CN113394523A - Acid adding and formation method for lead storage battery - Google Patents
Acid adding and formation method for lead storage battery Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/08—Selection of materials as electrolytes
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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Abstract
The invention discloses an acid adding and formation method of a lead storage battery, belonging to the field of lead storage battery manufacture and comprising the following steps: (1) adding low-density electrolyte with the volume of 60-70% of the pressurized imbibing volume of the pole group and the density of 1.10-1.20 g/mL, and adding under the condition of negative pressure pumping; (2) adding electrolyte to enable the electrolyte to reach the joint of a safety valve hole of the battery and the acid pot, and adding the electrolyte with medium density of 1.25-1.35 g/mL under the condition of negative pressure; (3) adding high-density electrolyte with the volume being 20-30% of the volume of the pressurized liquid absorption of the partition plate and the density being 1.40-1.55 g/mL, and adding by means of gravity; (4) and (4) formation. The invention adds the electrolytes with different densities and volumes in different modes, and combines with the formation process, thereby shortening the formation time, reducing the energy consumption and improving the formation efficiency and the production efficiency.
Description
Technical Field
The invention belongs to the field of lead storage battery manufacturing, and mainly relates to an acidification and formation method of a lead storage battery.
Background
The lead storage battery still has great advantages in the secondary battery due to the economy and safety, but the two main tasks of the development of the lead storage battery are to improve the performance of the lead storage battery and reduce the production cost of the lead storage battery under the impact of other secondary batteries. Formation is one of the main processes for producing the lead storage battery, and the improvement of the formation efficiency of the lead storage battery has important significance for reducing the production cost. The pole plate of the flooded lead storage battery is thin, the density of the added electrolyte is low, the formation time is usually from dozens of hours to more than thirty hours, however, the thickness of the pole plate of the AGM lead storage battery is thick, the density of the added electrolyte is also high, the formation efficiency is low, and the formation time needs three days. In the prior art, the formation time is shortened to 43-48 h by generally controlling parameters such as formation voltage, potential, current, temperature and the like of the lead storage battery.
Patent document CN111628229A discloses a method for manufacturing a lead-acid battery, wherein a first density sulfuric acid solution is added into a lead-acid battery to be formed, and the density is 1.04g/cm3～1.28g/cm3The electrified current is less than 0.35C, the solution is completely formed, and then a second density sulfuric acid solution is added into the battery, wherein the density of the sulfuric acid solution is 1.25g/cm3～1.60g/cm3In the meantime. The manufacturing method of the storage battery in the method can accurately obtain the capacity of the lead-acid storage battery and realize flexible production.
Patent document CN111682273A discloses a lead storage battery formation method, which is to add 1.1-1.4 times of saturated liquid absorption amount and mass concentration into a lead storage batteryCarrying out first-stage formation on a sulfate aqueous solution with the temperature of 0.4-0.8%, then carrying out first-stage formation on a 1.0-1.5C current, and controlling the boiling point of water to be 50-60 ℃ by pumping in the battery; (2) adding 1.2-1.8 times of saturated liquid absorption amount and 1.19-1.25 g/mL of sulfuric acid solution into the battery, then carrying out second-stage formation at 0.8-1.0 ℃, and controlling the boiling point of water to be 40-50 ℃ by pumping in the battery. According to the method, the aqueous solution containing sulfate is added firstly, the temperature rise of a battery is avoided, the alkaline maintaining time of formation is obviously prolonged, the temperature of formation is controlled to be 50-60 ℃ through the vacuum degree, the rapid formation can be carried out by adopting large current, and the method is beneficial to alpha-PbO2Under the formation conditions of alpha-PbO, increase in the content of alpha-PbO2And (4) content. Then, sulfuric acid solution with certain concentration is added in the second stage, and battery formation is continued under the condition of certain vacuum degree, so that rapid formation can be realized. Post-cell formation alpha-PbO2The content is improved, and the service life of the battery is prolonged.
Therefore, it is a problem to be solved by those skilled in the art to improve the formation efficiency, cycle life and production efficiency of lead-acid batteries.
Disclosure of Invention
The invention provides an acidification and formation method of a lead storage battery, and aims to improve the formation efficiency, cycle life and production efficiency of the lead storage battery.
An acid adding and formation method for a lead storage battery, which uses an acid adding pot to add acid to the lead storage battery, comprises the following steps:
(1) adding low-density electrolyte with the volume of 60-70% of the pressurized imbibing volume of the pole group and the density of 1.10-1.20 g/mL, and adding under the condition of negative pressure pumping;
the electrode group imbibition volume is the total volume of electrolyte that the electrode group can absorb in the lead storage battery cell.
After the low density electrolyte is added, a portion of the electrolyte reacts with the plate to form 3BS and 1 BS. The higher the density of the added electrolyte, the higher the content of the formed 1BS, which is not beneficial to the service life of the polar plate. The addition of the low-density electrolyte is beneficial to prolonging the service life of the lead storage battery. And a protective layer is formed on the outer surface of the polar plate by adding the low-density electrolyte, so that the electrolyte in the separator is delayed to continuously diffuse to the center of the polar plate, and the protective layer comprises most of 3BS and less of PbO, 1BS and PbSO4, and is beneficial to formation. The low-density electrolyte and the polar plate have little reaction heat, and the temperature rise of the lead storage battery is relatively low.
(2) Adding electrolyte to enable the electrolyte to reach the joint of a safety valve hole of the lead storage battery and an acid pot and medium-density electrolyte with the density of 1.25-1.35 g/mL, and adding the electrolyte under the condition of negative pressure pumping;
the negative pressure condition of the added electrolyte with medium density is weaker than that of the electrolyte with low density. If the negative pressure is too high, the diffusion of the electrolyte with medium density to the inside of the polar plate is accelerated, so that the content of 1BS and PbSO4 in the polar plate is increased, the formation process is not facilitated, and the service life of the lead storage battery is not prolonged. The aperture of the safety valve is small, and the diffusion of the subsequently added high-density electrolyte into the partition plate is delayed.
(3) Adding high-density electrolyte with the volume of 20-30% of the pressurized imbibition volume of the pole group and the density of 1.40-1.55 g/mL, and adding by gravity;
the open-circuit voltage of the lead storage battery is lower after only adding the low-density electrolyte and/or the medium-density electrolyte, and the problem of lower voltage can be solved by adding the high-density electrolyte. The high-density electrolyte is added by gravity, so that the diffusion speed of the high-density electrolyte to the partition plate can be delayed. The lead storage battery does not generate gas in the initial stage of formation by adding the high-density electrolyte, and the high-density electrolyte slowly diffuses into the separator. As the formation proceeds, sulfuric acid in the plates is released, increasing the electrolyte density in the separator. In the later period of formation, the lead storage battery is subjected to massive gassing, so that the diffusion of the electrolyte in the partition and the electrolyte in the acid kettle is accelerated, and the dispersion of the electrolyte in the partition is balanced.
(4) And (4) formation.
The negative pressure pumping condition in the step (1) is as follows: under the negative pressure of 0.085-0.095 MPa, the negative pressure is firstly pumped for 5-8S, then the air is discharged for 3-5S, and the process is repeated for 2-3 times.
The emptying process is to stop pumping negative pressure in the process of pumping negative pressure so that the internal air pressure of the lead storage battery is communicated with the atmospheric pressure.
And negative pressure is pumped for 2-3 times, so that the low-density electrolyte after reaction can be diffused to the center of the polar plate as much as possible.
The low-density electrolyte added in the step (1) contains sulfate, and the mass fraction of the sulfate is 1.5-2.5%.
The sulfate is at least one of sodium sulfate, magnesium sulfate, potassium sulfate or lithium sulfate.
The mass fraction of the sulfate is 1.5-2.5%, and the mass fraction of the sulfate in the conventional electrolyte is only 0.5-1.0%. The added sulfate has the function of conductive ions and can be used as supporting electrolyte in the formation process, thereby being beneficial to reducing the internal resistance in the initial charging stage and improving the utilization rate of current.
The temperature of the low-density electrolyte added in the step (1) is 0-10 ℃.
The negative pressure pumping condition in the step (2) is as follows: and continuously pumping for 5-8S under the negative pressure of 0.055-0.065 MPa.
The temperature of the electrolyte added in the step (2) and the step (3) is 0-35 ℃.
And (4) carrying out formation in circulating water at the temperature of 30-35 ℃.
The formation step in the step (4) is as follows:
step 1, 2.5A, constant current charging is carried out for 0.5 h;
step 2, 3.5A, constant current charging is carried out for 0.5 h;
step 3, 4.5A, constant current charging is carried out for 0.5 h;
step 4, 6A, constant current charging is carried out for 0.5 h;
step 5, 8A constant current charging for 4 h;
6, 6A, charging for 0.5h at constant current;
step 7, charging the battery to 16V at a constant current of 15A; then charging with 16V constant voltage until the current is 6A;
step 8, 5A, constant current charging for 1 h;
9, discharging the 10A at constant current to 11.5V;
step 10, charging the 18A to 16V with a constant current; then charging with 16V constant voltage until the current is 8A;
step 11, 8A constant current charging for 1 h;
step 12, 5A constant current charging is carried out for 0.5 h;
step 13, discharging the 15A at constant current to 11.5V;
step 14, charging the 18A to 16V by constant current; then charging with 16V constant voltage until the current is 8A;
step 15, 8A constant current charging for 1 h;
step 16, 5A, constant current charging for 1 h;
step 17, 3.5A, charging for 1.5h at constant current;
step 18, discharging the 10A at constant current to 10.5V;
step 19, 18A constant current charging for 1 h;
step 20, 5A, constant current charging for 1 h;
step 21, 3A, constant current charging for 1 h;
and step 22, charging the 1A for 1h at constant current.
And (3) performing charged acid extraction after the step 22 is completed: and (4) taking out the redundant electrolyte while charging at the current of 1A, and stopping charging after the redundant electrolyte is taken out to finish formation.
The total time of the formation process is 24-25 h, and the net charge amount in the formation process is 140-150 Ah.
Compared with the prior art, the invention has the following advantages:
according to the invention, the low-density electrolyte is added firstly, the low-density electrolyte reacts with the polar plate to release less heat, and the temperature rise of the lead storage battery is relatively low; the added low-density electrolyte contains sulfate which has good conductive ion effect and can be used as a supporting electrolyte in the formation process, so that the internal resistance of the lead storage battery in the initial charging stage is reduced, the utilization rate of current is improved, and the formation time is shortened. In the invention, the high-density electrolyte is added finally, the high-density electrolyte is slowly diffused in the separator and does not generate gas in the early stage of formation. In the later formation stage, a large amount of gas is separated out from the lead storage battery, so that the diffusion rate of the electrolyte in the partition plate and the diffusion rate of the electrolyte in the acid kettle are increased, and the electrolyte in the partition plate is dispersed to be balanced. According to the invention, the electrolytes with different densities and different volumes are added in sequence and matched with the formation process, so that the formation time can be shortened, the energy consumption in the formation process is reduced, and the aims of improving the formation efficiency and the production efficiency are fulfilled.
Drawings
Fig. 1 shows a positive plate of a lead-acid battery after formation in example 1.
Fig. 2 shows a positive plate of a lead-acid battery after formation in example 2.
Fig. 3 shows a positive plate of a lead-acid battery after formation in comparative example 1.
Fig. 4 shows a positive plate of the lead-acid battery after formation in comparative example 2.
Detailed Description
Example 1
Taking a lead storage battery with the model of 12V and 20Ah, adding a low-density electrolyte with the density of 1.10g/mL accounting for 60% of the pressurized imbibition volume of a pole group into the lead storage battery by using an acid adding kettle, wherein the temperature of the low-density electrolyte is 10 ℃, and the mass fraction of sodium sulfate in the low-density electrolyte is 2.5%; after the low-density electrolyte is added, vacuumizing is firstly carried out for 5S under the negative pressure of 0.095MPa, then emptying is carried out for 3S, and the steps are repeated for 3 times. After the lead storage battery is in a stable state, adding medium-density electrolyte with the density of 1.35g/mL to the joint of the safety valve hole and the acid pot, wherein the temperature of the medium-density electrolyte is 0 ℃, adding the medium-density electrolyte, vacuumizing for 8S under the negative pressure of 0.055MPa, and emptying for 2S. After the lead storage battery is in a stable state, high-density electrolyte with the density of 1.55g/mL accounting for 20% of the pressurized imbibing volume of the separator is added by gravity, and the temperature of the high-density electrolyte is 35 ℃. After the high-density electrolyte is added, the lead storage battery is placed in circulating water at the temperature of 30-35 ℃ for formation, and the formation steps are shown in table 1.
TABLE 1 formation procedure of lead-acid battery
Disassembling the lead storage battery, wherein the disassembled positive plate is shown in figure 1, and PbO is contained in the positive plate2The contents are shown in Table 3.
Example 2
Taking lead storage battery with the model of 12V and 20Ah, and adding acid pot to leadAdding low-density electrolyte with the density of 1.20g/mL accounting for 70% of the pressurized liquid absorption volume of the pole group into the storage battery, wherein the temperature of the low-density electrolyte is 0 ℃, and the mass fraction of magnesium sulfate in the low-density electrolyte is 1.5%; after the low-density electrolyte is added, vacuumizing is firstly carried out for 8S under the negative pressure of 0.095MPa, then emptying is carried out for 5S, and the steps are repeated for 2 times. After the lead storage battery is in a stable state, adding medium-density electrolyte with the density of 1.25g/mL to the joint of the safety valve hole and the acid pot, wherein the temperature of the medium-density electrolyte is 35 ℃, adding the medium-density electrolyte, vacuumizing for 5S under the negative pressure of 0.065MPa, and emptying for 2S. After the lead storage battery is in a stable state, high-density electrolyte with the density of 1.40g/mL accounting for 30% of the pressurized imbibing volume of the separator is added by gravity, and the temperature of the high-density electrolyte is 0 ℃. After the high-density electrolyte is added, the lead storage battery is placed in circulating water at the temperature of 30-35 ℃ for formation, and the formation steps are shown in table 1. Disassembling the lead storage battery, wherein the disassembled positive plate is shown in figure 2, and PbO is contained in the positive plate2The contents are shown in Table 3.
Comparative example 1
Taking a lead storage battery with the model of 12V and 20Ah, adding electrolyte with the density of 1.255g/ml which is 1.5 times of the imbibition volume of a pole group into the lead storage battery by using an acid adding kettle, wherein the temperature of the electrolyte is 10 ℃, the mass fraction of sodium sulfate in the electrolyte is 0.8%, vacuumizing the electrolyte for 10 seconds under the negative pressure of 0.085Mpa after adding the electrolyte, then emptying the electrolyte for 5 seconds, and repeating the steps for 4 times. And then placing the mixture into cooling water at the temperature of 10-20 ℃ for standing for 0.5h, and charging the mixture into the product in circulating water at the temperature of 30-40 ℃ after standing. The formation steps are shown in Table 2.
TABLE 2 formation procedure of lead-acid battery
| No. | Mode of operation | Current (A) | Jump toCondition |
| 1 | Constant current charging | 2.5 | The time is more than or equal to 0.5h |
| 2 | Constant current charging | 3.5 | The time is more than or equal to 0.5h |
| 3 | Constant current charging | 4.5 | The time is more than or equal to 0.5h |
| 4 | Constant current charging | 5 | The time is more than or equal to 2.0h |
| 5 | Constant current charging | 6.5 | The time is more than or equal to 7h |
| 6 | Constant current discharge | -10 | The time is more than or equal to 0.3h |
| 7 | Constant current charging | 8 | The time is more than or equal to 0.4h |
| 8 | Constant current charging | 6 | The time is more than or equal to 1h |
| 9 | Constant current discharge | -10 | The time is more than or equal to 0.5h |
| 10 | Constant current charging | 8 | The time is more than or equal to 0.7h |
| 11 | Constant current charging | 6 | The time is more than or equal to 1.0h |
| 12 | Constant current discharge | -10 | The time is more than or equal to 0.7h |
| 13 | Constant current charging | 8 | The time is more than or equal to 0.9h |
| 14 | Constant current charging | 6 | The time is more than or equal to 2h |
| 15 | Constant currentDischarge of electricity | -10 | The time is more than or equal to 0.9h |
| 16 | Constant current charging | 8 | The time is more than or equal to 0.9h |
| 17 | Constant current charging | 6 | The time is more than or equal to 2h |
| 18 | Constant current discharge | -10 | The time is more than or equal to 1.2h |
| 19 | Constant current charging | 8 | The time is more than or equal to 1.2h |
| 20 | Constant current charging | 6 | The time is more than or equal to 7h |
| 21 | Constant current charging | 5.5 | The time is more than or equal to 3.5h |
| 22 | Constant current charging | 3.5 | The time is more than or equal to 2h |
| 23 | Constant current discharge | -10 | The time is more than or equal to 1.9h |
| 24 | Constant current charging | 8 | The time is more than or equal to 2.4h |
| 25 | Constant current charging | 6 | The time is more than or equal to 2h |
| 26 | Constant current charging | 5 | The time is more than or equal to 1.0h |
| 27 | Constant current charging | 3 | The time is more than or equal to 1h |
| 28 | Constant current charging | 1 | The time is more than or equal to 1h |
Disassembling the lead storage battery, and making the disassembled positive plate as shown in figure 3, wherein PbO is contained in the positive plate2The contents are shown in Table 3.
Comparative example 2
Taking a lead storage battery with the model of 12V and 20Ah, adding a low-density electrolyte with the density of 1.10g/mL accounting for 60% of the pressurized imbibition volume of a pole group into the lead storage battery by using an acid adding kettle, wherein the temperature of the low-density electrolyte is 0 ℃, and the mass fraction of magnesium sulfate in the low-density electrolyte is 2.5%; after the low-density electrolyte is added, vacuumizing is firstly carried out for 8S under the negative pressure of 0.095MPa, then emptying is carried out for 5S, and the steps are repeated for 2 times. After the lead storage battery is in a stable state, adding medium-density electrolyte with the density of 1.27g/mL to the joint of the safety valve hole and the acid pot, wherein the temperature of the medium-density electrolyte is 35 ℃, adding the medium-density electrolyte, vacuumizing for 5S under the negative pressure of 0.055MPa, and emptying for 2S. After the lead storage battery is in a stable state, high-density electrolyte with the density of 1.40g/mL accounting for 30% of the pressurized imbibing volume of the separator is added by gravity, and the temperature of the high-density electrolyte is 0 ℃. After the high-density electrolyte is added, the lead storage battery is placed in circulating water at the temperature of 30-35 ℃ for formation, and the formation steps are shown in table 2. Disassembling the lead storage battery, and making the disassembled positive plate as shown in figure 4, wherein PbO is contained in the positive plate2The contents are shown in Table 3.
As can be seen from the appearances of the positive plates in fig. 1 to 4, the appearance of the plate in comparative example 2 is the best, the appearance of the plate in examples 2 and 1 is the next to the appearance of the plate in comparative example 1, and the appearance of the plate in comparative example 1 is the worst, which indicates that the acid addition method of the present invention is favorable for improving the formation efficiency.
Application example 1
And detecting the lead storage battery according to the GB/T22199-2017 standard. Discharge time of 2 hr: in 25 ℃ + -2 ℃ environment, the fully charged battery is discharged to 10.5V at 10A, and the maximum value of 2hr capacity is obtained by continuously measuring for 3 times. -18 ℃ low temperature discharge time: the fully charged cells were discharged at-18 ℃ for a period of 10A to 10.5V. Large current discharge time: discharging at 36A in 25 + -2 deg.C environment to 10.5V. The results are shown in Table 3.
TABLE 3 test results of lead storage battery performance
As can be seen from Table 3, in examples 1 and 2, the net charge amount was 50Ah less and the formation time was 21h less in examples 1 and 2, compared with comparative example 1, but the open circuit voltage, PbO, was lower in examples 1 and 22The content, 2hr capacity, low temperature at-18 deg.C and large current discharge performance are equivalent to those of comparative example 1. The acidification forming method can effectively shorten the forming time, improve the forming efficiency, save the electric energy and does not influence the performance of the lead storage battery.
Comparative example 2 the acid addition method in the example and the formation method in comparative example 1 were used, comparative example 2 compared to comparative example 1, PbO in comparative example 22The higher the content and the open-circuit voltage, the acid addition method in the embodiment is favorable for improving the performance of the lead storage battery.
Claims (10)
1. An acid adding and forming method for a lead storage battery, which uses an acid adding pot to add acid to the lead storage battery, is characterized by comprising the following steps:
(1) adding low-density electrolyte with the volume of 60-70% of the pressurized imbibing volume of the pole group and the density of 1.10-1.20 g/mL, and adding under the condition of negative pressure pumping;
(2) adding electrolyte to enable the electrolyte to reach the joint of a safety valve hole of the lead storage battery and an acid pot and medium-density electrolyte with the density of 1.25-1.35 g/mL, and adding the electrolyte under the condition of negative pressure pumping;
(3) adding high-density electrolyte with the volume being 20-30% of the volume of the pressurized liquid absorption of the partition plate and the density being 1.40-1.55 g/mL, and adding by means of gravity;
(4) and (4) formation.
2. The acidification and chemical formation method of claim 1, wherein the negative pressure condition in step (1) is: and under the negative pressure of 0.095MPa, firstly pumping for 5-8S, then emptying for 3-5S, and repeating for 2-3 times.
3. The acid-adding chemical synthesis method as claimed in claim 1, wherein the low-density electrolyte added in step (1) contains sulfate, and the mass fraction of the sulfate is 1.5% to 2.5%.
4. The method of claim 3, wherein the sulfate is at least one of sodium sulfate and magnesium sulfate.
5. The method of claim 1, wherein the low-density electrolyte added in step (1) has a temperature of 0 to 10 ℃.
6. The acidification and chemical synthesis method of claim 1, wherein the negative pressure condition in step (2) is: and continuously pumping for 5-8S under the negative pressure of 0.055-0.065 MPa, and emptying for 2S.
7. The acid-adding chemical synthesis method according to claim 1, wherein the temperature of the electrolyte added in the step (2) is 0 to 35 ℃.
8. The acid-adding chemical synthesis method according to claim 1, wherein the temperature of the electrolyte added in the step (3) is 0 to 35 ℃.
9. The acid-adding chemical synthesis method according to claim 1, wherein the chemical synthesis in the step (4) is performed in circulating water at 30 to 35 ℃.
10. The acid-adding chemical synthesis method according to claim 1, wherein the chemical synthesis in step (4) comprises the following steps:
step 1, 2.5A, constant current charging is carried out for 0.5 h;
step 2, 3.5A, constant current charging is carried out for 0.5 h;
step 3, 4.5A, constant current charging is carried out for 0.5 h;
step 4, 6A, constant current charging is carried out for 0.5 h;
step 5, 8A constant current charging for 4 h;
6, 6A, charging for 0.5h at constant current;
step 7, charging the battery to 16V at a constant current of 15A; then charging with 16V constant voltage until the current is 6A;
step 8, 5A, constant current charging for 1 h;
9, discharging the 10A at constant current to 11.5V;
step 10, charging the 18A to 16V with a constant current; then charging with 16V constant voltage until the current is 8A;
step 11, 8A constant current charging for 1 h;
step 12, 5A constant current charging is carried out for 0.5 h;
step 13, discharging the 15A at constant current to 11.5V;
step 14, charging the 18A to 16V by constant current; then charging with 16V constant voltage until the current is 8A;
step 15, 8A constant current charging for 1 h;
step 16, 5A, constant current charging for 1 h;
step 17, 3.5A, charging for 1.5h at constant current;
step 18, discharging the 10A at constant current to 10.5V;
step 19, 18A constant current charging for 1 h;
step 20, 5A, constant current charging for 1 h;
step 21, 3A, constant current charging for 1 h;
and step 22, charging the 1A for 1h at constant current.
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Cited By (2)
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| CN113937434A (en) * | 2021-10-12 | 2022-01-14 | 浙江天能动力能源有限公司 | Segmented acid adding process for lead-acid storage battery |
| CN114361609A (en) * | 2021-12-10 | 2022-04-15 | 安徽力普拉斯电源技术有限公司 | High-temperature-resistant acid adding process for container formation of power battery |
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| CN113394523B (en) | 2022-09-20 |
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