CN114551815A - Lead storage battery pole plate curing method - Google Patents
Lead storage battery pole plate curing method Download PDFInfo
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- CN114551815A CN114551815A CN202210140766.4A CN202210140766A CN114551815A CN 114551815 A CN114551815 A CN 114551815A CN 202210140766 A CN202210140766 A CN 202210140766A CN 114551815 A CN114551815 A CN 114551815A
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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
- H01M4/20—Processes of manufacture of pasted electrodes
- H01M4/21—Drying of pasted electrodes
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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 lead storage battery pole plate curing method, and relates to the technical field of lead storage battery production. The invention comprises spraying silicon dioxide emulsion mixed solution on the surface of the pole plate by circulating air in the curing stage; the emulsion mixture is prepared by the following method: weighing fumed silica, polyacrylamide and pure water for later use; putting pure water into a high-speed stirring and strong shearing nano material mixing integrated machine body; starting a vacuum high-speed stirring and strong shearing nano material mixing all-in-one machine, starting a vacuum system to suck the needed fumed silica and polyacrylamide powder, and stirring at a high speed; after stirring, the emulsion is subjected to positive and negative strong shearing in a mixing all-in-one machine, and the completely and uniformly prepared milky mixed solution containing silicon dioxide is obtained. According to the invention, a small amount of emulsified mixed liquid of silicon dioxide after shearing is sprayed in two stages and attached to the surface of the pole plate along with circulating air to form a protective layer, so that the phenomenon that the wet-grown pole plate loses water too fast under the action of circulating air is improved.
Description
Technical Field
The invention belongs to the technical field of lead storage battery production, and particularly relates to a method for curing a lead storage battery plate.
Background
In the manufacturing of the lead-acid battery, the pole plate solidification is a special process in the battery production process, the quality of the pole plate is determined by the quality of the solidification effect, and the discharge capacity of the assembled battery, the consistency of the battery capacity and the cycle life are determined.
The curing and drying of the polar plate of the battery of the production enterprise are generally carried out in three steps, the first step is a high-humidity stage, and the high-humidity standing of the stage aims to ensure that lead sulfate generated in the paste mixing process gradually changes to basic lead sulfate 3 PbO. PbSO with crystal water4·H2O and 4 PbO. PbSO4The transformation of (3); the second stage is a lead plaster dehydration free lead oxidation stage and forms a grid corrosion layer, the free lead oxidation in the stage is related to the environment humidity, the lead plaster water content and the circulating air, the outer side polar plate or the polar plate at the position with larger serial hanging gap on the curing frame is influenced by the circulating air and is dehydrated and cured before the middle polar plate in the serial hanging state, so that the curing synchronism in the stage is poor, and the outer side polar plate or the polar plate at the position with larger serial hanging gap is dehydrated and cured too quickly to form a cracked polar plate; the third stage is a drying process of the polar plate, and the chemical change of the third stage is not great.
In order to obtain the consistency of the polar plates, some production enterprises lay gunny bags on a curing frame in the curing and drying process to prevent the polar plates on the outer sides from being dehydrated too fast, and take out the gunny bags to directly dry the polar plates during drying. When the polar plate is cured in the mode, only a small amount of circulating air participates in the curing for a long time due to the blockage of the gunny bag to the air, and the polar plate is not suitable for large-scale mass production and has low production efficiency.
Disclosure of Invention
The invention aims to provide a lead storage battery pole plate curing method, which comprises the steps of spraying a silicon dioxide emulsion mixed solution into a curing chamber through circulating air during the curing and drying stages, and distributing the silicon dioxide emulsion mixed solution on the surfaces of pole plates at the outer sides of series connection or the positions with larger series connection gaps so as to balance and improve the dehydration condition during oxidation during the curing of the pole plates and obtain a good curing effect; the polar plate has no crack, the surface layer has less floating powder, and the discharging consistency of the battery after the battery is assembled and charged is strong.
In order to solve the technical problems, the invention is realized by the following technical scheme:
the invention relates to a method for curing a lead storage battery plate, which comprises the step of spraying a silicon dioxide emulsion mixed solution on the surface of the plate through circulating air in the curing stage.
As a preferable technical scheme of the invention, the emulsion mixed liquor is prepared by the following method:
stp 1; weighing fumed silica, polyacrylamide and pure water for later use;
stp2 and pure water are put into a high-speed stirring and strong shearing nanometer material mixing integrated machine body;
stp3, starting a vacuum high-speed stirring and strong shearing nano material mixing all-in-one machine, starting a vacuum system to suck the needed fumed silica and polyacrylamide powder, and stirring at high speed;
stp4, after stirring, the emulsion is strongly sheared in the mixing machine to obtain the completely uniform milky mixed liquid containing silicon dioxide.
In a preferred embodiment of the present invention, in stp1, the fumed silica and the polyacrylamide are 0.4 to 0.5 wt% and 0.05 to 0.06 wt%, respectively, based on the total raw material.
In a preferred embodiment of the present invention, in stp1, the fumed silica and polyacrylamide are contained in an amount of 0.5 wt% and 0.05 wt%, respectively, based on the total raw material.
In a preferable technical scheme of the invention, in the Stp4, the forward shearing rotation speed is 3000r/min, the reverse shearing rotation speed is 1500r/min, and the shearing time is 10-15 min.
As a preferable technical solution of the present invention, the method further comprises a first curing stage performed before the second curing stage; in the first stage of curing, the polar plate is placed under the conditions that the relative humidity is 98-100%, the air speed and the air quantity are set to be proportional to the air quantity set to be 0-30%, the curing temperature is gradually increased to 65-80 ℃, and then the polar plate is kept at the temperature for 3-5 hours.
As a preferred technical scheme, in the curing stage, the curing temperature is gradually reduced to 45-65 ℃ within 3-5 hours, the humidity is gradually reduced to 80-85%, and the air speed and the air volume are gradually increased to 40% according to a set proportion;
then adjusting the air speed and the air quantity to 70% in a set proportion, spraying a high-speed stirring emulsion mixed solution of silicon dioxide into the curing chamber through a spraying device, and bringing the mixture to the surface of the polar plate through circulating air;
and then, at the temperature of 45-65 ℃, the relative humidity is gradually reduced to 60% within 25 hours, and the air speed and the air volume are gradually increased to 80% according to the set proportion.
As a preferable technical scheme of the invention, the spraying amount of the liquid mixture is measured by each cubic meter of the curing chamber, the spraying speed is 0.3-0.5L/min, and the time is controlled to be 8-10 min.
As a preferred embodiment of the present invention, the method further comprises a curing step, which is performed after the curing step, wherein the curing step comprises drying the plate for 10 hours under conditions of a temperature of 80 ℃, a relative humidity of 0% and a circulation air speed of 100%.
The method for curing the polar plate of the lead storage battery according to claim 6, wherein before the first stage of curing, a procedure of starting a curing chamber is included, the curing chamber is heated and humidified by steam to reach the relative humidity of 98-100% and the temperature of 38-40 ℃, and the smear and the wet-grown polar plate which is hung on a curing frame after being dried are sequentially placed into the curing chamber.
The invention has the following beneficial effects:
the invention sprays a small amount of emulsified mixed liquid of silicon dioxide after shearing at the two stages, and the emulsified mixed liquid is attached to the surface of the pole plate along with circulating wind to form a protective layer, thereby improving the excessive water loss of the wet-grown pole plate under the action of the circulating wind.
The silicon dioxide emulsion mixed liquid is brought to the raw plate through the circulating air, so that the silicon dioxide emulsion mixed liquid is more through the places with more circulating air volume, the silicon dioxide emulsion mixed liquid is less through the places with less circulating air volume, the dehydration amount of the wet polar plates in different areas is balanced in the solidification, and the cracking caused by the too fast dehydration of the polar plates at the outer side or the polar plates at the positions with larger serial gaps is prevented.
The surface emulsion of the green plate is tightly combined with the lead plaster. The acid-added charged battery is dissolved in the electrolyte to supplement the colloidal electrolyte and is harmless to the battery
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Detailed Description
Example 1
And (3) sequentially placing the 6-DZF-20 wet green plate which is smeared and dried on the surface and then hung on a curing frame into a curing chamber with the relative humidity of 98-100% and the temperature of 38-40 ℃.
The drying was cured according to the procedure of the following table.
Table one:
the process is carried out according to the degree shown in the table I, and when the mixed liquid is sprayed on the two-stage remark column, the milky mixed liquid of silicon dioxide which is stirred at a high speed (the rotating speed is 1500 r/min) is sprayed into the chamber through a spraying device and is brought to the surface of the polar plate through circulating air, the spraying amount of the mixed liquid is measured by each cubic meter of the curing chamber, and the spraying speed is 0.5L/min.
After the curing and drying are finished, the polar plates at two sides of the same frame of the curing chamber are taken, the middle polar plate is checked for cracks by a visual light transmission method, and three horizontal free drop weight loss tests with the height of 1 meter are carried out.
Table two: the measured data are as follows,
example 2
And (3) sequentially placing the 6-DZF-20 wet green plate which is smeared and dried on the surface and then hung on a curing frame into a curing chamber with the relative humidity of 98-100% and the temperature of 38-40 ℃.
Curing and drying are carried out according to the following three procedures.
Table three:
the three degrees of the above are carried out, and when the mixed liquid is sprayed on the two-stage remark column, the milky mixed liquid of silicon dioxide which is stirred at a high speed (the rotating speed is 800 r/min) is sprayed into the chamber through a spraying device and is brought to the surface of the polar plate through circulating air, the spraying amount of the mixed liquid is measured by each cubic meter of the curing chamber, and the spraying speed is 0.3L/min.
After the curing and drying are finished, the polar plates at two sides of the same frame of the curing chamber are taken, the middle polar plate is checked for cracks by a visual light transmission method, and three horizontal free drop weight loss tests with the height of 1 meter are carried out.
Table four: the data were obtained as follows from the measurements,
example 3
Sequentially placing the 6-DZF-20 wet green polar plate which is smeared and dried on the surface and then hung on a curing frame into a curing chamber with the relative humidity of 98-100% and the temperature of 38-40 ℃; the curing and drying were carried out according to the following five procedures.
Table five:
and the five degrees of the above are carried out, and when the mixed liquid is sprayed on the two-stage remark column, the milky mixed liquid of silicon dioxide which is stirred at a high speed (the rotating speed is 1000 revolutions per minute) is sprayed into the chamber through a spraying device and is brought to the surface of the polar plate through circulating air, the spraying amount of the mixed liquid is measured by each cubic meter of the curing chamber, and the spraying speed is 0.4L/min.
After the curing and drying are finished, the polar plates at two sides of the same frame of the curing chamber are taken, the middle polar plate is checked for cracks by a visual light transmission method, and three horizontal free drop weight loss tests are carried out at the height of 1 m.
Table six: the data were obtained as follows from the measurements,
comparative example 1
And (3) placing the 6-DZF-20 wet green plate which is coated and dried on the surface and then hung on a curing frame into a curing chamber with the relative humidity of 98-100% and the temperature of 38-40 ℃ in sequence, and curing and drying according to the seven procedures in the following table.
TABLE VII:
after the curing and drying are finished, the polar plates at two sides of the same frame of the curing chamber are taken, the middle polar plate is checked for cracks by a visual light transmission method, and three horizontal free drop weight loss tests with the height of 1 meter are carried out.
Table eight: the data were obtained as follows from the measurements,
comparative example 2
Sequentially placing the 6-DZF-20 wet green polar plate which is smeared and dried on the surface and then hung on a curing frame into a curing chamber with the relative humidity of 98-100% and the temperature of 38-40 ℃; curing and drying were carried out according to the nine procedures shown below.
Table nine:
after the curing and drying are finished, the polar plates at two sides of the same frame of the curing chamber are taken, the middle polar plate is checked for cracks by a visual light transmission method, and three horizontal free drop weight loss tests with the height of 1 meter are carried out.
TABLE Ten: the data were obtained as follows from the measurements,
comparative example 3
And (3) placing the 6-DZF-20 wet green plate which is coated and dried on the surface and then hung on a curing frame into a curing chamber with the relative humidity of 98-100% and the temperature of 38-40 ℃ in sequence, and curing and drying according to the eleventh procedure in the following table.
Table eleven:
after the curing and drying are finished, the polar plates at two sides of the same frame of the curing chamber are taken, the middle polar plate is checked for cracks by a visual light transmission method, and three horizontal free drop weight loss tests with the height of 1 meter are carried out.
Table twelve: the measured data are as follows:
the positive plate and the negative plate prepared in example 1 and comparative example 1 were assembled into batteries (6-DZF-20, 50 batteries per type) of the same specification by selecting the outer plate serially hung on the curing frame or the plate at the position with larger serial hanging gap, the middle plate and the mixed plate respectively, and the detection was performed.
In example 1, 50 batteries assembled with the outer plates serially connected on the curing rack or the plates at the positions where the serially connected gaps are larger were subjected to acid charging and finishing, and then subjected to capacity detection. The single cell was left to stand at 25. + -. 1 ℃ for 10h and then discharged at 10A to an average cell voltage of 1.75V and the discharge time was recorded. The discharge time is 128.0-132.0 min, and the discharge time range is 4.0 min.
In example 1, 50 batteries assembled on the middle plate serially hung on the curing rack were subjected to acid charging and finishing, and then subjected to capacity detection. The single cell was left to stand at 25. + -. 1 ℃ for 10h and then discharged at 10A to an average cell voltage of 1.75V and the discharge time was recorded. The discharge time is 128.0-131.5 min, and the discharge time range is 3.5 min.
In example 1, 50 batteries assembled by mixing plates in a curing frame were subjected to acid charging and finishing, and then subjected to capacity detection. The single cell was left to stand at 25. + -. 1 ℃ for 10h and then discharged at 10A to an average cell voltage of 1.75V and the discharge time was recorded. The discharge time is 128.0-131.5 min, and the discharge time range is 3.5 min.
In comparative example 1, 50 batteries assembled with the outer plates serially hung on the curing rack or the plates at the positions with larger serial hanging gaps were subjected to acid charging and finishing, and then capacity detection was performed. The single cell was left to stand at 25. + -. 1 ℃ for 10h and then discharged at 10A to an average cell voltage of 1.75V and the discharge time was recorded. The discharge time is 124.5-131.5 min, and the discharge time range is 7.0 min.
In comparative example 1, 50 cells assembled from middle plates serially hung on a curing frame were subjected to acid charging and finishing, and then subjected to capacity detection. The single cell was left to stand at 25. + -. 1 ℃ for 10h and then discharged at 10A to an average cell voltage of 1.75V and the discharge time was recorded. The discharge time is 127.5-131.5 min, and the discharge time range is 4.0 min.
In comparative example 1, 50 cells assembled with mixed plates in a curing frame were subjected to acid charging and finishing, and then subjected to capacity detection. The single cell was left to stand at 25. + -. 1 ℃ for 10h and then discharged at 10A to an average cell voltage of 1.75V and the discharge time was recorded. The discharge time is 125.0-131.0 min, and the discharge time range is 6.0 min.
The above comparative results show that:
in the light transmission crack inspection and the falling weight loss detection of the examples 1, 2 and 3 and the comparative examples 1, 2 and 3, the cracking improvement of the serial outer side polar plate or the polar plate at the position with larger serial gap is obvious, and the falling average weight loss is reduced by more than 50%. Through the comparison of the battery capacity tests of the embodiment 1 and the battery assembled by the outer side polar plates which are hung in series or the polar plates at the positions with larger gaps in series, the middle polar plates which are hung in series and the mixed polar plates in series in the comparison example 1, the battery assembled at different positions in the embodiment 1 has small difference value of the discharge time, and is better than the battery assembled at different positions in the comparison example 1, and the discharge consistency is obviously improved.
In the above-described embodiments 1 to 3,
the emulsion mixture is prepared by the following method:
stp 1; weighing fumed silica, polyacrylamide and pure water for later use, wherein the fumed silica and the polyacrylamide respectively account for 0.5 wt% and 0.05 wt% of the total raw materials, and the balance is the pure water;
stp2 and pure water are put into a high-speed stirring and strong shearing nanometer material mixing integrated machine body;
stp3, starting a vacuum high-speed stirring and strong shearing nano material mixing all-in-one machine, starting a vacuum system to suck the needed fumed silica and polyacrylamide powder, and stirring at high speed;
stp4, after stirring, carrying out positive and negative strong shearing on the emulsion in a mixing all-in-one machine, wherein the positive shearing rotating speed is 3000r/min, the reverse shearing rotating speed is 1500r/min, and the shearing time is 10-15 min, thus obtaining the completely uniform milky mixed liquid containing silicon dioxide.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (10)
1. A method for curing a lead storage battery plate is characterized by comprising the following steps: comprises spraying silicon dioxide emulsion mixture on the surface of the pole plate by circulating air in the curing stage.
2. The method for curing a lead-acid battery plate according to claim 1, wherein the emulsion mixture is prepared by the following method:
stp 1; weighing fumed silica, polyacrylamide and pure water for later use;
stp2 and pure water are put into a high-speed stirring and strong shearing nanometer material mixing integrated machine body;
stp3, starting a vacuum high-speed stirring and strong shearing nano material mixing all-in-one machine, starting a vacuum system to suck the needed fumed silica and polyacrylamide powder, and stirring at high speed;
stp4, after stirring, the emulsion is strongly sheared in the mixing machine to obtain the completely uniform milky mixed liquid containing silicon dioxide.
3. The method for curing a lead acid battery plate according to claim 2, wherein the ratios of fumed silica and polyacrylamide to the total raw materials in stp1 are 0.4 to 0.5 wt% and 0.05 to 0.06 wt%, respectively.
4. The method according to claim 3, wherein the ratio of fumed silica and polyacrylamide to the total raw material in stp1 is 0.5 wt% and 0.05 wt%, respectively.
5. The method for curing a lead storage battery plate according to any one of claims 2 to 4, wherein the Stp4 has a forward shear rotation speed of 3000r/min, a reverse shear rotation speed of 1500r/min and a shear time of 10-15 min.
6. The method of claim 1, further comprising a curing stage prior to the curing stage; in the first stage of curing, the polar plate is placed under the conditions that the relative humidity is 98-100%, the air speed and the air quantity are set to be proportional to the air quantity set to be 0-30%, the curing temperature is gradually increased to 65-80 ℃, and then the polar plate is kept at the temperature for 3-5 hours.
7. The method for curing the lead storage battery plate according to claim 6, wherein in the curing stage, the curing temperature is gradually reduced to 45-65 ℃ within 3-5 hours, the humidity is gradually reduced to 80-85%, and the air speed and the air volume are gradually increased to 40% according to a set proportion;
then adjusting the air speed and the air quantity to 70% in a set proportion, spraying a high-speed stirring emulsion mixed solution of silicon dioxide into the curing chamber through a spraying device, and bringing the mixture to the surface of the polar plate through circulating air;
then, at the temperature of 45-65 ℃, the relative humidity is gradually reduced to 60% within 25 hours, and the air speed and the air volume are gradually increased to 80% according to the set proportion.
8. The method of claim 7, wherein the amount of the liquid mixture is 0.3-0.5L/min per cubic meter of the curing chamber, and the time is controlled to be 8-10 min.
9. The method of claim 6, further comprising a curing step after the curing step, wherein the curing step comprises drying the plate for 10 hours at 80 ℃, a relative humidity of "0" and a circulation air speed of 100%.
10. The method for curing the polar plate of the lead storage battery according to claim 6, wherein before the first stage of curing, a procedure of starting a curing chamber is included, the curing chamber is heated and humidified by steam to reach the relative humidity of 98-100% and the temperature of 38-40 ℃, and the smear and the wet-grown polar plate which is hung on a curing frame after being dried are sequentially placed into the curing chamber.
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| CN112768641A (en) * | 2021-01-20 | 2021-05-07 | 天能电池集团股份有限公司 | Preparation method of lead storage battery polar plate and lead storage battery polar plate |
| CN113506859A (en) * | 2021-07-08 | 2021-10-15 | 江苏理士电池有限公司 | Curing and drying method for long-life valve-regulated lead-acid storage battery wet lead plaster polar plate |
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