Method for repairing power return lead-acid storage battery by using zwitter-ion additive

Abstract

The invention provides a method for repairing an electric return lead-acid storage battery by using a zwitter-ion additive, which comprises the following steps of: preparing the zwitter-ion additive with sulfonic acid group and amino group, and compounding the zwitter-ion additive with conductive carbon with acidified surface to prepare repairing liquid; opening an upper cover plate and a safety valve of the battery, adding a certain amount of deionized water, standing, and extracting redundant flowing liquid; after a certain amount of repairing liquid is added, low-current charging is adopted, and electrified pumping is in a barren solution state; the steps are repeated, overcharging is carried out with smaller current, and stopping is carried out; and then the battery air hole cover is reset and fixed again. And finally, testing the repaired battery, and checking the repairing effect. The method can solve the problems that the residual capacity of the returned lead-acid storage battery for electric power is high, and resources are wasted when the lead-acid storage battery is directly subjected to hazardous waste treatment; and meanwhile, the updating frequency of the lead-acid storage battery for power is reduced, and the power operation cost is reduced.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of environmental protection and electrochemical energy storage, and particularly relates to a method for repairing power returned lead-acid storage batteries by using zwitterionic additives. BACKGROUND

[0002] In power systems, lead-acid storage batteries are mainly used in substation / converter station DC power sources, communication power sources, UPS power sources, computer and data centers, power distribution automation terminals, transmission line monitoring terminals, and substation detection terminals, and are responsible for important DC load power supply tasks such as relay protection, automatic devices, automation equipment, circuit breaker tripping and closing mechanisms. When AC power is lost, the charger cannot output DC power, and the battery pack serves as the only DC power source to power the DC load. The failure of the battery in an emergency situation could lead to a major operational accident in the substation. Therefore, the battery pack is the core of the DC power supply system, and its performance and quality are related to the safe and stable operation of power equipment.

[0003] According to incomplete statistics, there are more than hundreds of thousands of substations in China, and the number of single batteries reaches 20 million. With the comprehensive and rapid development of China's power grid construction, the number of newly used single batteries will be very large. About 7 million returned batteries are generated in China every year, 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 returned batteries has a capacity of more than 50%, which has the value of repair and reuse.

[0004] With the country's unprecedented emphasis on environmental protection, achieving coordinated and win-win development of power grid construction and operation and environmental protection is an inevitable trend in the development of the power industry. In the process of accelerating the green and low-carbon transformation of the power system, carrying out efficient repair of returned lead-acid storage batteries is an important way to delay battery retirement, reduce operating costs, and reduce environmental load. In the repair of returned lead-acid storage batteries, some beneficial exploratory work has been carried out at home and abroad. Battery desulfurization repair technology has been developed by Bollegraaf Battery Company in Canada and some enterprises and research institutions in Israel, mainly through methods such as large-current charging, full charging and full discharging repair, shallow cycle large-current charging, adding active agents, pulse repair, and water therapy to eliminate battery plate sulfuration. In China, strategies such as pulse repair and nano carbon repair are mainly used. However, the current repair technology has limited effect on reversing negative sulfation, resulting in insignificant repair effect. SUMMARY

[0005] The present application aims to overcome the defects of the prior art and provides a method for repairing power returned lead-acid batteries by using a zwitterionic additive, a zwitterionic additive is developed and used in the repair of returned lead-acid batteries in combination with acidified conductive carbon. The adsorption effect of the zwitterion can inhibit the sulfation of the lead negative electrode, and the conductive carbon can improve the conductivity between lead sulfate particles and improve the utilization rate of the electrode active material. On the one hand, the present application can solve the problem of high residual capacity of power returned lead-acid batteries, which will cause resource waste if directly put into hazardous waste treatment; on the other hand, the present application can reduce the replacement frequency of power lead-acid batteries and reduce the power operation cost.

[0006] The present application is implemented as follows: The present application provides a method for repairing power returned lead-acid batteries by using a zwitterionic additive, which comprises a zwitterionic nano-activator synthesis process and a returned lead-acid battery repair process. 1) The zwitterionic nano-activator synthesis process comprises the following steps: S11. Dissolve a sultone in ethanol under nitrogen protection; S12. Add an amine to the solution obtained in S11 and stir at 25°C for 12 h; S13. Add diethyl ether to the solution obtained in S12, filter, wash and dry the precipitate to obtain a zwitterionic additive; S14. Take conductive carbon and acid in a round-bottom flask, ultrasonically treat and then heat and stir in a water bath to obtain a suspension; S15. Dilute the suspension obtained in S14, wash by suction filtration until the filtrate is neutral, dry and grind the filtered material to obtain acidified conductive carbon; S16. Configure the acidified conductive carbon and the zwitterionic additive obtained in S13 into a repair solution in a certain proportion; 2) The returned lead-acid battery repair process comprises the following steps: S21. Open the upper cover plate and safety valve of the returned lead-acid battery, add deionized water, the amount of deionized water added is 50-200 mL / 100 Ah, and then extract the excess flowing liquid after standing; S22. Add the repair solution to the power returned lead-acid battery, charge with a small current, and extract as a poor liquid state; S23. Repeat steps S21 and S22 until the repair effect is achieved, and stop operation; S24. Reset the battery air hole cover and fix it.

[0007] Further, the zwitterion is an organic small molecule containing a sulfonic acid group and an amine group.

[0008] Further, the sulfone lactone in S11 is one or more of 1,3-propane sulfone lactone, 1,4-butane sulfone lactone, 2,4-butane sulfone lactone, 1,3-propylene sulfone lactone, tetrafluoroethane sulfone lactone.

[0009] Further, the amine in S12 is one or more of ethylamine, triethylamine, triethanolamine, phenethylamine, propylamine, tri-n-propylamine, iso-propylamine, diisopropylamine.

[0010] Further, the conductive carbon in S14 is one or more of acetylene black, activated carbon, carbon nanotube, graphene, ketchen black, electrodeposited carbon powder.

[0011] Further, the acid in S14 is one or more of hydrochloric acid, nitric acid, perchloric acid.

[0012] Further, the mass ratio of the conductive carbon to the zwitterionic additive in S16 is 1:1 to 10:1.

[0013] Further, the current density during the small current charging is 0.05 to 0.2 C.

[0014] Further, the lead-acid battery includes one or more of substation / conversion station DC power supply, communication power supply, UPS power supply, computer and data center power supply, power distribution automation terminal power supply, power transmission line monitoring terminal power supply, transformer detection terminal power supply, electric bicycle power supply.

[0015] Further, the capacity of the lead-acid battery ranges from 2 to 200 Ah, and the voltage of the battery ranges from 2 to 24 V.

[0016] The present application has the following beneficial effects: 1. The present application develops a zwitterionic additive, and the sulfonic acid group and amine group on the zwitterion can respectively adsorb Pb 2+ cations and SO4 2- anions in the solution, thereby reducing the supersaturation of Pb 2+ to a certain extent. The reduction of supersaturation can inhibit the crystallization and growth of lead sulfate, and avoid the formation of a dense lead sulfate layer on the plate surface. The zwitterion as a nucleating agent can accelerate the crystallization rate, increase the crystallization density, and promote the grain size refinement, thereby inhibiting sulfatization.

[0017] 2. The acidified conductive carbon has good dispersibility in the electrolyte, which can improve the conductivity between lead sulfate particles and improve the utilization rate of electrode active material.

[0018] 3. The present application develops a high-efficiency and low-cost process for repairing returned lead-acid batteries, and the repaired battery can continue to serve in the power system, which has significant economic and environmental benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0020] Figure 1 This is a flow chart of a method for repairing a decommissioned lead-acid battery using a zwitterionic additive according to an embodiment of the present invention; Figure 2 The hydrogen and carbon nuclear magnetic resonance spectra of the zwitterionic additive triethylamine propylsulfonate prepared in Example 1 of the present invention are shown; Figure 3 1 is a Raman spectrum of Ketjen Black before and after acidification in Example 2 of the present invention; Figure 4 IR spectra of graphene before and after acidification in Example 3 of the present invention; Figure 5 The following are scanning electron microscope photos of the negative plate of the lead-acid battery before and after repair in Example 1 of the present invention; Figure 6 The internal resistance distribution diagram of ten groups of lead-acid batteries before and after repair in Example 2 of the present invention; Figure 7 1 and 2 are discharge curves of three groups of lead-acid batteries before and after repair in Example 3 of the present invention. DETAILED DESCRIPTION

[0021] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention. Example

[0022] See also Figure 1 , a method for repairing a power-depleted lead-acid battery using a zwitterionic additive, comprising; 1) Synthesis of nano-activators: S11. Under nitrogen, 1,3-propane sultone was dissolved in ethanol; S12. Add triethylamine to the solution obtained in S11 and stir at 25 °C for 12 h. S13. Diethyl ether was added to the solution obtained in S12, and the precipitate was filtered, washed, and dried to obtain a zwitterionic additive; S14. Take carbon nanotubes and nitric acid in a round-bottom flask, after ultrasonic treatment, water bath heating and stirring treatment; S15. Dilute the suspension obtained in S14, filter and wash until the filtrate is neutral, and then dry and grind the filtered material to obtain acidified carbon nanotubes.

[0023] S16. Configure the acidified conductive carbon and the zwitterionic additive into a repair solution at a mass ratio of 1:1.

[0024] 2) The 2 Ah retired lead-acid battery repair process includes the following steps: S21. Open the upper cover plate and safety valve of the retired lead-acid battery, add 4 mL of deionized water, and then extract the excess flowing liquid after standing; S22. Add a certain amount of repair solution, directly charge at 0.2 C, and extract the poor liquid state under electricity; S23. Repeat steps S21 and S22 until the repair effect is achieved, and stop operation; S24. Reset the battery air hole cover and fix it. Example

[0025] Please refer to Figure 1 A method for repairing power retired lead-acid batteries using a zwitterionic additive, comprising: 1) Synthesis of nano-activating agent: S11. Dissolve 2,4-butane sulfone lactone in ethanol under nitrogen protection; S12. Add ethylamine to the solution obtained in S11 and stir at 25°C for 12 h; S13. Add diethyl ether to the solution obtained in S12, filter, wash and dry the precipitate to obtain a zwitterionic additive; S14. Take Ketjen black and hydrochloric acid in a round-bottom flask, after ultrasonic treatment, water bath heating and stirring treatment; S15. Dilute the suspension obtained in S14, filter and wash until the filtrate is neutral, and then dry and grind the filtered material to obtain acidified Ketjen black.

[0026] S16. Configure the acidified conductive carbon and the zwitterionic additive into a repair solution at a mass ratio of 5:1.

[0027] 2) 100 Ah retired lead-acid battery repair process includes the following steps: S21. Open the upper cover plate and safety valve of the retired lead-acid battery, add 100 mL of deionized water, and then extract the excess flowing liquid after standing; S22. Add a certain amount of repair solution, directly charge at 0.05 C, and extract the poor liquid state under electricity; S23. Repeat steps S21 and S22 until the repair effect is achieved, and stop the operation; S24. Reset the battery vent cap and fix it. Embodiment

[0028] Please refer to Figure 1 A method for repairing a power returned lead-acid battery by using a zwitterionic additive, comprising: 1) Synthesis of nano-activator: S11. Dissolve 1,3-propylene sulfone lactone in ethanol under nitrogen protection; S12. Add isopropylamine to the solution obtained in S11, and stir at 25°C for 12 h; S13. Add diethyl ether to the solution obtained in S12, filter, wash and dry the precipitate to obtain a zwitterionic additive; S14. Take graphene and perchloric acid in a round-bottom flask, and treat by ultrasonic and water bath heating and stirring; S15. Dilute the suspension obtained in S14, wash by suction filtration until the filtrate is neutral, and dry and grind the filtered material to obtain acidified graphene.

[0029] S16. Configure the acidified graphene and the zwitterionic additive into a repair solution according to a mass ratio of 10:1.

[0030] 2) The repair process for a 200 Ah returned lead-acid battery comprises the following steps: S21. Open the upper cover plate and safety valve of the returned lead-acid battery, add 100 mL of deionized water, and then extract the excess flowing liquid after standing; S22. Add a certain amount of repair solution, directly charge at 0.1 C, and extract the poor liquid state under electricity; S23. Repeat steps S21 and S22 until the repair effect is achieved, and stop the operation; S24. Reset the battery vent cap and fix it.

[0031] Figure 2 NMR hydrogen spectrum and carbon spectrum of the zwitterionic additive propyl sulfonic acid triethylamine prepared in Example 1. The characteristic peaks correspond to the correct structure and there are no other impurity peaks, indicating that the product has high purity.

[0032] Figure 3 Raman spectra of the Ketjen black before and after acidification in Example 2. The I D / I GThe increase indicates that the graphitization degree of the acid-treated Ketjen black is reduced, and more structural defects are formed after the surface and edge functional groups are treated.

[0033] Figure 4 The infrared spectra of graphene before and after acidification in Example 3 are shown. The peaks of hydroxyl (-OH) and carbon-oxygen double bond (-C=O) in the acid-treated sample are obviously enhanced, indicating that the acid treatment successfully introduces abundant hydroxyl and carboxyl groups on the surface of graphene.

[0034] Figure 5 The scanning electron microscope photos of the negative plates of lead-acid batteries before and after repair in Example 1 are shown. It can be seen that the negative Pb plate has obvious sulfation phenomenon before repair, and the large particles of PbSO4 formed have a size of 2-10 μm, which is difficult to be reduced in the subsequent charging process. The surface of the negative electrode particles is completely covered with Ketjen black and fluffy lead after repair, and almost no large particles of PbSO4 can be detected, indicating that the sulfation of the negative electrode is effectively inhibited Figure 6 The internal resistance distribution diagrams of ten groups of lead-acid batteries before and after repair in Example 2 are shown. It can be seen that, before repair, the internal resistance of the batteries is distributed in the range of 1-5.6 mΩ, and the average internal resistance is 3.144 mΩ; after repair, the internal resistance is distributed in the range of 0.9-4.6 mΩ, and the average internal resistance is 2.599 mΩ, which is reduced by an average of 17.3%.

[0035] Figure 7 The discharge curves of three groups of lead-acid batteries before and after repair in Example 3 are shown, and the discharge current is 20 A. It can be seen that the capacities of the three groups of batteries are 112.2, 150.4 and 173.2 Ah, and the average working voltages are 1.95, 1.96 and 1.96 V, respectively. After repair, the capacities are 158.5, 174.9 and 193.1 Ah, and the average working voltages are 1.98, 1.98 and 1.97 V, respectively. It can be seen that the capacity of the lead-acid battery after repair is greatly improved, and the working voltage is also slightly improved compared with that before repair.

[0036] The present application develops a kind of zwitterionic additive, which is compounded with conductive carbon after acidification and used in the repair of lead-acid battery returned from transportation.The adsorption effect of zwitterion can inhibit the sulfation of lead negative electrode, and conductive carbon can improve the conductivity between lead sulfate particles and improve the utilization rate of electrode active material.A set of efficient and convenient repair technology for lead-acid battery returned from transportation for electric power is developed, which can greatly improve the performance of battery, prolong the service life of battery, shorten the replacement cycle of battery, and has significant economic and environmental benefits.

[0037] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A method for repairing decommissioned lead-acid batteries using zwitterionic additives, characterized in that: Including the synthesis process of zwitterionic nano-activator and the repair process of returned lead-acid batteries; 1) The synthesis process of the zwitterionic nano-activator comprises the following steps: S11. Under nitrogen, sultone was dissolved in ethanol; S12. Add amine to the solution obtained in S11 and stir at 25 °C for 12 h. S13. Diethyl ether was added to the solution obtained in S12, and the precipitate was filtered, washed, and dried to obtain a zwitterionic additive; S14. Take conductive carbon and acid in a round-bottom flask, ultrasonically heat in a water bath and stir to obtain a suspension; S15 S14 obtained suspension was diluted, filtered and washed until the filtrate was neutral, the filtrate was dried and ground to obtain an acidified conductive carbon; S16. The acidified conductive carbon and the zwitterionic additive obtained in S13 are configured in a certain ratio to form a repair solution; 2) The repair process for returned lead-acid batteries includes the following steps: S21. Open the upper cover and safety valve of the returned lead-acid battery, add deionized water, add deionized water in an amount of 50-200mL / 100Ah, and extract the excess flowing liquid after standing; S22 to the power return lead-acid battery to add the repair liquid, using a small current charging, charged to the lean state; S23 repeat steps S21 and S22 until the repair effect is achieved, stop the operation; S24. Replace the battery vent cover and secure it.

2. The method for repairing a degraded lead-acid battery using a zwitterionic additive as claimed in claim 1, wherein: The zwitterion is an organic small molecule containing both a sulfonic acid group and an amine group.

3. The method for repairing a degraded lead-acid battery using a zwitterionic additive as claimed in claim 1, wherein: The sultone in S11 is one or more of 1,3-propane sultone, 1,4-butane sultone, 2,4-butane sultone, 1,3-propylene sultone, and tetrafluoroethane sultone.

4. The method for repairing a degraded lead-acid battery using a zwitterionic additive as claimed in claim 1, wherein: The amine in S12 is one or more of ethylamine, triethylamine, triethanolamine, phenylethylamine, propylamine, tri-n-propylamine, monoisopropylamine, and diisopropylamine.

5. The method for repairing a degraded lead-acid battery using a zwitterionic additive as claimed in claim 1, wherein: The conductive carbon in S14 is one or more of acetylene black, activated carbon, carbon nanotubes, graphene, Ketjen black, and electrodeposited carbon powder.

6. The method for repairing a degraded lead-acid battery using a zwitterionic additive as claimed in claim 1, wherein: The acid in S14 is one or more of hydrochloric acid, nitric acid, and perchloric acid.

7. The method for repairing a degraded lead-acid battery using a zwitterionic additive as claimed in claim 1, wherein: The mass ratio of the conductive carbon to the zwitterionic additive in the S16 is 1:1 to 10:

1.

8. The method for repairing a degraded lead-acid battery using a zwitterionic additive as claimed in claim 1, wherein: The current density during small current charging of S22 is 0.05~0.2 C.

9. The method for repairing a degraded lead-acid battery using a zwitterionic additive according to any one of claims 1 to 8, wherein: The lead-acid battery includes one or more of the following: substation / converter station DC power supply, communication power supply, UPS power supply, computer and data center power supply, distribution automation terminal power supply, transmission line monitoring terminal power supply, substation detection terminal power supply, and electric bicycle power supply.

10. The method for repairing a degraded lead-acid battery using a zwitterionic additive as claimed in claim 9, wherein: The capacity range of the lead-acid battery is 2-400 Ah, and the voltage range of the battery is 2-24 V.

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