A method for repairing lead-acid batteries using a cascade utilization battery activation liquid

Abstract

The application belongs to the technical field of battery repair, and particularly relates to a storage battery activation liquid for gradient utilization, which is characterized by being compounded by a carbon material, an active agent solution and a sulfuric acid solution; the application further discloses a method for repairing a lead-acid storage battery; the application has the beneficial effects of simple formula, simple operation, improved battery use efficiency, inhibited hydrogen evolution, refined metal lead particles, refined anode lead oxide particles, improved battery charging and discharging rate, improved utilization rate of active substances, improved battery capacity, high reliability and the like.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of battery repair, and particularly relates to a stepwise utilization battery activating liquid and a method for repairing lead-acid batteries. BACKGROUND

[0002] Waste batteries are listed in the National Hazardous Waste List published by the State Environmental Protection Department and the National Development and Reform Commission. The design service life of these batteries is 8-10 years, while the actual service life of the batteries under the conditions of a substation is generally 3-4 years. According to the above incomplete statistical data, about 7 million retired batteries are generated in the country every year on average, which also means that at least 7 million new batteries need to be purchased every year, and the cost is huge. In fact, a considerable part of the retired batteries has a capacity of more than 40%, which has the value of repair and stepwise utilization. In addition, a large number of waste lead-acid batteries retired from substations will cause serious safety and environmental pollution hazards if not properly stored and treated. For example, the residual part of the battery capacity may cause an explosion; the heavy metal components such as lead, antimony, arsenic and tin in the grid and electrode may cause environmental, air and soil pollution, and cause human poisoning hazards.

[0003] Since the actual service life of the lead-acid batteries in substations is less than half of the design life, except for about 20% of the waste lead-acid batteries that cannot be restored due to physical damage, most of them have the possibility of effective restoration and reuse. Taking the example of only 20% (7.4 million single batteries per year) being repaired and reused, even if the life is only extended by 1 year, millions of new battery costs can be saved every year, and the direct economic benefits are significant; the extension of the service life of the battery also means that the generation of waste is reduced, the energy consumption and pollutant emissions of the lead regeneration and battery production process are reduced, and significant social, economic and environmental benefits are achieved. In addition, the research on the safe collection and storage technical conditions of waste lead-acid batteries in substations will also reduce the environmental risks caused by waste lead-acid batteries in the process of storage, repair, recombination, etc.

[0004] In the prior art, CN111725557A discloses an activation method for a lithium manganese oxide battery. The positive electrode active material of the lithium manganese oxide battery is lithium manganese oxide, and the chemical formula of the lithium manganese oxide is LiMn1-xNixO2, where x = 0-0.1. The electrolyte of the lithium manganese oxide battery contains vinylene carbonate and 1,4-butanesulfonate lactone, wherein the volume ratio of vinylene carbonate to 1,4-butanesulfonate lactone is 1:2. The activation method includes: 1) adjusting the battery voltage to the storage voltage, storing for a predetermined time, and measuring the open-circuit voltage of the lithium manganese oxide battery; 2) comparing the open-circuit voltage with a first predetermined voltage. If the open-circuit voltage is lower than the first predetermined voltage, proceed to step 3; otherwise, proceed to step 4, where the first predetermined voltage is lower than the storage voltage; 3) 1) Charge the battery at a constant current of no more than 0.02C to the second predetermined voltage, and charge it at a constant voltage of the second predetermined voltage until the charging current drops to the charging cutoff current and the second predetermined voltage is higher than the charging cutoff voltage; discharge the battery at a constant current to the first predetermined voltage; 2) Charge the battery at a constant current of no more than 0.02C to the charging cutoff voltage; charge it at a constant voltage of the charging cutoff voltage until the charging current drops to the charging cutoff current; 3) Adjust the battery temperature to above 50 degrees Celsius and charge it at a constant voltage of the charging cutoff voltage until the charging current drops to the charging cutoff current; 4) Adjust the battery temperature to room temperature and discharge it at a constant current to the first predetermined voltage; 5) Perform a constant current charge-discharge cycle between the first predetermined voltage and the storage voltage several times; 6) Perform a constant current charge-discharge cycle between the charging cutoff voltage and the discharging cutoff voltage several times.

[0005] The aforementioned existing technology has the following drawbacks: the activation method is relatively complex and inconvenient to operate.

[0006] For example, CN102013534B discloses a capacity activating fluid for valve-regulated lead-acid batteries based on positive electrode protection, characterized in that it is composed of the following raw materials in weight percentage: sodium sulfate 2-5%; potassium sulfate 2-4%; aluminum sulfate 0.2-0.5%; sodium bicarbonate 1-3%; ammonium sulfate 1-2%; phosphoric acid 0.5-2%; sodium pyrophosphate 1-1.5%; citric acid 0.05-0.15%; disodium ethylenediaminetetraacetate 0.2-0.4%; and deionized water as the balance.

[0007] The aforementioned existing technologies have the following drawbacks: they are relatively complex in composition and relatively expensive. Summary of the Invention

[0008] To address the aforementioned problems, the present invention aims to disclose a battery activator for cascade utilization and a method for repairing lead-acid batteries, which is achieved through the following technical solution.

[0009] A battery activator for cascaded use is characterized by being a compound of carbon materials, an activator solution, and a sulfuric acid solution.

[0010] The battery activation liquid for cascade utilization, according to the above-mentioned, characterized in that the carbon material is acidified acetylene black or acidified carbon nanotube or electrodeposited carbon powder, and the mass concentration of the carbon material is 1.0 g / L.

[0011] The battery activation liquid for cascade utilization, according to the above-mentioned, characterized in that the active agent is sodium dodecyl sulfate (SDS) solution or cetyltrimethylammonium bromide (CTAB) solution or polyvinyl alcohol (PVA) solution.

[0012] The battery activation liquid for cascade utilization, according to the above-mentioned, characterized in that the mass concentration of the active agent solution is 0.1-0.5 g / L.

[0013] The battery activation liquid for cascade utilization, according to the above-mentioned, characterized in that when the active agent is sodium dodecyl sulfate (SDS) solution, the mass concentration of the sodium dodecyl sulfate (SDS) solution is 0.1 g / L.

[0014] The battery activation liquid for cascade utilization, according to the above-mentioned, characterized in that the molar concentration of the sulfuric acid solution is 5 mol / L.

[0015] A method for repairing lead-acid batteries, characterized in that the battery activation liquid for cascade utilization is used, comprising the following steps:

[0016] Step 10: Open the upper cover plate and safety valve of the battery, and use an endoscope to check whether there is water loss in the battery. If there is water loss, add a certain amount of deionized water, and the liquid level of the deionized water should not exceed the diaphragm. After standing for 6-10 hours, extract the excess flowing liquid, and ensure that the diaphragm is fully wetted, but there is no flowing liquid.

[0017] Step 20: First, use 0.05C constant current charging for 2h, then use 0.1C constant current charging for 2h, and stand for 0.5h; then use 0.10C constant current charging for 7h, stand for 0.5h; then use 0.08C constant current charging for 3h, stand for 1h; then use 0.05C constant current charging for 3h, stand for 0.5h; finally, use 0.03C constant current charging for 5h;

[0018] Step 30: Add a certain amount of battery activation liquid, and do not discharge the battery. Use 0.15C current overcharging for 3h, and extract the battery as a poor liquid type. Add battery activation liquid again, and use 0.1C current overcharging for 2h, and extract the battery as a poor liquid type. Add battery activation liquid again, and use 0.05C current overcharging for 1h, during which the free electrolyte is extracted to a poor liquid state, and then stop, and then discharge.

[0019] Step 40: After the end of discharging, the constant current and constant voltage mode of multiple charging and discharging is carried out according to step 20, and the battery capacity is calibrated and the self-discharge test is carried out, and the capacity and self-discharge rate requirements are the same as the charging process in step 30.

[0020] Step 50: After multiple charging and discharging, when the battery capacity recovers to more than 90% of the rated capacity, the charging and discharging is ended, and after 2-4h of complete charging and static, the excess flowing liquid is extracted, the diaphragm is fully wetted but without flowing liquid, and then 0.1C is used for a charging and discharging, the battery capacity is calibrated, and the battery is fully charged and stored.

[0021] Step 60: The battery is repaired to meet the recycling requirements, and the battery air hole cover is reset and fixed.

[0022] The method for repairing the lead-acid storage battery described above, characterized in that if the storage battery has a heating phenomenon, the battery needs to be placed in a circulating cooling water bath for heat dissipation and charging.

[0023] The method for repairing the lead-acid storage battery described above, characterized in that the temperature of the electrolyte in the storage battery does not exceed 40℃.

[0024] The method for repairing the lead-acid storage battery described above, characterized in that the deionized water is added at 90-130mL per 100Ah of battery capacity.

[0025] The method for repairing the lead-acid storage battery described above, characterized in that the storage battery activating liquid is added at 5-10mL per 100Ah of battery capacity.

[0026] Therefore, the present application has the beneficial effects of simple formula, easy operation, improved battery use efficiency, inhibited hydrogen evolution, refined lead particles, refined anode lead oxide particles, improved charging and discharging rate of the battery, improved utilization rate of active material, improved battery capacity, and high reliability. BRIEF DESCRIPTION OF DRAWINGS

[0027] Fig. 1 is a comparison chart of acetylene black in the active agent solution in the present application after standing for 40min after ultrasonic treatment.

[0028] Fig. 2 is a comparison chart of carbon nanotubes in the active agent solution in the present application after standing for 40min after ultrasonic treatment.

[0029] Fig. 3 is a comparison chart of electrodeposited carbon powder in the active agent solution in the present application after standing for 40min after ultrasonic treatment.

[0030] Fig. 4 is a comparison chart of acetylene black in the active agent solution in the present application after standing for 170h.

[0031] Fig. 5 is the contrast chart of carbon nanotube in the active agent solution in the application after 170 hours of standing.

[0032] Fig. 6 is the contrast chart of the electrodeposited carbon powder in the active agent solution in the application after 170 hours of standing.

[0033] In the figure: left, middle, right are SDS solution, CTAB solution, PVA solution. DETAILED DESCRIPTION

[0034] The application will be further described in detail below in combination with the drawings and specific embodiments.

[0035] A battery activation liquid for cascade utilization, characterized in that it is compounded by a carbon material, an active agent solution and a sulfuric acid solution, the carbon material is acidified acetylene black or acidified carbon nanotube or electrodeposited carbon powder, the mass concentration of the carbon material is 1.0 g / L, the active agent is sodium dodecyl sulfate (SDS) solution or cetyltrimethylammonium bromide (CTAB) solution or polyvinyl alcohol (PVA) solution, the mass concentration of the active agent solution is 0.1-0.5 g / L, and the molar concentration of the sulfuric acid solution is 5 mol / L.

[0036] The acidification treatment method of the acidified acetylene black or acidified carbon nanotube is: taking acetylene black or carbon nanotube, ultrasonic treatment with concentrated nitric acid at a ratio of 1 ml:1.25 ml for 1 h, then stirring treatment at 140 DEG C for 1.5 h, after the device is cooled, the suspension is diluted and used for suction filtration with a microporous filter membrane until the filtrate is neutral, and the filtered product is dried and ground to obtain the acidified acetylene black or carbon nanotube;

[0037] The applicant has made the following test on the battery activation liquid: three portions of 5 mg acetylene black, three portions of 5 mg carbon nanotube and three portions of 5 mg electrodeposited carbon powder dispersed in aqueous solution are added into three groups of 5 ml active agent solution respectively after ultrasonic treatment for 40 min and standing, the first group of active agent solution: SDS with a mass concentration of 0.1 g / L, CTAB with a mass concentration of 0.1 g / L, PVA with a mass concentration of 0.1 g / L, the second group of active agent solution: SDS with a mass concentration of 0.25 g / L, CTAB with a mass concentration of 0.25 g / L, PVA with a mass concentration of 0.25 g / L, and the third group of active agent solution: SDS with a mass concentration of 0.5 g / L, CTAB with a mass concentration of 0.5 g / L, PVA with a mass concentration of 0.5 g / L.

[0038] As Figs. 1 to 3After ultrasonic treatment, carbon nanotubes in all CTAB solutions were observed to settle quickly, and the dispersion in the 0.25 g / L CTAB solution was relatively good, indicating that this mass concentration was more conducive to the suspension of carbon nanotubes. The situation of electrodeposited carbon powder was the same, and all CTAB solutions settled quickly, and the dispersion in the 0.25 g / L CTAB solution was relatively good. Except for these two cases, the dispersion of carbon materials in other dispersants was good.

[0039] As Figs. 4 to 5 After 170 hours (one week): acetylene black settled in the 0.5 g / L SDS solution, all CTAB solutions and PVA solutions, and settled severely in the 0.1 g / L CTAB solution, and only a small amount or even slightly settled in the rest. The dispersion of acetylene black in the 0.1 g / L SDS solution and the 0.25 g / L SDS solution was still good;

[0040] Carbon nanotubes were well dispersed in all concentrations of SDS solution and PVA solution, and settled severely in CTAB;

[0041] Electrodeposited carbon powder settled significantly in all concentrations of active agent.

[0042] Test conclusion: the settlement in the SDS solution was better, and the dispersion in the 0.1 g / L SDS solution was relatively most stable.

[0043] A method for repairing lead-acid storage batteries, characterized in that a storage battery activating liquid for step-by-step utilization is used, comprising the following steps:

[0044] Step 10: open the upper cover plate and safety valve of the battery, use an endoscope to check whether the battery has a water loss phenomenon, if there is a water loss phenomenon, add a certain amount of deionized water (in general, 90-130 mL is added per single cell with a capacity of 100 Ah), after adding water, check again to ensure that the liquid level does not exceed the diaphragm, and then stand for 6-10 hours to extract the excess flowing liquid, and ensure that the diaphragm is fully wet but there is no flowing liquid.

[0045] Step 20: first use 0.05C constant current charging for 2h, then use 0.1C constant current charging for 2h, stand for 0.5h; then use 0.10C constant current charging for 7h, stand for 0.5h; then use 0.08C constant current charging for 3h, stand for 1h; then use 0.05C constant current charging for 3h, stand for 0.5h; finally use 0.03C constant current charging for 5h;

[0046] Step 30: Add a certain amount of battery activating liquid (5-10 mL of battery activating liquid per 100 Ah battery), do not discharge the battery, directly overcharge for 3 h using 0.15C current, and extract the liquid in a poor state while the battery is electrified; then add the battery activating liquid according to the above method, and overcharge for 2 h using 0.1C current, and extract the liquid in a poor state while the battery is electrified; then add the battery activating liquid, and overcharge for 1 h using 0.05C current (during which the free electrolyte is extracted to a poor state), stop, and then discharge;

[0047] Step 40: After the end of the discharge, perform multiple charging and discharging in a constant current and constant voltage mode according to step 20, calibrate the battery capacity, and perform self-discharge testing, and the capacity and self-discharge rate are required to be the same as in the charging process in step 30.

[0048] Step 50: When the battery capacity is restored to more than 90% of the rated capacity after multiple charging and discharging, end the charging and discharging, extract the excess flowing liquid after 2-4 h of complete charging and static state, ensure that the separator is fully wet but there is no flowing liquid, and then perform a charging and discharging using 0.1C to calibrate the battery capacity, and store the battery after full charging.

[0049] Step 60: For the batteries that meet the requirements for reuse after repair, reset and fix the battery air hole cover.

[0050] During the charging and activating process, if the battery generates heat, the battery needs to be placed in a circulating water bath for cooling and charging, so that the temperature of the electrolyte in the battery does not exceed 40℃.

[0051] The technician prepared 24 groups of batteries to be activated, and activated and repaired the 24 groups of batteries, with the following results:

[0052]

[0053] Conclusion: All batteries have been greatly improved after activation, and the test is qualified.

[0054] The technology has obtained certain popularization and application experience in the scenes of temporary power supply, square temporary power supply, rural irrigation, and rural government temporary power supply, effectively proving the reliability of the technology.

[0055] In the present application, the activating liquid formula only has three materials, the formula is simple, the relative cost is low, and the solution is simple to prepare.

[0056] In the present application, the activating liquid is stable in dispersion and can be stored for a long time. When precipitation occurs, it can be used again by shaking, and will not deteriorate.

[0057] In the present application, the activating method is simple and easy to learn, and is convenient to operate.

[0058] In the application, the activation repair solution reduces the crystallization rate of lead sulfate, promotes the formation of fine lead sulfate grains, slows down the sulfatation rate, and improves the service life of the battery.

[0059] In the application, the functional groups adsorbed on the surface of the activation repair agent have a significant effect on inhibiting hydrogen evolution and refining metal lead particles, and also have an effect on refining lead oxide particles of the anode;

[0060] In the application, the addition of a certain concentration of carbon material can increase the electrical conductivity between active material particles, improve the pore structure of the electrode reaction layer, and improve the utilization rate of active materials;

[0061] In the application, the activated power storage device has obtained certain popularization and application experience in the scenes of temporary power supply in test classes, temporary power supply in squares, rural irrigation, and temporary power supply in rural government light fields, effectively proving the reliability of the technology.

[0062] The application can prolong the service life of the battery, reuse the originally discarded battery, save the use cost, and reduce the heavy metal pollution of the discarded battery.

[0063] The application can be used in the case where the battery is seriously sulfated.

Claims

1. A method for repairing lead-acid batteries, employing a recycled battery activating solution, wherein the recycled battery activating solution is composed of carbon material, an activator solution, and a sulfuric acid solution; the carbon material is acidified acetylene black, acidified carbon nanotubes, or electrodeposited carbon powder, with a carbon material mass concentration of 1.0 g / L; the activator solution is sodium dodecyl sulfate solution, hexadecyltrimethylammonium bromide solution, or polyvinyl alcohol solution, with an activator solution mass concentration of 0.1–0.5 g / L; the sulfuric acid solution has a molar concentration of 5 mol / L; characterized in that: The method for repairing a lead-acid battery includes the following steps: Step 10: Open the battery's top cover and safety valve, and use an endoscope to check if the battery has lost water. If water loss is present, add a certain amount of deionized water, ensuring the deionized water level does not exceed the separator. Let it stand for 6-10 hours, then remove any excess liquid. Step 20: First, charge at a constant current of 0.05C for 2 hours, then charge at a constant current of 0.1C for 2 hours, and let stand for 0.5 hours; then charge at a constant current of 0.10C for 7 hours, and let stand for 0.5 hours; then charge at a constant current of 0.08C for 3 hours, and let stand for 1 hour; then charge at a constant current of 0.05C for 3 hours, and let stand for 0.5 hours; finally, charge at a constant current of 0.03C for 5 hours. Step 30: Add a certain amount of battery activator fluid, without discharging the battery, and overcharge it for 3 hours with a 0.15C current, then drain the electrolyte while it is charged to a lean state; add more battery activator fluid, and overcharge it for 2 hours with a 0.1C current, then drain the electrolyte while it is charged to a lean state; add more battery activator fluid, and overcharge it for 1 hour with a 0.05C current, during which the free electrolyte is drained to a lean state, then stop the overcharge and discharge the battery. Step 40: After the discharge is completed, perform constant current charging and discharging multiple times according to step 30, and calibrate the battery capacity and perform self-discharge test. The capacity and self-discharge rate requirements are the same as those in the discharge process of step 30. Step 50: After multiple charge and discharge cycles, when the battery capacity recovers to more than 90% of the rated capacity, end the charge and discharge cycle. After fully charging and resting for 2-4 hours, remove excess liquid. Then, perform a charge and discharge cycle at 0.1C to calibrate the battery capacity. Finally, fully charge the battery and store it. Step 60: After repairing the battery to meet the reuse requirements, reposition and secure the battery vent cap.

2. The method for repairing a lead-acid battery according to claim 1, characterized in that: If the battery is overheating, it needs to be placed in a circulating cooling water bath to dissipate heat and recharge.

3. The method for repairing a lead-acid battery according to claim 2, characterized in that: The temperature of the electrolyte inside the battery should not exceed 40℃.

4. The method for repairing a lead-acid battery according to claim 3, characterized in that: Add 90-130 mL of deionized water per cell for every 100 Ah of battery capacity; add 5-10 mL of battery activator for every 100 Ah of battery capacity.

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