which lead red is mixed in the positive electrode active material, the specific gravity of dilute sulfuric acid injected before battery formation is set to low specific gravity, and high specific gravity sulfuric acid is injected after battery formation to increase the current. The battery case formation method of stirring with water has not yet been put to practical use.

Means for Solving the Problems The present invention is a method for forming a battery of a lead-acid battery in which lead-acid is mixed in such a positive electrode active material, when stirring at a large current when using the above method, the positive electrode active material Is to improve the big problem of peeling off from the lattice. As a specific means, the specific gravity of the diluted sulfuric acid injected before the formation of the battery tank is 1.15.
0 to 1.180 or less, and after inversion of the battery after inversion of the battery tank, sulfuric acid having a specific gravity of 1.290 to 1.400 was added, and then
The battery is recharged at a current of 50A or more and 80A or less, and by gas generation by electrolysis, the low-concentration electrolytic solution remaining inside the battery after dewatering and the high-concentration sulfuric acid added after dewatering are agitated, and any electrolytic This is a battery case formation method with a liquid specific gravity. Further, after injecting dilute sulfuric acid before forming the battery case, after leaving for a period of 5 minutes or more and 120 minutes or less, preferably 30 minutes or more and 120 minutes or less, the battery case formation is started. .

Action In other words, the specific gravity of the liquid injected before the battery formation in the conventional battery case formation is very low at 1.150 or less, so that the specific gravity of the electrolyte after the battery formation is extremely low. Therefore, even if dewatering is performed after the formation of the battery tank, a considerable amount of electrolyte remains inside the battery, such as in the electrode plate, so that the specific gravity of sulfuric acid added after dewatering should be as high as 1.450 or more in order to obtain an arbitrary electrolyte specific gravity. There is a need to.
For this reason, when trying to stir the low specific gravity electrolytic solution remaining inside the battery and the high specific gravity sulfuric acid added after the liquid removal by recharging in a short time, a large current charging of about 100 A or more to about 400 A is required. Electrolysis when charged with such a large current becomes very active, and the amount of gas generated thereby becomes extremely intense. As a result, the binding force between the grid and the active material is reduced in the positive electrode plate in which the lead material is mixed in the active material, and the vigorous gas generation causes the grid and the active material to peel off, shortening the battery life. Become.

On the other hand, the present invention examines a range that does not hinder the rationalization of the amount of electricity of the battery formation as a specific gravity of the diluted sulfuric acid injected before the battery formation by various tests. It was found that there is no problem if the range is 1.150 or more and 1.180 or less. As a result, the specific gravity of the electrolytic solution after the formation of the battery container can be increased, so that the specific gravity of the sulfuric acid added after the dewatering can be significantly reduced.
It became possible to respond from 1.290 to 1.400.

Therefore, gas generation due to electrolysis required for stirring can be reduced, so that sufficient stirring can be performed if the current at the time of recharging is also 50 A or more. Thus, it is possible to prevent separation of the grid and the active material due to gas generation at the time of recharging at the time of stirring, and it is possible to rationalize the amount of battery formation electricity without lowering the life characteristics of the battery. Was.

Further, in the present invention, after dilute sulfuric acid is injected before forming the battery case,
After leaving the battery for 5 minutes to 120 minutes, preferably 30 minutes to 120 minutes, and then starting the battery formation, the sulfuric acid in the diluted sulfuric acid reacts with the active material in the electrode plate to cause electrolysis. The liquid concentration becomes extremely low, and α-PbO ₂
Are generated at the interface between the lattice and the active material. This α-
Since PbO ₂ has high conductivity but poor reactivity, it can increase the bonding force between the lattice and the active material and maintain the high bonding force for a long period of time. As a result, it was possible to further improve the problem of separation of the grid and the active material due to gas generation during stirring, and it was possible to further improve the life characteristics of the battery.

Examples Hereinafter, examples of the present invention will be described.

First, a 12V48Ah battery with a capacity of 5 HR was prepared using a positive electrode plate containing 40% of lead red in the paste active material, and then this battery was injected with various dilute sulfuric acids shown in Table 1 before battery formation. The mixture was liquefied and charged for 16H with a current of 10A to form a battery case.
Thereafter, the positive electrode plate was taken out of the battery, and the result of quantitative analysis of PbO _{2 in} the active material is shown in FIG.

As is evident from FIG. 1, the amount of PbO ₂ generated after the formation of the battery is almost constant if the specific gravity of the liquid before the formation of the battery is 1.150 or less, even if the specific gravity of the injected solution is 1.150 or more, which has been conventionally used as the upper limit of the low specific gravity. It can be seen that there is no difference and the efficiency of battery case formation is the same. When the specific gravity of the diluted sulfuric acid to be injected exceeds 1.180 and becomes 1.190
It can also be seen that the production amount of PbO ₂ has decreased, and the efficiency of battery formation has decreased. Next, the specific gravity of the diluted sulfuric acid to be injected before the formation of the battery was 1.180, and the battery was formed under various conditions according to the standing time after the injection and the current at the time of stirring after the completion of the formation of the battery as shown in Table-2. After completing the above, a cycle test was performed to examine the influence on the life, such as the state of separation between the lattice and the active material. The conditions are as follows: Discharge at 9.6 A until the terminal voltage of the battery drops to 10.5 V, charge at 120 A of the discharge capacity at 14.6 A, and the time when the capacity at the time of discharge becomes 50% of the 5HR capacity. Life time.
Table 3 shows the results. In addition, the current and the time at the time of battery case formation were both 16 A at 10 A.

From the results in Table-3, it is clear that the number of cycles in E of 100 A and F of 80 A in the stirring time is 3 minutes and the number of cycles in F is clearly larger than that in the decomposition after the test. In E, the separation between the lattice and the active material is remarkable, and the influence of the stirring current is clear. In addition, when the stirring current is the same at 80 A and the leaving time after injection is 3 minutes F and 5 minutes G, G has a larger number of cycles, and the leaving time after injection is 5 minutes or more. This shows that the life is prolonged. Next, it can be seen that the cycle is further extended in H and I where the discharge time is 30 minutes or more than in F, and it is preferable that the leaving time is 30 minutes or more. It is desirable that the standing time after the pouring is up to 120 minutes, since if it exceeds 120 minutes, the active material becomes stable lead sulfate during the standing time and the conversion efficiency is lowered.

Effects of the Invention As described above, according to the present invention, in a conventional lead-acid battery in which lead tin is mixed in a positive electrode active material, the specific gravity of dilute sulfuric acid injected before battery formation is set to a low specific gravity, and the specific gravity is increased after the formation. It solves a major problem with the battery case formation method of adding specific sulfuric acid and stirring and charging with a large current, the problem of separation between the grid and the active material, improving the battery life characteristics and improving the battery case formation. It is intended to improve efficiency.

[Brief description of the drawings]

Fig. 1 shows the specific gravity of dilute sulfuric acid injected before battery formation.
FIG. 3 is a view showing the amount of PbO ₂ generated in a positive electrode active material after chemical formation.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Naoto Hoshihara 1006 Oaza Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (56) References JP-A-52-118223 (JP, A) 93857 (JP, A) JP-A-62-93858 (JP, A) JP-A-63-13263 (JP, A) JP-B-39-9923 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) H01M 4/22

Claims (2)

(57) [Claims] In a method for forming a battery of a lead-acid battery using a paste containing mixed lead as a positive electrode active material, the specific gravity of dilute sulfuric acid injected before the formation of the battery is set to 1.150 or more and 1.180 or less. After the battery is inverted and drained, sulfuric acid with a specific gravity of 1.290 to 1.400 is added, and then recharged with a current of 50 A to 80 A, and the low concentration remaining inside the battery after the liquid is removed due to gas generation by electrolysis. A method for forming a battery case of a lead-acid battery by stirring an electrolytic solution and high-concentration sulfuric acid added after the liquid removal to obtain an arbitrary specific gravity of the electrolytic solution. 2. After the diluted sulfuric acid is injected before the formation of the battery tank, it is required
2. The battery case forming method for a lead-acid storage battery according to claim 1, wherein the battery case formation is started after leaving for a period of 0 minute or less.