KR20030003029A - Electrolyte filling equipment for case formation and procedure for case formation - Google Patents

Abstract

PURPOSE: To provide a lead-acid battery having an excellent electrical characteristic by realizing battery jar formation capable of smoothly filling the electrolyte with an accurate filling quantity of the electrolyte and realizing the battery jar formation capable of preventing intrusion of the side air during the formation of the lead-acid battery using an exterior-fitted electrolyte storage tank. CONSTITUTION: This battery jar forming solution filling device 1 consists of a solution storage tank 3 provided with a seal valve 7 and a tube for liquid- tightly connecting the solution storage tank and a solution filling port of the battery to each other, and the device 1 is provided with a narrow tube 5 for connecting an inner space of a cell and an inner space of the solution storage tank to each other through the inside of the described tube, and an opening provided in an upper wall of the solution storage tank is sealed with the valve. A battery jar forming method for the lead-acid battery uses this battery jar forming solution filling device to fill the whole of a cell with the predetermined quantity of the electrolyte solution filled in the solution storage tank in a formation process.

Description

ELECTROLYTE FILLING EQUIPMENT FOR CASE FORMATION AND PROCEDURE FOR CASE FORMATION

In particular, the present invention relates to a liquid injecting device for pre-harmonizing a sealed lead acid battery of a liquid-limiting type and a pre-harmonizing method using the same.

The most common method of pre-harmonization is the method of carrying out chemical conversion by charging the total amount of the electrolyte solution previously required in a cell. In this case, the injected electrolyte solution does not penetrate into the electrode plate group in an instant and stays in the spaces of the upper and peripheral portions of the electrode plate group. In addition, Mars entails gassing from the plate group, pushing up the electrolyte. Therefore, in the above method, it is necessary to secure sufficient space in the cell in order to accommodate the electrolyte solution once retained and to prevent the liquid from overflowing even when gassing.

However, in recent years, in order to increase the volumetric efficiency of batteries, it is required to increase the charging volume of the electrode plate group. Therefore, there is no choice but to reduce the volume of space for removing the group of plates in the cell.

The electrolyte solution injected as described above is not absorbed in the electrode plate group in an instant, but requires a certain time. Mars also involves gassing from the plates. Therefore, when the space volume that can be secured in the battery becomes small, it is impossible to inject a predetermined amount of electrolyte solution at one time, or the electrolyte solution remaining on the upper portion by the gassing overflows, contaminating the peripheral portion or causing electrolyte shortage. There was concern.

In order to eliminate the drawbacks of the conventional method, a method of preparing an externally mounted liquid holding tank containing electrolyte, connecting the liquid holding tank and a cell constituting the battery by a pipe, and supplying the electrolyte to the cell through the pipe has been proposed. have. However, in the conventionally proposed method, since the substitution of the gas in the cell and the electrolyte in the holding tank does not proceed smoothly, there is a concern that a predetermined amount of liquid cannot be injected during the chemical conversion process.

As described above, gas is generated from the electrode plate group during the chemical conversion process. If the cell and the holding tank are hermetically sealed, the internal pressure increases due to the gas generation. Conventionally, in order to discharge the generated gas to the outside, the opening was made in the upper surface of the holding liquid tank, and it was set as an open system. However, in this open system pour apparatus, it was not possible to prevent outside air from invading into the cell after mars progressed and all of the electrolyte solution was absorbed by the electrode plate group. In the liquid-limiting lead acid battery, gas tends to diffuse in the electrode plate group due to its structure, and as a result, the negative electrode plate is oxidized by oxygen contained in the outside air, which may deteriorate battery characteristics.

The present invention has been made in view of the drawbacks of the above-mentioned conventional electrochemically injectable liquid injector, and there is no fear that the electrolyte in the chemical will overflow, and the liquid of the electrolytic solution is smooth and the amount of the electrolyte is high. . It also achieves harmonization without fear of outside air invading Mars.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a perspective view showing a state in which a premixable pouring device according to the present invention is connected to a lead acid battery.

2 is a partially cut-away sectional view of the pre-melting pouring apparatus according to the present invention.

(Description of Major Symbols in Drawings)

1: Pre-harmonization injection device

3: maintenance tank

4: tube for connection

5: customs

7: seal valve

The premixing liquid injector for lead-acid batteries according to the present invention comprises a liquid retaining tank and a tube for tightly connecting the liquid retaining tank and the liquid injector of the battery, and the liquid retaining tank is the same as the cells constituting the battery. A liquid injection device having the above-mentioned room and one connection pipe in this room, and having a customs pipe passing through the inside of the pipe to connect the inner space of the cell and the inner space of the holding tank.

Moreover, the pre-harmonization pouring apparatus which concerns on this invention is provided with the seal valve for preventing invasion of external air to the said holding liquid tank.

In the pre-harmonization method according to the present invention, a predetermined amount of electrolyte is filled in each room of the liquid holding tank, an electrolyte solution is injected into a cell, and a battery is formed at the same time. This is to inject all the electrolyte solution.

Embodiment of the invention

FIG. 1 is a view in which the electrolytic solution pouring device 1 according to the present invention is mounted on a sealed lead acid battery 2. The premixing liquid injector 1 is composed of an electrolyte holding tank 3 and a tube 4 for tightly connecting the tank and electricity 2. In the example shown in the figure, the battery 2 is a monoblock type battery composed of six cells. A liquid injection hole 9 is formed in each of the six cells, and the inner space of each cell is connected to the inner space of the liquid holding tank 3 through the pipe 4.

The holding liquid tank 3 of the pre-harmonizing liquid injector 1 is a container made of polypropylene, for example, and is divided into partitions equal to the number of cells in the battery by the partition wall. Each room is filled with a predetermined amount of electrolyte solution.

In addition, as described above, in each room of the holding liquid tank 3, a pipe 4 for connecting with the liquid inlet of the lead storage battery is arranged. The material and dimensions of this pipe 4 are not particularly limited. For example, it is a tube of synthetic rubber. One end of the pipe 4 is connected in a liquid-tight manner to a liquid discharge port 8 formed in the lower surface of the liquid holding tank 3 (not shown in Fig. 1, as shown in Fig. 2 to be described later), and the other end of the lead. It is connected liquid-tightly to the injection hole 9 of the cell of the storage battery 2. In addition, the liquid discharge port 8 formed on the lower surface of the liquid holding tank 3 is projected downward in a cylindrical shape and formed into a shape that can be fitted with the liquid filling hole 9 so that the liquid holding tank 3 and the pipe 4 can be fitted. It can also be integrated. The inner diameter of this pipe 4 is 3-10 mm, the length is about 10-100 mm, The opening valve 6 is formed in the upper wall of each room of the holding liquid tank 3, The seal valve 7 which mentions this opening later is 7 To close.

2 is a cross-sectional view showing the internal structure of one side of the holding liquid tank 3. As shown in FIG. The liquid discharge port 8 is formed in the lower surface of the holding liquid tank 3, and one end of the pipe 4 is fitted. The other end of this tube 4 is fitted to the injection hole 9 of the battery 2. In the liquid holding tank 3 of the pre-harmonizing liquid injecting device 1 according to the present invention, as shown in FIG. 2, a customs pipe 5 extending from the upper portion of the inner space of the cell to the upper portion of the room space of the holding liquid tank as shown in FIG. 2. ). This tubular pipe 5 is fixed to the inner wall of the pipe 4. This capillary tube 5 is a tube made of polypropylene or polytetrafluoroethylene having an outer diameter of 2 to 5 mm and an inner diameter of 0.5 to 3 mm, for example.

The inner space of the cell to which the electrolyte tank filled with electrolyte is connected is sealed. Therefore, in order to transfer the electrolyte solution from the holding tank into the cell, the gas in the cell must be discharged. In the conventional liquid injecting device, since the gas in the cell is not provided with a function of discharging the gas, the replacement of the gas in the cell and the electrolyte filled in the liquid holding tank does not proceed smoothly.

In the case of a liquid injector according to the present invention, the tubules 5 serve as a passage when the gas in the cell moves to the space in the liquid holding tank when the electrolyte is injected into the cell. In order to facilitate the discharge of the gas, it is preferable that the upper end 10 of the tubule comes above the liquid level of the electrolyte solution 11 filled in the holding liquid tank.

As described above, since the space inside the cell and the liquid tank are tightly connected, gassing occurs in the cell at the time of chemical conversion, and even if the electrolyte in the cell is pushed up, the pushed liquid is transferred into the liquid tank and does not leak. . Therefore, it is possible to inject a predetermined amount of liquid precisely by completing the injection of all liquids at the end of chemical conversion without losing the liquid charged in the chemical conversion process.

In the state where the liquid injector according to the present invention is connected to the cell, the space in the cell and the liquid holding tank is a closed system. That is, the opening 6 is formed in the upper wall of each room of a holding liquid tank, and this opening is closed by the seal valve 7. As shown in FIG. When the internal pressure in the cell and in the holding tank is increased, the seal valve is opened to release gas from the tank to the outside to suppress the internal pressure increase. On the other hand, when the outside air tries to invade, the valve is closed to prevent the intrusion of the outside air. By attaching this seal valve, it is possible to prevent outside air from entering the cell during the chemical conversion process.

The structure of the said seal valve is not specifically limited. The exhaust valve of lead acid battery can be applied. As a simple structure, for example, as shown in Fig. 2, a hat-shaped flexible rubber valve 7 is fitted over the cylindrical opening 6 drilled in the upper wall of the holding fluid tank to close the opening. A sealing agent such as silicon oil is filled between the inner wall of the rubber valve and the outer wall of the cylindrical opening to ensure airtightness. If necessary, a part of the periphery of the rubber plate is fixed to the holding liquid tank, and when the portion is made free, the internal portion of the tank is lifted, so that the portion of the free material is lifted, so that a gap is formed from the wall of the holding liquid tank. On the other hand, when gas is going to invade from the outside, the rubber valve comes into close contact with the wall of the liquid holding tank by pressing by the outside air, thereby preventing the intrusion of outside air. Although the opening valve pressure of this valve is not specifically limited, It is preferable to set to 0.1-0.5 kg / cm <2> which is a range which does not adversely affect a battery and a holding liquid tank.

Hereinafter, the present invention will be described in detail with reference to one embodiment.

Example

The liquid injecting device provided with the seal valve in the opening of the upper part of the pipe | tube and the liquid holding tank in the pipe which concerns on the said invention was applied to the sealed lead acid battery of the capacity | capacitance 5Ah of 6-cell structure. After each of the six chambers of the holding tank was connected to each cell of the battery, the opening of the holding tank was once opened, and 50 ml of diluted sulfuric acid, which was an electrolyte solution, was filled in each of the holding tanks. After the liquid filling, the opening was closed by the seal valve, and chemical conversion was carried out.

(Comparative Example 1)

Chemical conversion was performed by applying a liquid injecting device having the same configuration as in Example 1 to a lead acid battery of the same type as in Example 1, except that the tube was not provided with a customs pipe.

Pre-harmonization was performed at the temperature of 40 degreeC. Charging conditions are current 2.5A {rate 0.5It (A)} with A pattern of 20 hours of charging time, current 1.5A {rate 0.3It (A)} with B pattern of 30 hours of charging time, current 1.2A {rate 0.24It (A)} and three types of C patterns with a charging time of 40 hours. After the end of chemical conversion, the amount of electrolyte remaining in the tank was investigated.

Table 1 and Table 2 show the results of the amount of electrolyte remaining in the holding tank after the end of chemical conversion. In Table 1, the remaining liquid amount for each battery which totaled 6 cells is shown, and in Table 2, the remaining liquid amount for each cell when formed by the A pattern is shown.

Mars Pattern Residual liquid in the holding tank (ml) A B C Battery NO. One 2 3 One 2 3 One 2 3 division In-house customs 0 0 0 0 0 0 0 0 0 No tubes 14.1 9.4 14.6 12.7 11.8 12.2 9.5 8.6 11.0

As shown in Table 1, in Example 1, the pouring of the total amount of the electrolyte solution filled in the holding tank was completed in all the batteries. On the contrary, in the case of the comparative example 1, the electrolyte solution which was not poured in the holding tank remained in all the batteries. As the filling time in the chemical conversion process becomes shorter, it is understood that the amount of remaining liquid in the tank increases.

Cell NO. Residual liquid in the liquid holding tank (ml) division Battery NO. One 2 3 4 5 6 In-house customs One 0 0 0 0 0 0 2 0 0 0 0 0 0 3 0 0 0 0 0 0 No customs in the jurisdiction One 2.7 1.4 3.1 2.9 3.4 0.6 2 0 1.7 4.1 0 3.5 0.1 3 2.4 1.6 1.1 3.2 3.3 3.0

Table 2 shows the results of the A pattern with the shortest filling time in the chemical conversion process. However, in the case of Example 1, in contrast to the completion of the pouring in all the cells, in Comparative Example 1, most of the cells remained in the liquid holding tank. The electrolyte can be seen, and the variation in the amount of remaining liquid in each cell is also large.

Moreover, Table 3 shows the result of having investigated the specific gravity of the electrolyte solution remaining in the liquid holding tank after chemical conversion without the in-tube customs shown in Table 2.

division Battery NO. Specific gravity of residual liquid in the holding tank One 2 3 4 5 6 Cell NO. No customs in the jurisdiction One 1.23 1.24 1.24 1.25 1.23 1.28 2 - 1.24 1.25 - 1.25 1.25 3 1.24 1.23 1.23 1.23 1.23 1.24

As shown in Table 3, the variation of each cell was found in the specific gravity of the liquid remaining in the liquid holding tank. Since the electrolyte specific gravity reflects the progress of Mars, the results in Table 3 suggest that there is a variation in the progress of Mars in each cell. This deviation is considered to be caused because of variations in the pouring of the electrolyte, and may adversely affect the cycle performance in addition to the initial characteristics of the battery.

The battery after chemical conversion was used for the discharge test with the battery 5A {rate 1It (A)} at room temperature. Table 4 shows the discharge duration of each battery.

Mars Pattern Discharge duration (minutes) A B C Battery NO. One 2 3 One 2 3 One 2 3 division In-house customs 48 48 48 48 48 49 49 49 48 No tubes 42 41 42 44 44 43 44 45 45

As shown in Table 4, the discharge capacities of the batteries formed by applying the pouring apparatus of Example 1 were all higher than the discharge capacities of the batteries formed by applying the injection apparatus of Comparative Example 1. In the case of the comparative example 1, it is thought that the fall of discharge capacity is because the amount of pouring liquid is insufficient, and there exists a difference in chemical conversion by a cell as mentioned above.

(Comparative Example 2)

The same chemical conversion as in Example 1 was carried out except that an open-type liquid injecting device was not applied to the opening formed in the upper wall of the holding liquid tank. The charging conditions in Mars were the same as in the above B pattern. In the case of Comparative Example 2, the amount of the remaining electrolyte solution in the liquid retaining tank after the termination of chemical conversion was 0. The battery synthesized in Comparative Example 2 was used for a discharge test under the same conditions as described above. The results are shown in Table 5.

Division Battery NO. Discharge duration (minutes) One 2 3 No seal valve 46 46 45

As shown in Table 5, in the case of Comparative Example 2, the discharge capacity was lower than in the case of Example 1 described in Table 3, although a predetermined amount of the electrolyte was injected. In the case of Comparative Example 2, this is considered to have an adverse effect because outside air invades into the cell in the chemical conversion step and the negative electrode plate is oxidized. When the negative electrode plate is subjected to air oxidation, lead sulfate is produced. The production of lead sulfate not only reduces the initial capacity, but also raises the float current to reduce the battery life. It is difficult to return lead sulfate produced by air oxidation to lead by chemical conversion, and the electrodepositing apparatus for pre-harmonizing according to the present invention has a function of preventing air infiltration into cells during chemical conversion. Effective for preventing air oxidation.

As described above, according to the present invention, it is possible to reliably inject a predetermined amount of the electrolytic solution in the chemical conversion step, thereby providing a lead acid battery having a small variation and excellent characteristics. In addition, oxidation of the negative electrode plate due to invasion of outside air in the chemical conversion process can be prevented, and a lead acid battery excellent in characteristics can be provided.

Claims (2)

Maintenance tank; And a pipe for fluidly connecting the cells of the liquid holding tank and the lead acid battery to each other, wherein the liquid filling device for pre-harmonizing is disposed to pass through the inside of the tube to connect the inner space of the cell and the inner space of the liquid holding tank. Pre-harmonizing pouring device of the lead acid battery, characterized in that. The preparative liquid injectable device for lead-acid battery according to claim 1, wherein a seal valve for preventing intrusion of outside air is disposed in the holding liquid tank.