CN111564670A - Method for manufacturing low-temperature stable lead storage battery - Google Patents
Method for manufacturing low-temperature stable lead storage battery Download PDFInfo
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- CN111564670A CN111564670A CN202010344223.5A CN202010344223A CN111564670A CN 111564670 A CN111564670 A CN 111564670A CN 202010344223 A CN202010344223 A CN 202010344223A CN 111564670 A CN111564670 A CN 111564670A
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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
- H01M10/12—Construction or manufacture
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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
- H01M10/446—Initial charging measures
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a manufacturing method of a low-temperature stable lead storage battery, which comprises the following steps: (1) preparing a sulfuric acid solution with the density of 1.05-1.15; (2) adding sodium lignosulfonate into the sulfuric acid solution until the sodium lignosulfonate is saturated in the sulfuric acid solution to prepare a solution for acid leaching; (3) coating lead paste on a negative plate grid to prepare a negative plate, conveying the solution for acid leaching prepared in the step (2) to an acid leaching press roller, and leaching acid on the negative plate; (4) curing and drying the acid-sprayed negative plate, assembling the acid-sprayed negative plate, the cured and dried positive plate and the AGM separator into a plate group, and putting the plate group into a battery box to obtain a finished battery; (5) and adding electrolyte into a battery box of the finished battery, and then forming the finished battery to obtain the lead storage battery with stable low temperature. By using the method of the invention, the consistency between the surface and the interior of the polar plate is good, thereby improving the low-temperature performance of the countermeasure and the cycle life thereof.
Description
Technical Field
The invention belongs to the technical field of lead storage battery preparation, and particularly relates to a manufacturing method of a low-temperature stable lead storage battery.
Background
In order to improve the battery performance of the lead-acid storage battery, different additives such as carbon materials, organic expanding agents, conductive agents, stabilizing agents and the like are added into a positive electrode and a negative electrode, and although the additives occupy a small proportion in lead paste, the additives can play an important role. Wherein the organic swelling agent is an indispensable one of the negative electrodes. Lignin is the most widely used additive in organic expanding agents, and has important influence on low-temperature performance, cycle life and the like of batteries. Lignin (sodium lignosulphonate) with different producing areas and different structures can play different roles, the specific surface area and the crystal morphology of the negative electrode are obviously changed, and different influences are generated on the battery.
The acid spraying process is used as an important means for solving the adhesion of the polar plate and improving the curing effect, and the key process is as follows: the density of the coated and filled polar plate is 1.05-1.2g/cm3The sulfuric acid solution on the left and the right is subjected to a leaching process.
However, most of the existing lignin contains a large amount of hydrophilic groups and has certain solubility in aqueous solution, particularly the lignin with low molecular weight can be 1g/L at most in sulfuric acid solution, namely the mass fraction of the lignin is about 0.1%. In addition, in the formula of basically all the negative pole lead pastes in the prior art, the content of lignin is only about 0.1-0.5%.
Therefore, after the polar plate is acid-showered, lignin on the surface of the polar plate is greatly lost, and the low-temperature performance of the battery is inevitably reduced due to the reduction of the content of the lignin. Meanwhile, the periodic replacement of the circulating acid leaching solution in the prior art can also cause the lignin content of polar plates in different batches to be inconsistent.
In order to improve this situation, chinese patent publication No. CN 105304898A discloses negative electrode lead paste containing modified lignin for a battery and a preparation method thereof, wherein the lignin is modified to reduce its solubility, and the functional groups of the lignin can be maximally maintained in a high-temperature electrolyte and can be maintained in the battery for a long time. However, the general storage battery plant cannot be used for modifying lignin, and the investment cost is relatively high, so the practicability is not good, and in addition, the cost is increased if the modified lignin is purchased.
Chinese patent publication No. CN 101330140a discloses a high-temperature lead-acid battery negative lead paste for vehicles and a preparation method thereof, which adopts high-temperature lignin to replace conventional lignin, effectively improves the performance of negative active materials in a high-temperature state, slows down shrinkage, and effectively improves the battery life. However, the price of the high-temperature lignin on the market is at least 30% higher than that of the conventional lignin, and a lot of companies have difficult resistance to implement under the pressure of the extremely high cost of the current lead-acid industry.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for manufacturing a low-temperature stable lead storage battery, which ensures that the consistency between the surface and the interior of a polar plate is good, thereby improving the low-temperature performance of a countermeasure and the cycle life of the battery.
The technical scheme of the invention is as follows:
a manufacturing method of a low-temperature stable lead storage battery comprises the following steps:
(1) preparing a sulfuric acid solution with the density of 1.05-1.15;
(2) adding sodium lignosulfonate into the sulfuric acid solution until the sodium lignosulfonate is saturated in the sulfuric acid solution to prepare a solution for acid leaching;
(3) coating lead paste on a negative plate grid to prepare a negative plate, conveying the solution for acid leaching prepared in the step (2) to an acid leaching press roller, and leaching acid on the negative plate;
(4) curing and drying the acid-sprayed negative plate, assembling the acid-sprayed negative plate, the cured and dried positive plate and the AGM separator into a plate group, and putting the plate group into a battery box to obtain a finished battery;
(5) and adding electrolyte into a battery box of the finished battery, and then forming the finished battery to obtain the lead storage battery with stable low temperature.
The invention provides a new process aiming at lignin loss caused by the surface of a negative plate by the existing acid leaching process, and the method adopts the dilute sulfuric acid solution containing saturated lignin to carry out acid leaching, so that the produced polar plate is ensured to have stable lignin content and good consistency between the surface and the interior of the polar plate, and the low-temperature performance of the countermeasure and the cycle life of the polar plate are improved.
In the step (1), preparing a sulfuric acid solution with the density of 1.08-1.12.
In order to dissolve or separate out the sodium lignosulfonate when the temperature of the solution for acid leaching changes and ensure that the acid leaching solution is a saturated solution of the sodium lignosulfonate, in the step (2), when the sodium lignosulfonate is added into the sulfuric acid solution, the temperature of the sulfuric acid solution is controlled to be 20-40 ℃.
Because lignin (sodium lignosulfonate) with different producing areas and different structures can play different roles, in the method, the same lignin is used in the lead plaster and the sodium lignosulfonate.
The temperature of the battery is increased after the acid is added, the diameter of colloid particles of the negative electrode expanding agent in sulfuric acid is increased due to the excessively high temperature, the aperture of a negative electrode plate is increased and is far larger than the median aperture of the AGM separator, so that the AGM separator is difficult to supply acid to the negative electrode, and the low-temperature performance of the battery is reduced. Therefore, the invention adopts the cooled electrolyte to reduce the temperature of the battery after the acid is added, and further controls the temperature of the battery formation process by combining the formation process of small current, so that the expanding agent in the negative plate is well adsorbed in the negative active material, and the low-temperature performance of the battery is comprehensively improved.
In the step (5), the temperature of the electrolyte is-25-10 ℃. Further, the temperature of the electrolyte is-10-5 ℃.
The temperature of the battery is increased due to the excessively high current density, and the sodium lignosulfonate forms large colloidal particles, so that the pore diameter of the negative plate is increased, and the performance of the battery is reduced. Too small current will prolong the formation time and will not meet the production requirements. In the step (5), the current density is controlled to be 2-4 mA/cm during formation2。
In the step (5), the formation time is 50-70 h.
Compared with the prior art, the invention has the following beneficial effects:
1. the method adopts the dilute sulfuric acid solution containing saturated lignin to carry out acid leaching, ensures that the produced polar plate has stable lignin content and good consistency between the surface and the interior of the polar plate, and ensures that the prepared lead storage battery has stable low-temperature performance.
2. In the charging formation process, the pre-cooled electrolyte is adopted, and the formation process of small current is matched, so that the temperature in the battery formation process is further controlled, the expanding agent in the negative plate is well adsorbed in the negative active material, and the low-temperature performance of the battery is comprehensively improved.
Drawings
Fig. 1 is a schematic flow chart of a manufacturing method of a low-temperature stable lead storage battery according to the invention.
Detailed Description
The present invention is further illustrated by the following examples, which are merely preferred, but not exhaustive, of the invention. Based on the embodiments in the implementation, other embodiments obtained by those skilled in the art without any creative efforts belong to the protection scope of the present invention.
Example 1
As shown in fig. 1, a method for manufacturing a low-temperature stable lead acid battery includes:
s01, preparing a sulfuric acid solution with the density of 1.10.
S02, adding sodium lignosulfonate into the sulfuric acid solution until the sodium lignosulfonate is saturated in the sulfuric acid solution, and preparing the solution for acid leaching. When preparing the solution, controlling the temperature of the sulfuric acid solution to be 50-80 ℃.
In the prepared solution, part of sodium lignosulfonate is not dissolved in the solution, and the sodium lignosulfonate is dissolved or separated out when the temperature is changed, so that the acid leaching solution is ensured to be a saturated solution of the sodium lignosulfonate.
And S03, coating the prepared lead paste on a negative plate grid through a plate coating machine head to prepare a negative plate, and conveying the solution for acid leaching configured in the step S02 to an acid leaching press roller to leach acid on the negative plate. The lignin in the lead plaster formula and the lignin in the sodium lignosulphonate are the same lignin.
S04, drying the surface of the negative plate after acid spraying through a drying line, then carrying out normal curing and drying processes, assembling the negative plate, the positive plate after curing and drying and an AGM separator into a plate group, and putting the plate group into a battery box to obtain a 60Ah finished battery;
s05, adding electrolyte with the temperature of 0 ℃ into a battery box of the finished battery, and adopting the current density of 2-4 mA/cm2And (4) carrying out formation on the finished product battery with the electrolyte to obtain the low-temperature stable lead storage battery.
The procedure of example 2 and example 3 was carried out in accordance with example 1, with the only difference being that the plates were produced at different time periods.
Comparative example 1
Step 1, preparing a sulfuric acid solution with the density of 1.10 as a solution for acid leaching.
And 2, coating the prepared lead plaster on a negative plate grid through a plate coating machine head to prepare a negative plate, conveying the solution for acid spraying prepared in the step 1 to an acid spraying press roller, and spraying acid on the negative plate.
And 3, drying the surface of the negative plate subjected to acid leaching by a drying line, then carrying out normal curing and drying processes, assembling the negative plate, the cured and dried positive plate and the AGM separator into a plate group, and putting the plate group into a battery box to obtain the 60Ah finished battery.
Step 4, adding electrolyte with the temperature of 0 ℃ into a battery box of the finished battery, and adopting the current density of 2-4 mA/cm2To addAnd (4) forming the finished product battery after the electrolyte to obtain the low-temperature stable lead storage battery.
The procedure of comparative example 2 and comparative example 3 was identical to that of comparative example 1 except that the plates were produced at different time periods.
Comparative example in comparison to the example, the procedure of the example is essentially identical except that the acid-showered sulfuric acid solution is lignin-free. The batteries manufactured in the examples and comparative examples were tested for low-temperature performance, and the results are shown in table 1.
TABLE 1
In the table, U10SRefers to the termination voltage, U, of a heavy current discharge of 10S30SRefers to the termination voltage of the large current discharge 30S. It can be seen that the U of the lead storage battery prepared in the example10SAnd U30SThe low-temperature performance of the lead storage battery is higher than that of the comparative example, the low-temperature performance of different batches of the embodiment is smaller, and the obtained lead storage battery has stable low-temperature performance.
According to the method, in the acid leaching process, the dilute sulfuric acid solution containing saturated lignin is used for acid leaching, so that the stable lignin content of the produced polar plate is ensured, the consistency between the surface and the inside of the polar plate is good, and the low-temperature performance of the prepared lead storage battery is stable. The test results shown in table 1 above also demonstrate the effects of the present invention.
The embodiments described above are intended to illustrate the technical solutions and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modifications, additions and equivalents made within the scope of the principles of the present invention should be included in the scope of the present invention.
Claims (8)
1. A manufacturing method of a low-temperature stable lead storage battery is characterized by comprising the following steps:
(1) preparing a sulfuric acid solution with the density of 1.05-1.15;
(2) adding sodium lignosulfonate into the sulfuric acid solution until the sodium lignosulfonate is saturated in the sulfuric acid solution to prepare a solution for acid leaching;
(3) coating lead paste on a negative plate grid to prepare a negative plate, conveying the solution for acid leaching prepared in the step (2) to an acid leaching press roller, and leaching acid on the negative plate;
(4) curing and drying the acid-sprayed negative plate, assembling the acid-sprayed negative plate, the cured and dried positive plate and the AGM separator into a plate group, and putting the plate group into a battery box to obtain a finished battery;
(5) and adding electrolyte into a battery box of the finished battery, and then forming the finished battery to obtain the lead storage battery with stable low temperature.
2. The method for manufacturing a low-temperature stable lead-acid battery according to claim 1, wherein in the step (1), a sulfuric acid solution having a density of 1.08 to 1.12 is prepared.
3. The method for manufacturing a low-temperature stable lead-acid battery according to claim 1, wherein in the step (2), the temperature of the sulfuric acid solution is controlled to be 20-40 ℃ when sodium lignosulfonate is added into the sulfuric acid solution.
4. The method for manufacturing a low-temperature stable lead-acid battery according to claim 1, wherein the lead paste and the sodium lignosulfonate are made of the same lignin.
5. The method for manufacturing a low-temperature stable lead-acid battery according to claim 1, wherein in the step (5), the temperature of the electrolyte solution is-25 to 10 ℃.
6. The method for manufacturing a low-temperature stable lead-acid battery according to claim 1, wherein in the step (5), the temperature of the electrolyte solution is-10 to 5 ℃.
7. The method for manufacturing a low-temperature stable lead-acid battery according to claim 1, wherein in the step (5), formation is performedThe current density is controlled to be 2-4 mA/cm2。
8. The method for manufacturing a low-temperature stable lead-acid battery according to claim 1, wherein the formation time in the step (5) is 50 to 70 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112768789A (en) * | 2021-01-27 | 2021-05-07 | 天能电池集团股份有限公司 | Formation method for improving low-temperature capacity of lead storage battery |
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