CN110544799B - Method for rapidly recovering capacity of lead-acid storage battery - Google Patents
Method for rapidly recovering capacity of lead-acid storage battery Download PDFInfo
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- CN110544799B CN110544799B CN201910908663.6A CN201910908663A CN110544799B CN 110544799 B CN110544799 B CN 110544799B CN 201910908663 A CN201910908663 A CN 201910908663A CN 110544799 B CN110544799 B CN 110544799B
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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
- H01M10/08—Selection of materials as electrolytes
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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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- 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
- H01M10/44—Methods for charging or discharging
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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
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
- H01M2300/0011—Sulfuric acid-based
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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
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Abstract
The invention discloses a method for quickly recovering the capacity of a lead-acid storage battery, which comprises the following steps: s1, preparing various raw materials of a functional repair liquid, including sulfuric acid electrolyte, sodium sulfate, isoascorbic acid, 2-acrylamide-2-methylpropanesulfonic acid and tetrabutylammonium chloride; s2, sodium sulfate, tetrabutylammonium chloride and sulfuric acid electrolyte are mixed to obtain a repair liquid base material; adding isoascorbic acid and 2-acrylamide-2-methylpropanesulfonic acid into ethanol, stirring, decompressing, and vacuumizing to obtain a functional mixture; adding the base material of the repairing liquid into the functional mixture to obtain functional repairing liquid; s3, fully discharging the lead-acid storage battery; s4, adding the functional repair liquid, and S5, fully charging the lead-acid storage battery. The recovery method provided by the invention has the advantages of low repair cost, simple operation, short time consumption and good repair effect.
Description
Technical Field
The invention relates to the technical field of lead-acid storage batteries, in particular to a method for quickly recovering the capacity of a lead-acid storage battery.
Background
The lead-acid storage battery has the advantages of good reversibility, stable voltage characteristic, capability of discharging large current, low production cost, wide application range and the like, is widely applied to the fields of transportation, communication, electric power, railways, mines, ports, national defense, computers, scientific research and the like, and is one of important products in social production and operation activities and human life. However, as the usage amount of lead-acid storage batteries increases, the number of waste batteries reported in the market also increases, and how to treat the waste batteries is also an urgent problem to be solved. The most ideal solution is to repair the scrapped battery again to prolong the service life of the battery. The scrapped batteries in the current market are mainly caused by the following reasons: the electrolyte is dried up, the charging speed is too slow, the discharging speed is too fast, lead sulfate crystals are aggregated, and the like, and the repairing method mainly comprises the following steps: the method comprises a large-current charging method, a hydrotherapy method, pulse repair and the like, but has the defects of unobvious repair effect, unqualified repaired capacity, high repair cost, complex repair method and the like. Based on the defects in the prior art, the invention provides a method for quickly recovering the capacity of a lead-acid storage battery.
Disclosure of Invention
The invention aims to solve the problems of unsatisfactory restoration effect, substandard capacity after restoration, high restoration cost and complex restoration method of the conventional restoration method, and provides a method for quickly restoring the capacity of a lead-acid storage battery.
A method for rapidly recovering the capacity of a lead-acid storage battery comprises the following steps:
s1, preparing functional repair liquid, and comprises the following raw materials: the electrolyte comprises, by weight, 80-93 parts of sulfuric acid electrolyte with the density of 1.32g/cm3, 0.02-0.04 part of sodium sulfate, 0.15-0.18 part of isoascorbic acid, 0.22-0.34 part of 2-acrylamido-2-methylpropanesulfonic acid and 0.04-0.08 part of tetrabutylammonium chloride;
s2, preparing a functional repair liquid: adding the sodium sulfate and tetrabutylammonium chloride prepared in the step S1 into the sulfuric acid electrolyte with the density of 1.32g/cm3 prepared in the step S1, and uniformly mixing to obtain a repair liquid base material; under a dark state, adding the isoascorbic acid and 2-acrylamido-2-methylpropanesulfonic acid prepared in the step S1 into ethanol, uniformly stirring, removing the ethanol under reduced pressure, and vacuumizing for 1-2 h under dark state to obtain a functional mixture; adding the base material of the repair liquid into the functional mixture in a dark state, stirring uniformly, and performing ultrasonic treatment for 20-30 min to obtain a functional repair liquid;
s3, fully discharging the lead-acid storage battery: discharging with 0.5-0.6C current until the voltage is 1.65-1.7V/cell, and modulating the magnetic field source to 10-14 kHz and 140-160 mW power value by the modulation device when the voltage is less than or equal to 1.95V/cell;
s4, adding a functional repair liquid: under a light-proof state, filling the functional repair liquid prepared in the step S2 into the lead-acid storage battery after full discharge in the step S3, wherein the acid adding amount per cell is 1.3-1.5 ml/Ah;
s5, fully charging the lead-acid storage battery: charging the cell with a current of 0.16-0.2C until the voltage is 2.55-2.58V/cell, and modulating the magnetic field source by a modulation device to a frequency of 16-18 kHz and a power value of 140-160 mW when the voltage is more than or equal to 2.35V/cell.
Preferably, the functional repair liquid comprises the following raw materials in parts by weight: 86 parts of sulfuric acid electrolyte with the density of 1.32g/cm3, 0.03 part of sodium sulfate, 0.17 part of isoascorbic acid, 0.28 part of 2-acrylamido-2-methylpropanesulfonic acid and 0.05 part of tetrabutylammonium chloride.
Preferably, the sulfuric acid electrolyte with the density of 1.32g/cm3 is diluted by concentrated sulfuric acid with the density of 1.84g/cm3 and distilled water.
Preferably, in step S2, the amount of ethanol added is 10 to 15 times the total mass of the erythorbic acid and the 2-acrylamido-2-methylpropanesulfonic acid.
Preferably, in step S3, the magnetic field source is modulated by the modulation device to a frequency of 12kHz and a power value of 150mW at a voltage of 1.95V/cell or less.
Preferably, in step S4, the amount of acid added to the solution is 1.4 ml/Ah.
Preferably, in step S5, the magnetic field source is modulated by the modulation device to a frequency of 17kHz and a power value of 150mW at a voltage of 2.35V/cell or higher.
Compared with the prior art, the repair method provided by the invention has the following advantages:
1. according to the repairing method provided by the invention, the waste lead-acid storage battery is repaired by a mode of combining full discharging, functional repairing liquid repairing and full charging, so that the repairing time of the lead-acid storage battery can be shortened, the capacity of the waste lead-acid storage battery is improved, the capacity reaches the standard of the original lead-acid storage battery, the repairing cost is low, the operation is simple, the defect of complicated operation caused by charging and discharging the lead-acid storage battery by using different currents in the traditional repairing method is avoided, the lead-acid storage battery is firstly discharged to a corresponding index by using a specific current, then the functional repairing liquid is supplemented, and finally the lead-acid storage battery is charged to the corresponding index by using the specific current, so that the repairing method is extremely convenient, short in time consumption and good in repairing;
2. the functional repair liquid used in the repair method provided by the invention is scientific and reasonable in proportion, takes sulfuric acid electrolyte with the density of 1.32g/cm3 as base liquid, improves the binding force of the sulfuric acid electrolyte with isoascorbic acid and 2-acrylamido-2-methylpropanesulfonic acid by adding tetrabutylammonium chloride, solves the common phenomenon of electrolyte lead sulfate crystal aggregation by adding sodium sulfate, and improves the repair capability of the functional repair liquid by adding isoascorbic acid and 2-acrylamido-2-methylpropanesulfonic acid in a reasonable proportion, so that the lead-acid storage battery is quickly repaired to standard capacity, and the service life of the lead-acid storage battery is prolonged;
3. in the preparation process of the functional repair liquid, the isoascorbic acid and the 2-acrylamide-2-methylpropanesulfonic acid are pretreated, and then the repair liquid base material mainly comprising sulfuric acid electrolyte is added, so that the preparation time of the functional repair liquid can be shortened, the stability of the functional repair liquid is improved, and the rapid fusion of the functional repair liquid and the electrolyte in the waste lead-acid storage battery is improved.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
Example 1
The invention provides a method for rapidly recovering the capacity of a lead-acid storage battery, which comprises the following steps:
s1, preparing functional repair liquid, and comprises the following raw materials: according to parts by weight, the electrolyte comprises 80 parts of sulfuric acid electrolyte with the density of 1.32g/cm3, 0.02 part of sodium sulfate, 0.15 part of isoascorbic acid, 0.34 part of 2-acrylamide-2-methylpropanesulfonic acid and 0.04 part of tetrabutylammonium chloride; the sulfuric acid electrolyte with the density of 1.32g/cm3 is diluted by concentrated sulfuric acid with the density of 1.84g/cm3 and distilled water;
s2, preparing a functional repair liquid: adding the sodium sulfate and tetrabutylammonium chloride prepared in the step S1 into the sulfuric acid electrolyte with the density of 1.32g/cm3 prepared in the step S1, and uniformly mixing to obtain a repair liquid base material; under a dark state, adding the isoascorbic acid and 2-acrylamido-2-methylpropanesulfonic acid prepared in the step S1 into ethanol, uniformly stirring, removing the ethanol under reduced pressure, and vacuumizing for 1h under dark state to obtain a functional mixture; adding the base material of the repair liquid into the functional mixture in a dark state, stirring uniformly, and performing ultrasonic treatment for 30min to obtain functional repair liquid; the adding amount of the ethanol is 10 times of the total mass of the isoascorbic acid and the 2-acrylamide-2-methylpropanesulfonic acid;
s3, fully discharging the lead-acid storage battery: discharging at 0.6 deg.C until voltage is 1.65V/cell, and modulating magnetic field source to 10kHz and 160mW by modulator when voltage is less than or equal to 1.95V/cell;
s4, adding a functional repair liquid: under a light-proof state, filling the functional repair liquid prepared in the step S2 into the lead-acid storage battery after full discharge in the step S3, wherein the acid adding amount per cell is 1.5 ml/Ah;
s5, fully charging the lead-acid storage battery: charging the sample to a voltage of 2.58V/cell at a current of 0.2C, and modulating the magnetic field source to a frequency of 16kHz and a power value of 160mW by the modulation device when the voltage is greater than or equal to 2.35V/cell.
Example 2
The invention provides a method for rapidly recovering the capacity of a lead-acid storage battery, which comprises the following steps:
s1, preparing functional repair liquid, and comprises the following raw materials: according to parts by weight, 86 parts of sulfuric acid electrolyte with the density of 1.32g/cm3, 0.03 part of sodium sulfate, 0.17 part of isoascorbic acid, 0.28 part of 2-acrylamide-2-methylpropanesulfonic acid and 0.05 part of tetrabutylammonium chloride are included; the sulfuric acid electrolyte with the density of 1.32g/cm3 is diluted by concentrated sulfuric acid with the density of 1.84g/cm3 and distilled water;
s2, preparing a functional repair liquid: adding the sodium sulfate and tetrabutylammonium chloride prepared in the step S1 into the sulfuric acid electrolyte with the density of 1.32g/cm3 prepared in the step S1, and uniformly mixing to obtain a repair liquid base material; adding the isoascorbic acid prepared in the step S1 and 2-acrylamido-2-methylpropanesulfonic acid into ethanol in a dark state, uniformly stirring, removing the ethanol under reduced pressure, and vacuumizing in the dark state for 1. Obtaining a functional mixture after 5 hours; adding the base material of the repair liquid into the functional mixture in a dark state, stirring uniformly, and performing ultrasonic treatment for 30min to obtain functional repair liquid; the adding amount of the ethanol is 13 times of the total mass of the isoascorbic acid and the 2-acrylamide-2-methylpropanesulfonic acid;
s3, fully discharging the lead-acid storage battery: discharging at 0.5C current until voltage is 1.65 per cell, and modulating magnetic field source to frequency of 12kHz and power value of 150mW by using a modulation device when voltage is less than or equal to 1.95V per cell;
s4, adding a functional repair liquid: under a light-proof state, filling the functional repair liquid prepared in the step S2 into the lead-acid storage battery after full discharge in the step S3, wherein the acid adding amount per cell is 1.4 ml/Ah;
s5, fully charging the lead-acid storage battery: charging the sample to a voltage of 2.56V/cell at a current of 0.18C, and modulating the magnetic field source to a frequency of 17kHz and a power value of 150mW by the modulation device when the voltage is greater than or equal to 2.35V/cell.
Example 3
The invention provides a method for rapidly recovering the capacity of a lead-acid storage battery, which comprises the following steps:
s1, preparing functional repair liquid, and comprises the following raw materials: the electrolyte comprises, by weight, 93 parts of sulfuric acid electrolyte with the density of 1.32g/cm3, 0.04 part of sodium sulfate, 0.18 part of isoascorbic acid, 0.22 part of 2-acrylamide-2-methylpropanesulfonic acid and 0.08 part of tetrabutylammonium chloride; the sulfuric acid electrolyte with the density of 1.32g/cm3 is diluted by concentrated sulfuric acid with the density of 1.84g/cm3 and distilled water;
s2, preparing a functional repair liquid: adding the sodium sulfate and tetrabutylammonium chloride prepared in the step S1 into the sulfuric acid electrolyte with the density of 1.32g/cm prepared in the step S1, and uniformly mixing to obtain a repair liquid base material; under a dark state, adding the isoascorbic acid and 2-acrylamido-2-methylpropanesulfonic acid prepared in the step S1 into ethanol, uniformly stirring, removing the ethanol under reduced pressure, and vacuumizing for 2 hours in the dark state to obtain a functional mixture; adding the base material of the repair liquid into the functional mixture in a dark state, stirring uniformly, and performing ultrasonic treatment for 20min to obtain a functional repair liquid; the adding amount of the ethanol is 15 times of the total mass of the isoascorbic acid and the 2-acrylamide-2-methylpropanesulfonic acid;
s3, fully discharging the lead-acid storage battery: discharging at 0.5C current until the voltage is 1.7V/cell, and modulating the magnetic field source to 14kHz through a modulation device when the voltage is less than or equal to 1.95V/cell, wherein the power value is 140 mW;
s4, adding a functional repair liquid: under a light-proof state, filling the functional repair liquid prepared in the step S2 into the lead-acid storage battery after full discharge in the step S3, wherein the acid adding amount per cell is 1.3 ml/Ah;
s5, fully charging the lead-acid storage battery: the sample is charged to a voltage of 2.55V/cell at a current of 0.16C, and when the voltage is greater than or equal to 2.35V/cell, the magnetic field source is modulated to a frequency of 18kHz and a power value of 140mW by a modulation device.
Comparative example 1
The same conditions as in example 1 were used except that the mass of sodium sulfate, erythorbic acid, 2-acrylamido-2-methylpropanesulfonic acid, tetrabutylammonium chloride and the like in step S1 and step S2 of example 1 was changed to a sulfuric acid electrolyte solution having a density of 1.32g/cm 3.
Comparative example 2
The invention provides a method for rapidly recovering the capacity of a lead-acid storage battery, which comprises the following steps:
s1, preparing functional repair liquid, and comprises the following raw materials: according to parts by weight, the electrolyte comprises 80 parts of sulfuric acid electrolyte with the density of 1.32g/cm3, 0.02 part of sodium sulfate, 0.15 part of isoascorbic acid, 0.34 part of 2-acrylamide-2-methylpropanesulfonic acid and 0.04 part of tetrabutylammonium chloride; the sulfuric acid electrolyte with the density of 1.32g/cm3 is diluted by concentrated sulfuric acid with the density of 1.84g/cm3 and distilled water;
s2, preparing a functional repair liquid: adding the sodium sulfate and tetrabutylammonium chloride prepared in the step S1 into the sulfuric acid electrolyte with the density of 1.32g/cm3 prepared in the step S1, and uniformly mixing to obtain a repair liquid base material; under a dark state, mixing the isoascorbic acid prepared in the step S1 with 2-acrylamide-2-methylpropanesulfonic acid, adding the base material of the repair liquid into the functional mixture, stirring uniformly, and performing ultrasonic treatment for 30min to obtain a functional repair liquid;
s3, fully discharging the lead-acid storage battery: discharging at 0.6 deg.C until voltage is 1.65V/cell, and modulating magnetic field source to 10kHz and 160mW by modulator when voltage is less than or equal to 1.95V/cell;
s4, adding a functional repair liquid: under a light-proof state, filling the functional repair liquid prepared in the step S2 into the lead-acid storage battery after full discharge in the step S3, wherein the acid adding amount per cell is 1.5 ml/Ah;
s5, fully charging the lead-acid storage battery: charging the sample to a voltage of 2.58V/cell at a current of 0.2C, and modulating the magnetic field source to a frequency of 16kHz and a power value of 160mW by the modulation device when the voltage is greater than or equal to 2.35V/cell.
Taking 5 groups of waste lead-acid storage batteries with similar capacities, respectively utilizing the above examples 1-3, comparative example 1 and comparative example 2 to carry out capacity recovery on the batteries, and testing the discharge time of the repaired lead-acid storage batteries, wherein the results are shown in the following table:
test results show that the repairing method of the embodiment 1-3 is obviously superior to the repairing method of the comparative example, the discharge time can reach more than 125min, and the addition of the sodium sulfate, the tetrabutyl ammonium chloride, the isoascorbic acid and the 2-acrylamido-2-methylpropanesulfonic acid in the functional repairing solution can obviously improve the battery capacity of the waste lead-acid storage battery, and the pre-treatment solution of the isoascorbic acid and the 2-acrylamido-2-methylpropanesulfonic acid has a certain effect of improving the battery capacity.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. A method for rapidly recovering the capacity of a lead-acid storage battery is characterized by comprising the following steps:
s1, preparing functional repair liquid, and comprises the following raw materials: the electrolyte comprises, by weight, 80-93 parts of sulfuric acid electrolyte with the density of 1.32g/cm3, 0.02-0.04 part of sodium sulfate, 0.15-0.18 part of isoascorbic acid, 0.22-0.34 part of 2-acrylamido-2-methylpropanesulfonic acid and 0.04-0.08 part of tetrabutylammonium chloride;
s2, preparing a functional repair liquid: adding the sodium sulfate and tetrabutylammonium chloride prepared in the step S1 into the sulfuric acid electrolyte with the density of 1.32g/cm3 prepared in the step S1, and uniformly mixing to obtain a repair liquid base material; under a dark state, adding the isoascorbic acid and 2-acrylamido-2-methylpropanesulfonic acid prepared in the step S1 into ethanol, uniformly stirring, removing the ethanol under reduced pressure, and vacuumizing for 1-2 h under dark state to obtain a functional mixture; adding the base material of the repair liquid into the functional mixture in a dark state, stirring uniformly, and performing ultrasonic treatment for 20-30 min to obtain a functional repair liquid;
s3, fully discharging the lead-acid storage battery: discharging with 0.5-0.6C current until the voltage is 1.65-1.7V/cell, and modulating the magnetic field source to 10-14 kHz and 140-160 mW power value by the modulation device when the voltage is less than or equal to 1.95V/cell;
s4, adding a functional repair liquid: under a light-proof state, filling the functional repair liquid prepared in the step S2 into the lead-acid storage battery after full discharge in the step S3, wherein the acid adding amount per cell is 1.3-1.5 ml/Ah;
s5, fully charging the lead-acid storage battery: charging the cell with a current of 0.16-0.2C until the voltage is 2.55-2.58V/cell, and modulating the magnetic field source by a modulation device to a frequency of 16-18 kHz and a power value of 140-160 mW when the voltage is more than or equal to 2.35V/cell.
2. The method for rapidly recovering the capacity of the lead-acid storage battery according to claim 1, wherein the functional repair liquid comprises the following raw materials in parts by weight: 86 parts of sulfuric acid electrolyte with the density of 1.32g/cm3, 0.03 part of sodium sulfate, 0.17 part of isoascorbic acid, 0.28 part of 2-acrylamido-2-methylpropanesulfonic acid and 0.05 part of tetrabutylammonium chloride.
3. A method for rapidly recovering the capacity of a lead-acid storage battery as claimed in claim 1 or 2, wherein the sulfuric acid electrolyte with the density of 1.32g/cm3 is diluted by concentrated sulfuric acid with the density of 1.84g/cm3 and distilled water.
4. The method for rapidly recovering the capacity of the lead-acid storage battery according to claim 1, wherein in the step S2, the adding amount of the ethanol is 10-15 times of the total mass of the isoascorbic acid and the 2-acrylamido-2-methylpropanesulfonic acid.
5. The method for rapidly recovering the capacity of the lead-acid storage battery according to claim 1, wherein in the step S3, when the voltage is less than or equal to 1.95V/cell, the magnetic field source is modulated by the modulation device to have the frequency of 12kHz and the power value of 150 mW.
6. The method for rapidly recovering the capacity of the lead-acid storage battery according to claim 1, wherein in the step S4, the acid addition amount per unit cell is 1.4 ml/Ah.
7. The method for rapidly recovering the capacity of the lead-acid storage battery according to claim 1, wherein in the step S5, when the voltage is greater than or equal to 2.35V/cell, the magnetic field source is modulated by the modulation device to have the frequency of 17kHz and the power value of 150 mW.
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