Colloidal lead acid battery processing
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- ZIBO TORCH ENERGY
- Filing Date
- 2026-02-03
- Publication Date
- 2026-06-19
Smart Images
Figure CN122246294A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of lead-acid battery technology, specifically relating to a processing technology for gel lead-acid batteries. Background Technology
[0002] Lead-acid batteries, as a mature energy storage device, are widely used in various fields such as new energy storage, electric vehicle auxiliary power supplies, and emergency power supply systems due to their low cost, readily available raw materials, and stable discharge performance. Gel batteries, a branch of lead-acid batteries, offer advantages over traditional full-electrode / starved-electrode batteries, including lower self-discharge, better temperature adaptability, non-stratifying electrolyte, and resistance to deep discharge, making them widely used in multiple fields.
[0003] However, current production processes for gel batteries still face numerous bottlenecks, severely restricting their large-scale production efficiency and product quality stability, and also driving up production costs. Specifically, traditional gel batteries produced using the internal formation process require vacuum filling to ensure the gel uniformly fills the internal gaps of the battery. However, thermal runaway is prone to occur during the internal formation stage, resulting in low initial capacity and a long production cycle. Gel batteries produced using the post-formation acid-pouring filling process require acid cycling, discharge, acid removal, filling, and charging, which is cumbersome. Furthermore, because the amount of electrolyte poured out from each battery during acid removal varies, the amount of filling for each battery also differs, leading to uncontrollable product quality and high production costs. Summary of the Invention
[0004] To overcome the aforementioned problems in the prior art, this invention provides a processing technology for gel lead-acid batteries. By adjusting the ratio of silica and sulfuric acid solution, as well as a specific gel cycle process and gel cycle connector, the production cycle and production cost are reduced, and product quality is improved.
[0005] The processing technology for colloidal lead-acid batteries described in this invention includes the following steps:
[0006] S1 Battery Acid Cycle Formation: After the battery completes acid cycle formation in the workshop, it is cooled down; S2 pre-cycle discharge: After cooling, the battery is transported to the glue cycle system area to install the glue cycle connector and connect the circuit for discharge. After discharge, the battery begins glue cycle. S3 Battery Adhesive Cycling: Add gaseous SiO2 and H2SO4 solution to the adhesive cycling system. After S2 is completed, start the adhesive cycling system to carry out adhesive cycling. S4 Battery Charging: At the end of the gel cycle, the battery is charged with constant current. After charging is completed, the gel cycle is stopped, the circulation pipe is removed, the battery is drained, and then charged with constant voltage.
[0007] In step S1, after acid cycling formation, the mass fraction of sulfuric acid in the battery is 36.8%-37.4%, and the temperature is reduced to 20-30℃ in 1-2 hours.
[0008] The sulfuric acid mass fraction of the battery after formation is adjusted to maintain consistency with that of the gel cycle system and the finished gel battery. This prevents concentration differences between the gel electrolyte and the sulfuric acid in the battery, which could lead to excessive heat generation during gel cycle mixing, causing premature gelation of the gel electrolyte and resulting in uneven gel cycle. Maintaining consistent sulfuric acid mass fraction across all three components reduces the calculation steps involved in sulfuric acid preparation during gel cycle. The use of industrial fans for cooling is necessary because the battery temperature is high after acid cycle formation; directly initiating gel cycle would also cause premature gelation of the gel electrolyte.
[0009] In step S2, the glue circulation connector includes a main body, which consists of a return glue tube channel, an inlet glue tube channel, an inlet glue tube body, and a return glue tube body. The return glue tube channel adopts a frustum design, and the inlet glue tube channel vertically penetrates the return glue tube channel. The inlet glue tube body and the return glue tube body are integrally vertically connected at the top of the inlet glue tube channel and the return glue tube channel, respectively. A sealing ring is also provided at the bottom of the main body to ensure the airtightness of the system when the glue circulation connector is in use.
[0010] In conventional acid circulation connectors, the angle between the inlet and return acid channels and the inlet and return acid tubes causes the colloidal electrolyte to accumulate and solidify into gel at the connection between the channel and the tube during the gel circulation process, clogging the pipe and significantly reducing the gel circulation flow rate, thus affecting the battery's gel circulation performance. In the aforementioned gel circulation connector, the return tube channel adopts a frustum design, with the return tube body vertically and integrally connected at its top, ensuring smooth return of the colloidal electrolyte and preventing gel blockage. The inlet tube channel and the inlet tube body are integrally and vertically connected through the return tube channel, preventing gel accumulation when the colloidal electrolyte enters and ensuring the return effect is not affected.
[0011] In step S2, the discharge process is as follows: the battery is discharged at a current of 0.1C5 for 20-40 minutes, and further, gel cycling is carried out within 10 minutes after discharge.
[0012] Discharging before gel cycling is to reduce the concentration of sulfuric acid electrolyte in the battery electrode group. During gel cycling, after the gel electrolyte enters the battery, it easily diffuses into the electrode group due to the concentration difference, thus improving the cycling effect. Gel cycling is carried out within 10 minutes after discharge because after the battery has been sitting for a long time, the electrolyte concentration inside and outside the electrode group tends to be uniform due to diffusion, which is not conducive to the diffusion of gel electrolyte. Gel cycling within 10 minutes after discharge is beneficial to improving the cycling effect of gel cycling.
[0013] In step S3, the acid content m of a single battery cell is known. 电池Given the minimum number of batteries (1) and the maximum number of batteries (n) required for recycling, the required mass of colloidal electrolyte (m) to be added to the system is calculated. 系统 The mass m of fumed silica 二氧化硅 The colloidal electrolyte is prepared by mixing fumed silica and sulfuric acid solution, with the sulfuric acid solution having a mass fraction of 36.8%-37.4% and the colloidal electrolyte having a solid content of 5wt.%-5.5wt.%, as shown in the calculation formula below: ; In the formula: m 二氧化硅 - Mass of fumed silica in the system before cycling, in kg. m 系统 - Total amount of colloidal electrolyte in the system before circulation, in kg. m 电池 - Acid content in the battery before cycle, in kg. n - The maximum number of batteries that need to be cycled, in units (batteries).
[0014] Preferably, the cycle results obtained using this calculation method meet the product design requirements, and subsequent cycles with different battery numbers do not require repeated calculations. It is only necessary to first calculate the fumed silica content in the system after the cycle based on the calculation formula, then add fumed SiO2 to adjust the fumed silica content back to the level before the cycle. The calculation formula for the fumed silica content ω1 in the system before the cycle is shown below: ; The formula for calculating the content ω2 of fumed silica in the system after circulation is: .
[0015] In step S3, the flow rate of the adhesive circulation process is 130L / h-160L / h, and the circulation time is 2.5h-3.5h.
[0016] In step S4, the constant current charging current is 0.07C5 (A), and the charging time is 0.5h-1h.
[0017] The reason for performing low-current constant-current charging in step S4 is that after gel cycling in step S3, the gel electrolyte in the battery undergoes gelation, which hinders further gel cycling. Under the action of the electric field, the three-dimensional structure of the gelled colloid is broken down and thinned, and then the gel electrolyte is reformed, allowing gel cycling to proceed further and improving the cycling effect. At the same time, the low-current constant-current charging time should not be too long, otherwise the temperature of the gel electrolyte will rise, and the gel will block the pipeline in the gel cycling pipeline.
[0018] In step S4, the specific process of battery electrolyte extraction and constant voltage charging is as follows: After the battery is removed from the gel circulation pipe, the gel electrolyte is extracted 2cm-3cm away from the injection port. Then, the battery is charged at a constant voltage of 2.45V-2.55V and a current limit of 0.1C5 (A) for 2h-3h.
[0019] The purpose of constant voltage and current limiting charging in step S4 is to improve the uniformity of the overall gel electrolyte inside the battery under the action of the electric field force, and to ensure that the battery is fully charged evenly. The reason why constant current charging is not used in this step is that a large number of bubbles will be generated at the end of constant current charging, which will affect the stability of the gel inside the battery.
[0020] Compared with the prior art, the present invention has the following beneficial effects: The gel lead-acid battery processing technology of this invention replaces vacuum gel tank and acid removal treatment with gel circulation. The operation process is simple and controllable, with a short production cycle and low cost. The prepared gel lead-acid battery has a uniform and stable gel electrolyte and excellent initial performance, meeting the needs of mass production. Secondly, by controlling the mass fraction of sulfuric acid, circulation parameters, and the design of a special gel circulation connector during the gel lead-acid battery processing, combined with low-current constant current charging and constant-voltage current-limiting charging, gel gel blockage is avoided, ensuring uniform and stable gel electrolyte and excellent and consistent initial battery performance. Attached Figure Description
[0021] Figure 1 This is a schematic cross-sectional view of the adhesive circulation connector described in this invention; Figure 2 This is a side view of the adhesive circulation connector described in this invention.
[0022] In the diagram: 1. Main body; 2. Inlet hose body; 3. Return hose body; 4. Inlet hose channel; 5. Return hose channel; 6. Sealing ring. Detailed Implementation
[0023] The present invention will be further described below with reference to the embodiments and comparative examples. Unless otherwise specified, the raw materials used in the embodiments and comparative examples are all conventional commercial raw materials, and the process methods used are all conventional methods in the art unless otherwise specified. The following embodiments and comparative examples use workshop PZV series batteries and manufacture test batteries according to the process described in the embodiments and comparative examples.
[0024] like Figures 1-2As shown, unless otherwise specified, the adhesive circulation connector structure used in the following embodiments and comparative examples is as follows: The adhesive circulation connector includes a main body 1, which consists of a return tube channel 5, an inlet tube channel 4, an inlet tube body 2, and a return tube body 3. The return tube channel 5 adopts a frustum design. The inlet tube channel 4 vertically penetrates the return tube channel 5. The inlet tube body 2 and the return tube body 3 are integrally vertically connected at the top of the inlet tube channel 4 and the return tube channel 5, respectively. A sealing ring 6 is also provided at the lower part of the main body 1 to ensure the airtightness of the system when the adhesive circulation connector is in use.
[0025] Example 1 This embodiment uses the 5-PZV-350 battery as the implementation object. The battery acid capacity is 4.3L, and the minimum number of batteries to be cycled is 1, and the maximum number is 30. The specific processing technology of this battery model includes the following steps: S1 Battery Acid Cycling Formation: The 5-PZV-350 battery is subjected to routine acid cycling formation in the workshop. At the end of the acid cycling formation, the mass fraction of sulfuric acid in the battery is adjusted to 36.8%, and an industrial fan is used to cool it down for 1 hour to reduce the temperature of sulfuric acid in the battery to 30°C. S2 pre-cycle discharge: After cooling, the battery is transported to the glue cycle system area to install the glue cycle connector and connect the circuit to discharge at a current of 0.1C5 for 20 minutes. After discharge, the battery is subjected to glue cycle within 10 minutes. S3 Battery Gel Cycling: Add 88.3 kg of fumed SiO2 and 1512 kg of 36.8 wt.% H2SO4 solution to the gel cycling system to prepare the gel electrolyte. (The solid content of the gel electrolyte in the system before cycling, i.e., the fumed silica content ω1 in the system before cycling, is 5.5 wt.%. When cycling subsequent batches, simply adjust the solid content of the gel electrolyte in the system back to 5.5 wt.%). After S2, start the gel cycling system to cycle the battery. The circulation flow rate during the gel cycling process is 130 L / h, and the cycling time is 2.5 h. S4 Battery Charging: At the end of the gel cycle, start the charger to carry out constant current charging while continuing the gel cycle. The constant current charging current is 0.07C5 (A), and the charging time is 0.5h. After the charging is completed, stop the gel cycle. After the battery is removed from the gel cycle pipeline, extract the gel electrolyte 2cm away from the injection port, and carry out constant voltage charging of 2.5V±0.05V and current limiting of 0.1C5 (A) for a single battery for 2h to obtain a gel lead-acid battery. Initial performance tests were conducted on the processed batteries. They were discharged for 5 hours according to the requirements of GB / T 7403.1-2018 standard, with a discharge cutoff voltage of 1.7V. The initial discharge capacity of the battery was measured to be 102.5% of the rated capacity, which met the process standard requirements.
[0026] Example 2 This embodiment uses a 6-PZV-420 battery as the implementation object. The battery acid capacity is 5.2L, and the minimum number of batteries to be cycled is 1, and the maximum number is 30. The specific processing technology of this battery model includes the following steps: S1 Battery Acid Cycling Formation: The 6-PZV-420 battery is subjected to routine acid cycling formation in the workshop. At the end of the acid cycling formation, the mass fraction of sulfuric acid in the battery is adjusted to 37.4%, and the battery is cooled by an industrial fan for 2 hours to reduce the temperature of sulfuric acid in the battery to 22°C. S2 pre-cycle discharge: After cooling, the battery is transported to the glue cycle system area to install the glue cycle connector and connect the circuit to discharge at a current of 0.1C5 for 40 minutes. After discharge, the battery is glue cycled within 10 minutes. S3 Battery Gel Cycling: Add 110kg of fumed SiO2 and 1890kg of 37.4wt.% H2SO4 solution to the gel cycling system to prepare the gel electrolyte. After S2, start the gel cycling system to cycle the battery. The circulation flow rate is 160L / h and the circulation time is 3.5h. S4 Battery Charging: At the end of the gel cycle, start the charger to carry out constant current charging while continuing the gel cycle. The constant current charging current is 0.07C5 (A), and the charging time is 1 hour. After the charging is completed, stop the gel cycle. After the battery is removed from the gel cycle pipeline, extract the gel electrolyte 3cm away from the injection port, and carry out constant voltage charging of 2.5V±0.05V and current limiting of 0.1C5 (A) for a single battery for 3 hours to obtain a gel lead-acid battery.
[0027] Initial performance tests were conducted on the processed batteries. They were discharged for 5 hours according to the requirements of GB / T 7403.1-2018 standard, with a discharge cutoff voltage of 1.7V. The measured initial discharge capacity of the battery was 101.7% of the rated capacity, which met the process standard requirements.
[0028] Example 3 This embodiment uses the 5-PZV-350 battery as the implementation object. The battery acid capacity is 5.2L, and the minimum number of batteries to be cycled is 1, and the maximum number is 30. The specific processing technology of this battery model includes the following steps: S1 Battery Acid Cycling Formation: The 5-PZV-350 battery is subjected to routine acid cycling formation in the workshop. At the end of the acid cycling formation, the mass fraction of sulfuric acid in the battery is adjusted to 37%, and an industrial fan is used to cool it down for 1.5 hours to reduce the temperature of sulfuric acid in the battery to 25°C. S2 pre-cycle discharge: After cooling, the battery is transported to the glue cycle system area to install the glue cycle connector and connect the circuit to discharge at a current of 0.1C5 for 30 minutes. After discharge, the battery is subjected to glue cycle within 10 minutes. S3 Battery Gel Cycling: 71.6 kg of fumed SiO2 and 1228 kg of 37 wt.% H2SO4 solution were added to the gel cycling system to prepare a gel electrolyte. After S2, the gel cycling system was started to cycle the battery. The circulation flow rate was 140 L / h and the circulation time was 3 h. S4 Battery Charging: At the end of the gel cycle, start the charger to carry out constant current charging while continuing the gel cycle. The constant current charging current is 0.07C5 (A), and the charging time is 45 minutes. After charging is completed, stop the gel cycle. After the battery is removed from the gel cycle pipeline, extract the gel electrolyte 2.5cm away from the injection port, and carry out constant voltage charging of 2.5V±0.05V and current limiting of 0.1C5 (A) for a single battery for 2.5 hours to obtain a gel lead-acid battery.
[0029] Initial performance testing was conducted on the processed batteries. They were discharged for 5 hours according to the requirements of GB / T 7403.1-2018 standard, with a discharge cutoff voltage of 1.7V. The measured initial discharge capacity of the battery was 103.1% of the rated capacity, which met the process standard requirements.
[0030] Comparative Example 1 This comparative example uses a 6-PZV-420 battery as the implementation object. The processing technology of this battery is the same as that of Example 2, except that the constant current discharge is not used in step S2.
[0031] Comparative Example 2 This comparative example uses a 6-PZV-420 battery as the implementation object. Except for step S2, which uses a conventional acid cycle connector, the processing technology of this battery is the same as that of Example 2. During step S3, the gel electrolyte partially clogs the tube at the angle between the inlet and outlet acid tube and the channel of the conventional acid cycle connector, causing the gel circulation flow rate to drop frequently.
[0032] Comparative Example 3 This comparative example uses a 6-PZV-420 battery as the implementation object. The processing technology of this battery is the same as that of Example 2, except that the circulation flow rate of the gel circulation process in step S3 is 100L / h. During step S3, the battery repeatedly experienced gel blockage and flow interruption of the gel electrolyte, indicating that the circulation flow rate is too small and not suitable for gel circulation.
[0033] Comparative Example 4 This comparative example uses a 6-PZV-420 battery as the implementation object. The processing technology of this battery is the same as that of Example 2, except that constant current charging is not used in step S4.
[0034] The batteries in the above embodiments and comparative examples underwent initial performance testing. They were discharged for 5 hours according to the requirements of GB / T 7403.1-2018 standard, and the initial discharge capacity is shown in Table 1 below. After the batteries completed the initial performance testing, they were left to stand for 24 hours. They were then dissected and sampled according to GB / T 42391-2023 standard, and the solid content of the colloidal electrolyte in the upper, middle and lower parts of the electrode group was tested. The test results are shown in Table 2 below.
[0035] Table 1. Initial Capacity Results of Comparative Examples
[0036] Table 2. Solid content detection results of the comparative examples in the embodiments.
[0037] By comparing Tables 1 and 2, and comparing Example 2 with Comparative Example 1, it can be seen that in step S2, no discharge is performed and the gel is directly cycled. As a result, after the gel electrolyte enters the battery during the gel cycle, the sulfuric acid concentration inside and outside the electrode group is the same, and the gel electrolyte is difficult to diffuse. Consequently, after the gel cycle is completed, the solid content of the gel electrolyte does not meet the standard, the upper and lower parts are uneven, and the initial discharge capacity is not as good as that of Example 2.
[0038] A comparison of Example 2 and Comparative Example 2 shows that step S2 uses a conventional acid circulation connector for gel circulation, which causes some gel to block the tube at the angle between the inlet and outlet acid tube and the channel of the conventional acid circulation connector. This results in frequent drops in gel circulation flow, uneven distribution of the gel electrolyte in the upper and lower parts, non-compliance with solid content standards, and failure to meet the initial discharge capacity standards.
[0039] A comparison of Example 2 and Comparative Example 3 shows that the circulation flow rate of the gel in step S3 is 100 L / h. The battery experienced multiple instances of gel blockage and flow interruption during step S3, indicating that the circulation flow rate is too small and not suitable for gel circulation. In this comparative example, the gel electrolyte is uneven in the upper and lower parts, the solid content does not meet the standard, and the initial discharge capacity does not meet the standard.
[0040] A comparison of Example 2 and Comparative Example 4 shows that when constant current charging is not used at the end of the gel cycle in step S4, the gel electrolyte in the battery exhibits gelation, which hinders further gel cycle of the battery. Consequently, after the gel cycle is completed, the solid content of the gel electrolyte does not meet the standard, the upper and lower parts are uneven, and the initial discharge capacity is less than that of Example 2.
[0041] The comparison between the above embodiments and comparative examples shows that the batteries manufactured by the processing technology of the embodiments have excellent performance, the colloid is stable and uniform, and the initial performance of the batteries can meet the standard requirements.
Claims
1. A processing technology for gel lead-acid batteries, characterized in that, Includes the following steps: S1 Battery Acid Cycle Formation: After the battery completes acid cycle formation in the workshop, it is cooled down; S2 pre-cycle discharge: After cooling, the battery is transported to the glue cycle system area to install the glue cycle connector and connect the circuit for discharge. After discharge, the battery begins glue cycle. S3 Battery Adhesive Cycling: Add gaseous SiO2 and H2SO4 solution to the adhesive cycling system. After S2 is completed, start the adhesive cycling system to carry out adhesive cycling. S4 Battery Charging: At the end of the gel cycle, the battery is charged with constant current. After charging is completed, the gel cycle is stopped, the circulation pipe is removed, the battery is drained, and then charged with constant voltage.
2. The processing technology for colloidal lead-acid batteries according to claim 1, characterized in that, In step S1, after acid cycling formation, the mass fraction of sulfuric acid in the battery is 36.8%-37.4%, and the temperature is reduced to 20-30℃ in 1-2 hours.
3. The processing technology for colloidal lead-acid batteries according to claim 1, characterized in that, In step S2, the glue circulation connector includes a main body (1), which is composed of a return glue tube channel (5), an inlet glue tube channel (4), an inlet glue tube body (2) and a return glue tube body (3). The return glue tube channel (5) adopts a frustum design. The inlet glue tube channel (4) vertically penetrates the return glue tube channel (5). The inlet glue tube body (2) and the return glue tube body (3) are vertically connected at the top of the inlet glue tube channel (4) and the return glue tube channel (5), respectively. A sealing ring (6) is also provided at the bottom of the main body (1).
4. The processing technology for colloidal lead-acid batteries according to claim 1, characterized in that, In step S2, the discharge process is as follows: the battery is discharged at a current of 0.1C5 for 20-40 minutes, and gel cycling is carried out within 10 minutes after discharge.
5. The processing technology for colloidal lead-acid batteries according to claim 1, characterized in that, In step S3, given the known acid content m of a single cell... 电池 Given the minimum number of batteries (1) and the maximum number of batteries (n) required for recycling, the required mass of colloidal electrolyte (m) to be added to the system is calculated. 系统 The mass m of fumed silica 二氧化硅 The colloidal electrolyte is prepared by mixing fumed silica and sulfuric acid solution, with the sulfuric acid solution having a mass fraction of 36.8%-37.4%. After cycling, the solid content of the colloidal electrolyte is 5wt.%-5.5wt.%, as calculated below: 。 6. The processing technology for colloidal lead-acid batteries according to claim 1, characterized in that, In step S3, during the glue circulation process, the circulation flow rate is 130L / h-160L / h, and the circulation time is 2.5h-3.5h.
7. The processing technology for colloidal lead-acid batteries according to claim 1, characterized in that, In step S4, the constant current charging current is 0.07C5 (A), and the charging time is 0.5h-1h.
8. The processing technology for colloidal lead-acid batteries according to claim 1, characterized in that, In step S4, the specific process of battery electrolyte extraction and constant voltage charging is as follows: After the battery is removed from the gel circulation pipe, the gel electrolyte is extracted 2cm-3cm away from the injection port. Then, the battery is charged at a constant voltage of 2.45V-2.55V and a current limit of 0.1C5 (A) for 2h-3h.