CN112421132B - Lead-acid battery repair liquid and preparation method and application thereof - Google Patents
Lead-acid battery repair liquid and preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4242—Regeneration of electrolyte or reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a lead-acid battery repair liquid, a preparation method and application thereof, wherein a three-dimensional conductive network is prepared by modifying carbon black and carbon nano tubes and dispersing graphene, and an inorganic-organic three-dimensional point, line and plane three-dimensional composite system is constructed by bonding chelating functional groups and mixing inorganic-organic mixed electrolyte salt, the system is effectively adsorbed on a battery polar plate to form a protective film, the obstruction of the lead sulfate film on electronic conduction is reduced, and meanwhile, the chelating functional groups attached on the structure can be combined with Pb 2+ Form stable soluble chelate, and can rapidly disintegrate large lead sulfate crystals to achieve the aim of high-efficiency sulfur removal. Meanwhile, the structure can reconstruct the morphology of the lead sulfate crystal, reduce the crystallinity of the lead sulfate crystal, enable the lead sulfate crystal to be more easily converted into Pb at low temperature, and improve the low-temperature performance of the battery. The invention effectively prolongs the service life of the new lead-acid battery, improves the capacity of the waste lead-acid battery and the low-temperature performance of the battery, has reasonable design and is easy to popularize.
Description
Technical Field
The invention belongs to the field of improving the performance of new lead-acid batteries and repairing waste lead-acid batteries, and particularly relates to a lead-acid battery repairing liquid and a preparation method and application thereof.
Background
Lead acid batteries are a mature technology as it has existed since the end of the 19 th century. They have a low cost, high performance, and are easily recycled and easily charged. The efficiency of lead acid batteries is relatively high, about 80-90%. However, when high power discharges, their available capacity can be greatly reduced. Therefore, the depth of discharge of lead-acid batteries is limited. At 80% depth of discharge, their typical cycle life is about 1500 cycles (IEC market strategy committee, 2011).
The electrochemical performance of the lead-acid battery is gradually reduced due to failure modes such as positive grid corrosion, easy sulfation of a negative electrode and the like in the use process. The design life of a common lead-acid battery is generally 2-3 years, and the actual service life of the common lead-acid battery is far shorter than the expected service life, but the actual service life of the common lead-acid battery is often only 1 year or less, which causes great waste. With exhaustion of fossil fuels, consumption of lead-acid batteries by society is increasing. The rapid development of new energy industry requires continuous support of new technology, and the service life of the lead-acid battery is prolonged by means of material addition, so that the lead-acid battery becomes a very economic and effective means. The service life of the lead-acid battery is prolonged by some reasonable means or the waste lead-acid battery can be repaired, the service life of a lead-acid battery product is prolonged, and the method is a low-cost and high-benefit technology and has quite optimistic industrialization prospect.
At present, the technical formula of electrolyte additives for repairing lead-acid storage batteries mainly comprises the steps that repairing factors are attached to the surface of an electrode material in a one-dimensional or two-dimensional mode, the sulfur removal effect is not obvious, only the effect of slightly cleaning the surface of lead sulfate can be achieved, lead sulfate cannot be thoroughly removed, and then lead sulfate crystallization can be attached to a polar plate again. Because it does not truly repair the battery, it cannot truly find wide popularization and application. Meanwhile, the lead-acid battery is greatly affected by the ambient temperature, so that the cycle performance of the lead-acid battery at low temperature is poor, and the existing repair technology can simultaneously recover the capacity and improve the low-temperature performance.
Disclosure of Invention
The invention aims to provide a lead-acid storage battery repair liquid and a preparation method and application thereof. The three-dimensional network repair structure system repair liquid designed by the invention can be effectively adsorbed on a polar plate of a lead-acid battery to form a protective film, reduce the obstruction of the lead sulfate film on the lead surface to electron conduction, and simultaneously the chelating functional group attached on the structure can be combined with Pb 2+ The stable soluble chelate is formed, the polar plate function can be quickly recovered, and the lead sulfate crystal with large disintegration achieves the purpose of high-efficiency sulfur removal, thereby prolonging the service life of the deep cycle of the battery. Meanwhile, the structure can reconstruct the morphology of the lead sulfate crystal, reduce the crystallinity of the lead sulfate and the crystallinity of the lead sulfate crystal, enable the lead sulfate crystal to be more easily converted into Pb in a low-temperature environment and improve the low-temperature performance of the battery. The lead-acid battery repair liquid has good effect, can effectively prolong the service life of a new lead-acid battery, improve the capacity of a waste lead-acid battery and the low-temperature performance of the battery, has reasonable design and mature technology, and is suitable for large-scale popularization. The invention also has the characteristics of safety, effectiveness and convenience.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a lead-acid storage battery repair liquid comprises the following steps:
step 1, respectively acidizing and modifying the carbon nano tube and the carbon black in sequence;
step 2, adding chitosan solution into the carbon nanotubes treated in the step 1, and fully dispersing; adding polyethylene glycol solution into the treated carbon black, fully dispersing, mixing the two dispersed liquids, and stirring at a high speed of 1000 revolutions per minute for 30 minutes to obtain a mixed solution A, so as to realize interpenetrating between polyethylene glycol polymer chains and chitosan polymer chains;
step 3, adding a pre-prepared sodium alginate-graphene oxide solution into the mixed solution A, and mechanically stirring for 30 minutes so as to form a self-assembly system between chitosan and sodium alginate through electrostatic action;
and 4, adding the aqueous solution of the inorganic-organic mixed electrolyte salt of small molecules into the mixed solution A, and carrying out ultrasonic heating and full mixing to obtain the lead-acid storage battery repairing liquid with the inorganic-organic three-dimensional point, line and surface three-dimensional composite network structure.
As an improvement, the acidification step in step 1 is as follows: firstly, mixing concentrated sulfuric acid with carbon nano tubes or carbon black according to the mass ratio of 100:5, and heating and acidifying for 2 hours at 80 ℃ to obtain acidified carbon nano tubes or acidified carbon black.
The modified material is obtained by dispersing acidified carbon nano tube and carbon black in aqueous solution of aminocarboxylic acid chelating agent and polycarboxylic acid chelating agent respectively, stirring at high speed for more than 12 hours, and filtering or centrifuging and drying; the mass ratio of the carbon nano tube to the aminocarboxylic acid chelating agent is 1:5-20, the mass ratio of the carbon black to the polycarboxylic acid chelating agent is 1:5-20, and the mass concentrations of the aminocarboxylic acid chelating agent and the polycarboxylic acid chelating agent are 1:50-500.
Further improvements are that the aminocarboxylic acid chelating agent is ethylenediamine tetraacetic acid (EDTA), aminotriacetic acid (also known as nitrilotriacetic acid NTA), or diethylenetriamine pentaacetic acid (DTPA) and salts thereof; the polycarboxylic acid chelating agent is polyacrylic acid (PAA), polymethacrylic acid, hydrolyzed polymaleic anhydride (HPMA), or fumaric acid-acrylic acid copolymer.
As an improvement, in the step 2, chitosan solution and polyethylene glycol solution are respectively and independently added into the carbon nano tube and carbon black which are sequentially acidified and modified, wherein the mass concentration of the chitosan in the step 2 is 0.1-1%, the mass concentration of the polyethylene glycol is 0.5-5%, and the carbon nano tube is prepared by the following steps: the mass ratio of the chitosan is 1:0.5-5, and the carbon black is as follows: the mass ratio of polyethylene glycol is 1:2-10;
as an improvement, the mass ratio of graphene oxide to sodium alginate in the sodium alginate-graphene oxide solution in the step 3 is 1:1-5, and the mass concentration of sodium alginate is 1:0.2-1%.
The improvement is that the mass concentration of the aqueous solution of the inorganic-organic mixed electrolyte salt added with the small molecules in the step 4 is 15-40%, the inorganic electrolyte salt consists of concentrated sulfuric acid, sodium sulfate, zinc nitrate and potassium chloride, and the mass ratio of the components is 1:5-10:2-5:1-3; an organic electrolyte composed of L-cysteine and sodium polystyrene sulfonate according to the mass ratio of 1:0.2-1; the mass ratio of the organic electrolyte to the inorganic electrolyte is 1:20-400.
As an improvement, the ultrasonic heating condition in the step 4 is that the temperature is 60-80 ℃, the ultrasonic treatment is carried out for 0.5-2 hours under the power of 300-600W, and then the stirring is carried out for 5 hours at the high speed of 1000 rpm.
The repairing liquid for the lead-acid battery is applied to the lead-acid battery powered by civil electric vehicles or engineering vehicles. It should be noted that the field of gel batteries or maintenance-free batteries is not included.
The lead-acid storage battery repairing liquid is prepared by the preparation method.
Working principle: adding chitosan solution with a certain concentration and polyethylene glycol solution with a certain amount into the carbon nano tube and the carbon black which are sequentially acidified and modified respectively, fully dispersing, mixing the two solutions, stirring at a high speed for a certain time to realize interpenetrating between a polyvinyl alcohol polymer chain and a chitosan polymer chain, adding a prepared sodium alginate graphene solution, mechanically stirring for a certain time to form a self-assembly system through electrostatic interaction between the chitosan and the sodium alginate, finally adding a small molecular inorganic-organic mixed electrolyte salt aqueous solution, and fully mixing through ultrasonic heating to finally realize the additive for the lead-acid battery with the inorganic-organic three-dimensional point, line and surface three-dimensional composite network structure.
Advantageous effects
Compared with the prior art, the preparation method and the application of the repair liquid for the lead-acid battery have the advantages that the chelate functional group attached to the three-dimensional structure can be combined with Pb 2+ Forming stable soluble chelate, capable ofThe function of the polar plate is quickly recovered, and the lead sulfate crystal with large disintegration achieves the aim of high-efficiency sulfur removal, thereby prolonging the service life of the deep cycle of the battery. The physical structure of the battery is not damaged, the chemical environment of the battery is not changed, a three-dimensional protective film can be formed on the surface of a battery polar plate, the deposition of newly generated lead sulfate crystals is inhibited, and the long-acting and stable repairing effect can be ensured; the nano carbon material (carbon black, carbon nano tube and graphene oxide) is introduced, so that the specific surface area of the electrode is greatly improved, the surface structure of the electrode is improved, the internal resistance is greatly reduced, the interface electron transfer efficiency is improved, the conductivity of electrolyte is enhanced, the capacity recovery performance and recharging acceptance of the storage battery after overdischarge are improved, the capacity of the battery can be recovered to the maximum extent, the service life of the battery is prolonged, the capacity of the restored storage battery can be recovered to more than 90%, and the service life can be prolonged by one time or more. Meanwhile, the three-dimensional structure can reconstruct the morphology of the lead sulfate crystal, reduce the crystallinity of the lead sulfate and the crystallinity of the lead sulfate crystal, enable the lead sulfate crystal to be more easily converted into Pb in a low-temperature environment, and improve the low-temperature performance of the battery.
Drawings
FIG. 1 is an effect diagram of the lead-acid storage battery repair liquid, namely 1-graphene oxide, 2-carbon nanotubes, 3-organic-inorganic three-dimensional network and 4-charger.
Description of the embodiments
Embodiments of the invention are further described below with reference to the accompanying drawings: the following examples are given by way of illustration of detailed embodiments and specific procedures based on the technical scheme of the present invention, but the scope of the present invention is not limited to the following examples.
Examples
A preparation method of a lead-acid storage battery repair liquid comprises the following steps:
firstly, mixing concentrated sulfuric acid with carbon nano tubes or carbon black according to the mass ratio of 100:5, and acidifying for 2 hours at 80 ℃ to obtain acidified carbon nano tubes or acidified carbon black.
Dispersing acidified carbon nano tube 2 g in a solution with a mass concentration of 1/500 EDTA (carbon nano tube: aminocarboxylic acid chelating agent mass ratio=1:5), carrying out ultrasonic treatment, and carrying out suction filtration and drying; dispersing acidified carbon black 2 g in a solution with the concentration of 1/50 PAA (carbon black: polycarboxylic acid chelating agent mass ratio=1:5), continuously stirring for 12 hours after ultrasonic treatment, and carrying out suction filtration and drying;
dispersing the modified carbon nano tube in 1000g of chitosan solution with the mass concentration of 0.1% (carbon nano tube: chitosan mass ratio=1:0.5), dispersing the modified carbon black in 500g of polyethylene glycol solution with the mass concentration of 1% (carbon black: polyethylene glycol mass ratio=1:2.5), mixing the two solutions after full dispersion, and stirring at a high speed for 12h;
further, dispersing 0.5g of graphene oxide powder in 500g of sodium alginate solution with concentration of 0.2% (graphene oxide: sodium alginate=1:2) by ultrasonic to prepare sodium alginate-graphene oxide solution, adding the sodium alginate-graphene oxide solution into the mixed solution, and continuously stirring at 1000 rpm for 12 hours at a high speed;
inorganic electrolyte composed of concentrated sulfuric acid, sodium sulfate, zinc nitrate and potassium chloride is dispersed in 3000 mL deionized water according to the mass ratio of 1:5:2:1, and the inorganic electrolyte is uniformly stirred by ultrasonic (the mass concentration is 23%).
L-cysteine: dispersing sodium polystyrene sulfonate in another 600: 600 mL deionized water in a mass ratio of 1:0.2, stirring uniformly by ultrasonic, dispersing the two solutions in the mixed solution in turn in a mass ratio of 1:150, heating by ultrasonic to mix thoroughly, performing ultrasonic treatment for 2 hours at 60 ℃ under 300W power, and stirring at 1000 rpm for 5 hours at high speed to prepare the high-efficiency lead-acid battery additive.
The operation method for repairing the lead-acid storage battery by using the method comprises the following steps:
and opening a liquid adding cover of the lead-acid battery, injecting repairing liquid according to 10% of the battery capacity (taking voltage of 2V as a basic unit), and covering the liquid adding cover to charge and discharge. And (3) detecting charge and discharge data indexes after 2-3 times of cyclic charge and discharge, wherein the battery repair is completed if the charge capacity of the battery is greatly improved.
Examples
A preparation method of a lead-acid storage battery repair liquid comprises the following steps:
firstly, mixing concentrated sulfuric acid with carbon nano tubes or carbon black according to the mass ratio of 100:5, and heating and acidifying for 2 hours at 80 ℃ to obtain acidified carbon nano tubes or acidified carbon black.
Dispersing acidified carbon nano tube 2 g in a solution with the concentration of 1/100 NTA (carbon nano tube: chelating agent=1:10), carrying out ultrasonic treatment, and carrying out suction filtration and drying; dispersing acidified carbon black 2 g in a solution of 1/50 of polymethacrylic acid (carbon black: chelating agent mass ratio=1:10), carrying out ultrasonic treatment, continuing stirring for 12h, and carrying out suction filtration and drying;
dispersing the modified carbon nano tube in 500g of 0.8% chitosan solution (carbon nano tube: chitosan=1:2), dispersing the modified carbon black in 500g of 2% polyethylene glycol solution (carbon black: polyethylene glycol=1:5), fully dispersing, mixing the two solutions, and stirring at high speed for 12h;
and dispersing 0.5g of graphene oxide powder in 500g of sodium alginate solution with concentration of 1% (graphene oxide: sodium alginate=1:10) by ultrasonic to prepare sodium alginate-graphene solution, adding the sodium alginate-graphene solution into the mixed solution, and continuously stirring at high speed for 12h. Dispersing inorganic electrolyte consisting of concentrated sulfuric acid, sodium sulfate, zinc nitrate and potassium chloride in 3000 mL deionized water according to the proportion of 1:8:3:2, stirring uniformly (the concentration is 30%) by ultrasonic wave,
l-cysteine: dispersing sodium polystyrene sulfonate in another 800 mL deionized water in a ratio of 1:0.5, stirring uniformly by ultrasonic, dispersing the organic electrolyte and the inorganic electrolyte in the mixed solution in sequence in a ratio of 1:20, and carrying out ultrasonic heating and full mixing on the two solutions, wherein the ultrasonic condition is that 600W power is subjected to ultrasonic treatment for 0.5h at 60 ℃, and then stirring at a high speed of 1000 rpm for 5h to prepare the high-efficiency lead-acid battery additive.
Example 3
A preparation method of a repair liquid for a lead-acid battery comprises the following steps:
firstly, mixing concentrated sulfuric acid with carbon nano tubes or carbon black according to the mass ratio of 100:5, and heating and acidifying for 2 hours at 80 ℃ to obtain acidified carbon nano tubes or acidified carbon black;
dispersing acidified carbon nano tube 2 g in a solution with a mass concentration of 1/50 DTPA (carbon nano tube: chelating agent mass ratio=1:20), carrying out ultrasonic treatment, and carrying out suction filtration and drying; dispersing acidified carbon black 2 g in a solution with a mass concentration of 1/500 HPMA (carbon black: chelating agent mass ratio=1:15), continuously stirring for 12 hours after ultrasonic treatment, and carrying out suction filtration and drying;
dispersing the modified carbon nano tube in 1000g of 1% chitosan solution (carbon nano tube: chitosan mass ratio=1:5), dispersing the modified carbon black in 500g of 4% polyethylene glycol solution (carbon black: polyethylene glycol mass ratio=1:10), mixing the two solutions after full dispersion, and stirring at a high speed of 1000 rpm for 12h;
and dispersing 0.5g of graphene oxide powder into 300g of sodium alginate solution with mass concentration of 0.8% (graphene oxide: sodium alginate mass ratio=1:4.8) by ultrasonic to prepare sodium alginate graphene solution, adding the sodium alginate graphene solution into the mixed solution, and continuously stirring at a high speed of 1000 revolutions per minute for 12 hours. Dispersing inorganic electrolyte consisting of concentrated sulfuric acid, sodium sulfate, zinc nitrate and potassium chloride in 3000 mL deionized water according to the mass ratio of 1:10:2:3, stirring uniformly by ultrasonic (the mass concentration is 36%),
l-cysteine: dispersing sodium polystyrene sulfonate in another 750: 750 mL deionized water in a ratio of 1:1, stirring uniformly by ultrasonic, dispersing an organic electrolyte and an inorganic electrolyte in the mixed solution in sequence in a ratio of 1:400, heating by ultrasonic to mix thoroughly, performing ultrasonic treatment for 1h at 80 ℃ under 500W power, and stirring at 1000 r/min for 5h at high speed to obtain the high-efficiency lead-acid battery additive.
The 24V/280AH cart battery used for two years is selected, the discharge time of the series of storage batteries is usually detected to be about 1.6-3 h, and the discharge time of the new storage battery is normally 5h. After the lead-acid storage battery repair liquid 300 mL prepared in the embodiment 1 is added and subjected to 1-time charge and discharge reaction, the discharge time of the storage battery is improved to about 4.1h, and after 5-time charge and discharge, the discharge time of the storage battery is stabilized to about 4.8 h, the actual discharge capacity of a monomer is 254AH, and 91% of the standard capacity of the battery is discharged. After the lead-acid storage battery repair liquid 300 mL prepared in the second embodiment is added and subjected to 1-time charge and discharge reaction, the discharge time of the storage battery is improved to about 4.2 hours, and after 5-time charge and discharge, the discharge time of the storage battery is stabilized to about 4.9 h, the actual discharge capacity of a monomer is 266AH, and 95% of the standard capacity of the battery is discharged. After the lead-acid storage battery repair liquid 300 mL prepared in the embodiment 2 is added and subjected to 1-time charge and discharge reaction, the discharge time of the storage battery is improved to be about 4.0 h, and after 5-time charge and discharge, the discharge time of the storage battery is stabilized to be about 4.75 h, the actual discharge capacity of a monomer is 253AH, and 90% of the standard capacity of the battery is discharged.
In summary, the invention can effectively dissolve and remove lead sulfate crystals on the battery plate, recover the function of the plate, recover the capacity of the recovered battery to more than 90% of the capacity of a new battery, and form a protective film on the surface of the battery plate so that the battery plate does not crystallize lead sulfate. The lead-acid storage battery repair liquid provided by the invention is injected into a new lead-acid storage battery, and can also prevent the sulfation of the battery.
In the foregoing, the protection scope of the present invention is not limited to the preferred embodiments of the present invention, and any simple changes or equivalent substitutions of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention disclosed in the present invention fall within the protection scope of the present invention.
Claims (6)
1. The preparation method of the repair liquid for the lead-acid battery is characterized by comprising the following steps of:
step 1, respectively and sequentially acidizing and modifying the carbon nano tube and the carbon black, wherein the modifying method comprises the steps of respectively dispersing the acidized carbon nano tube and the carbon black in aqueous solutions of an amino carboxylic chelating agent and a polycarboxylic chelating agent, stirring at an ultrasonic-high speed for more than 12 hours, and then filtering or centrifugally drying to obtain a modified material; the mass ratio of the carbon nano tube to the aminocarboxylic acid chelating agent is 1:5-20, the mass ratio of the carbon black to the polycarboxylic acid chelating agent is 1:5-20, and the mass concentrations of the aminocarboxylic acid chelating agent and the polycarboxylic acid chelating agent are 1:50-500;
step 2, adding chitosan solution into the carbon nanotubes treated in the step 1, and fully dispersing; adding polyethylene glycol solution into the treated carbon black, fully dispersing, mixing the two dispersed liquids, and stirring at a high speed of 1000 revolutions per minute for 30 minutes to obtain a mixed solution A, so as to realize interpenetrating between polyethylene glycol polymer chains and chitosan polymer chains;
step 3, adding a pre-prepared sodium alginate-graphene oxide solution into the mixed solution A, and mechanically stirring for 30 minutes so as to form a self-assembly system between chitosan and sodium alginate through electrostatic action;
step 4, adding aqueous solution of inorganic-organic mixed electrolyte salt of small molecules into the mixed solution A, and carrying out ultrasonic heating and full mixing to obtain the lead-acid storage battery repairing liquid of an inorganic-organic three-dimensional point, line and surface three-dimensional composite network structure, wherein the mass concentration of the aqueous solution of the inorganic-organic mixed electrolyte salt of small molecules is 15-40%, the inorganic electrolyte salt is composed of concentrated sulfuric acid, sodium sulfate, zinc nitrate and potassium chloride, and the mass ratio of each component is 1:5-10:2-5:1-3; an organic electrolyte composed of L-cysteine and sodium polystyrene sulfonate according to the mass ratio of 1:0.2-1; the mass ratio of the organic electrolyte to the inorganic electrolyte is 1:20-400.
2. The method for preparing a repair liquid for lead-acid batteries according to claim 1, wherein the acidification step in step 1 is as follows: mixing concentrated sulfuric acid with carbon nano tube or carbon black according to the mass ratio of 100:5, and heating at 80 ℃ to acidify for 2 hours to obtain the acidified carbon nano tube or acidified carbon black.
3. The method for preparing a repair liquid for lead-acid batteries according to claim 1, wherein the amino carboxylic acid chelating agent is ethylenediamine tetraacetic acid, aminotriacetic acid or diethylenetriamine pentaacetic acid and salts thereof; the polycarboxylic acid chelating agent is polyacrylic acid, polymethacrylic acid, hydrolyzed polymaleic anhydride or fumaric acid-propylene sulfonic acid copolymer.
4. The method for preparing the repair liquid for the lead-acid battery according to claim 1, wherein in the step 2, the mass concentration of chitosan is 0.1-1%, the mass concentration of polyethylene glycol is 0.5-5%, and the mass concentration of carbon nanotubes is as follows: the mass ratio of the chitosan is 1:0.5-5, and the carbon black is as follows: the mass ratio of polyethylene glycol is 1:2-10; in the sodium alginate-graphene oxide solution, the mass ratio of graphene oxide to sodium alginate is 1:1-5, and the mass concentration of sodium alginate is 1:0.2-1%.
5. The method for preparing a repair liquid for lead-acid batteries according to claim 1, wherein the ultrasonic heating condition in the step 4 is that the temperature is 60-80 ℃, the power of 300-600W is treated by ultrasonic for 0.5-2 hours, and then the repair liquid is stirred for 5 hours at 1000 rpm.
6. Use of the repair liquid for lead-acid batteries based on the lead-acid battery obtained in claim 1 in lead-acid batteries powered by civil electric vehicles or engineering vehicles.
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