CN114551815B - Lead storage battery polar plate curing method - Google Patents
Lead storage battery polar plate curing method Download PDFInfo
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- CN114551815B CN114551815B CN202210140766.4A CN202210140766A CN114551815B CN 114551815 B CN114551815 B CN 114551815B CN 202210140766 A CN202210140766 A CN 202210140766A CN 114551815 B CN114551815 B CN 114551815B
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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 method for curing a lead storage battery polar plate, and relates to the technical field of lead storage battery production. The invention comprises spraying silicon dioxide emulsion mixture on the surface of the polar plate by circulating air in the solidification stage; the emulsion mixture is prepared by the following steps: weighing fumed silica, polyacrylamide and pure water for later use; pure water is put into a body of the high-speed stirring and strong shearing nano material mixing integrated machine; starting a vacuum high-speed stirring and strong shearing nano material mixing integrated machine, starting a vacuum system to suck the required fumed silica and polyacrylamide powder, and stirring at a high speed; after the stirring is completed, the emulsion is subjected to positive and negative strong shearing in a mixing integrated machine, and the completely uniform emulsion mixed liquid containing silicon dioxide is prepared. The small amount of the emulsion mixture of the sheared silicon dioxide sprayed in two stages is attached to the surface of the polar plate along with circulating wind to form a protective layer, so that the problem that the wet polar plate is too fast in water loss under the action of the circulating wind is solved.
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 polar plate.
Background
In the manufacturing of lead-acid batteries, the curing of the polar plates is a special process in the production process of the batteries, and the quality of the polar plates is determined by the curing effect, so that the discharge capacity of the assembled batteries, the consistency of the battery capacity and the cycle life of the assembled batteries are ensured.
The plate curing and drying of the battery in the production enterprise is generally carried out in three steps, the first step is a high-humidity stage, and the purpose of high-humidity standing in the stage is to gradually lead sulfate generated in the paste mixing process to basic lead sulfate 3 PbO.PbSO with crystal water 4 ·H 2 O and 4 PbO.PbSO 4 Is transformed by (a); the second stage is a free lead oxidation stage of lead plaster dehydration and forms a grid corrosion layer, wherein the free lead oxidation is related to the environmental humidity, the moisture content of the lead plaster and the circulating wind, the outer side polar plate or polar plate with larger series-hanging gap on the curing frame is influenced by the circulating wind, and the dehydration and curing of the middle polar plate of the series-hanging are carried out before the dehydration and curing of the middle polar plate of the series-hanging, so that the curing synchronism of the stage is poor, and the outer side polar plate or series-hanging gap is formedThe polar plate with too fast water loss at the bigger part forms cracking; the third stage is the plate drying process, which has little chemical change.
In order to obtain the consistency of the polar plates, the manufacturing enterprises spread gunny bags on the curing frame to prevent the polar plates at the outer sides from being dehydrated too quickly in the curing and drying process, and take out the gunny bags to directly dry the polar plates during drying. When the method is used for curing, the polar plate is blocked by the gunny bag to the wind, only a small amount of circulating wind participates in the curing for a long time, and the polar plate is not suitable for mass production and has low production efficiency.
Disclosure of Invention
The invention aims to provide a method for curing a lead storage battery plate, which is characterized in that in the two stages of curing and drying, circulating air is sprayed into emulsion mixed liquid of silicon dioxide in a curing chamber and is more distributed on the surface of a plate at the outer side of a serial-hanging plate or a plate at a position with a larger serial-hanging gap so as to balance and improve the dehydration condition of the plate in the process of oxidizing in curing, so that a good curing effect is obtained; the polar plate has no crack, less surface layer floating powder and strong discharge consistency of the assembled and charged battery.
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 polar plate, which comprises spraying an emulsion mixture of silicon dioxide on the surface of the polar plate through circulated air in a curing stage.
As a preferable technical scheme of the invention, the emulsion mixture is prepared by the following steps:
stp1; weighing fumed silica, polyacrylamide and pure water for later use;
stp2 and pure water are placed into a body of the high-speed stirring and strong shearing nano material mixing all-in-one machine;
stp3, starting a vacuum high-speed stirring and strong shearing nano material mixing integrated machine, starting a vacuum system to suck the required fumed silica and polyacrylamide powder, and stirring at a high speed;
and after Stp4 is stirred, the emulsion is subjected to positive and negative strong shearing in a mixing integrated machine, and the emulsion mixture completely and uniformly containing silicon dioxide is prepared.
As a preferable technical scheme of the invention, in the stp1, the proportion of the fumed silica and the polyacrylamide in the total raw materials is respectively 0.4-0.5 wt% and 0.05-0.06 wt%.
As a preferred embodiment of the present invention, in the stp1, the fumed silica and the polyacrylamide are present in an amount of 0.5wt% and 0.05wt%, respectively, based on the total raw material.
As a preferable technical scheme of the invention, in Stp4, the forward shearing rotating speed is 3000r/min, the reverse shearing rotating speed is 1500r/min, and the shearing time is 10-15 min.
As a preferred technical scheme of the invention, the method further comprises a first curing stage which is performed before the second curing stage; the first stage of curing is to place the polar plate under the conditions of 98-100% of relative humidity and 0-30% of wind speed and wind quantity, raise the curing temperature to 65-80 deg.c and maintain the temperature for 3-5 hr.
As a preferable technical scheme of the invention, when the curing phase is in the curing phase, 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 air quantity setting proportion is gradually increased to 40%;
then the wind speed and the wind quantity are adjusted to 70 percent, and emulsion mixed liquid of high-speed stirred silicon dioxide is sprayed into a curing chamber through a spraying device and is brought to the surface of the polar plate through circulating wind;
then the relative humidity is gradually reduced to 60% in 25 hours at the temperature of 45-65 ℃, and the wind speed and the wind quantity set proportion is gradually increased to 80%.
As a preferable technical scheme of the invention, the spraying rate of the mixed liquid is 0.3-0.5L/min according to the per cubic meter of the curing chamber, and the time is controlled to be 8-10min continuously.
As a preferred technical scheme of the invention, the method further comprises a three-stage curing process carried out after the two-stage curing process, wherein the three-stage curing process comprises the step of putting the polar plate into a condition of 80 ℃ and having a relative humidity of 0 and a circulating air speed of 100% and drying for 10 hours.
The method according to claim 6, wherein before the first stage of curing, the method comprises starting a curing chamber program, heating the curing chamber to humidify the curing chamber to 98-100% relative humidity and 38-40 ℃ by steam, and sequentially placing the smear and the wet green electrode plate strung on the curing frame after surface drying into the curing chamber.
The invention has the following beneficial effects:
the invention forms a protective layer on the surface of the polar plate along with circulating wind by spraying a small amount of silicon dioxide emulsion mixture after shearing in two stages, and improves the excessive water loss of the wet polar plate under the action of the circulating wind.
The emulsion mixture of silicon dioxide is carried to the green plate through the circulating air, so that the emulsion mixture of the attached silicon dioxide is more through the place with more circulating air quantity, and the emulsion mixture of the attached silicon dioxide is less through the place with less circulating air quantity, so that the dewatering quantity of wet polar plates in different areas is balanced in solidification, and the polar plates at the outer side of the cross hanging or the positions with larger cross hanging gaps are prevented from being dehydrated too quickly to generate cracking.
The emulsion on the surface layer of the green plate is tightly combined with the lead plaster. The battery is charged after being added with acid and then dissolved in electrolyte to be used as the supplement of colloid electrolyte, and is harmless to the battery.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Detailed Description
Example 1
The 6-DZF-20 wet green polar plate which is serially hung on a curing frame after the smear and the surface are dried is sequentially placed 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 procedure shown in Table I.
Table one:
the process is carried out according to the first degree of the table, and during the procedure of spraying the mixed solution in the two-stage remarking column, the emulsion mixed solution of the silicon dioxide which is stirred at high speed (rotating speed is 1500 revolutions per minute) is sprayed into the chamber through a spraying device, the emulsion mixed solution is brought to the surface of the polar plate through circulating air, and the spraying rate of the mixed solution is 0.5L/min according to each cubic meter of the curing chamber.
And after the solidification and drying are finished, taking the side polar plates on the two sides of the same frame of the solidification chamber, checking cracks on the middle polar plate by using a visual light transmission method, and carrying out three-time horizontal free falling weightlessness test at a height of 1 meter.
And (II) table: the data were measured as follows,
example 2
The 6-DZF-20 wet green polar plate which is serially hung on a curing frame after the smear and the surface are dried is sequentially placed 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 following procedure three.
Table three:
the process is carried out according to the three degrees of the table, and during the procedure of spraying the mixed liquid in the two-stage remarking column, the emulsion mixed liquid of the silicon dioxide which is stirred at high speed (the rotating speed is 800 revolutions per minute) is sprayed into the chamber through a spraying device, the emulsion mixed liquid is brought to the surface of the polar plate through circulating air, and the spraying rate of the mixed liquid is 0.3L/minute according to each cubic meter of the curing chamber.
And after the solidification and drying are finished, taking the side polar plates on the two sides of the same frame of the solidification chamber, checking cracks on the middle polar plate by using a visual light transmission method, and carrying out three-time horizontal free falling weightlessness test at a height of 1 meter.
Table four: it is measured that the data is as follows,
example 3
The 6-DZF-20 wet green polar plates which are serially hung on a curing frame after the smear and the surface are dried are sequentially placed 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 procedure shown in Table five.
Table five:
the procedure is carried out according to the fifth degree of the table, and during the procedure of spraying the mixed solution in the two-stage remarking column, the emulsion mixed solution of the silicon dioxide which is stirred at high speed (rotating speed 1000 rpm) is sprayed into the chamber through a spraying device, the emulsion mixed solution is brought to the surface of the polar plate through circulating air, and the spraying rate of the mixed solution is 0.4L/min according to each cubic meter of the curing chamber.
And after the solidification and drying are finished, taking the side polar plates on the two sides of the same frame of the solidification chamber, checking cracks on the middle polar plate by using a visual light transmission method, and carrying out three-time horizontal free falling weightlessness test at a height of 1 meter.
Table six: it is measured that the data is as follows,
comparative example 1
The 6-DZF-20 wet green polar plate which is serially hung on a curing frame after the smear and the surface are dried is sequentially placed into a curing chamber with the relative humidity of 98-100% and the temperature of 38-40 ℃ for curing and drying according to the following seven procedures.
Table seven:
and after the solidification and drying are finished, taking the side polar plates on the two sides of the same frame of the solidification chamber, checking cracks on the middle polar plate by using a visual light transmission method, and carrying out three-time horizontal free falling weightlessness test at a height of 1 meter.
Table eight: it is measured that the data is as follows,
comparative example 2
The 6-DZF-20 wet green polar plates which are serially hung on a curing frame after the smear and the surface are dried are sequentially placed 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 procedure shown in Table nine.
Table nine:
and after the solidification and drying are finished, taking the side polar plates on the two sides of the same frame of the solidification chamber, checking cracks on the middle polar plate by using a visual light transmission method, and carrying out three-time horizontal free falling weightlessness test at a height of 1 meter.
Table ten: it is measured that the data is as follows,
comparative example 3
The 6-DZF-20 wet green polar plate which is serially hung on a curing frame after the smear and the surface are dried is sequentially placed into a curing chamber with the relative humidity of 98-100% and the temperature of 38-40 ℃ for curing and drying according to the eleventh procedure of the table.
Table eleven:
and after the solidification and drying are finished, taking the side polar plates on the two sides of the same frame of the solidification chamber, checking cracks on the middle polar plate by using a visual light transmission method, and carrying out three-time horizontal free falling weightlessness test at a height of 1 meter.
Table twelve: the measured data are as follows:
the positive plate and the negative plate prepared in the example 1 and the comparative example 1 are respectively selected from an outer side polar plate strung with a curing frame or a polar plate with a larger strung gap, a middle polar plate and a mixed polar plate to be assembled into batteries (6-DZF-20, 50 batteries of each type) with the same specification, and detection is carried out.
In example 1, 50 batteries assembled by the outer electrode plates strung on the curing frame or the electrode plates with larger strung gaps were subjected to capacity detection after acid charging and finishing. The single cell was left to stand for 10 hours at 25.+ -. 1 ℃ 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 is extremely poor at 4.0min.
In example 1, 50 batteries assembled by a middle plate strung on a curing frame were subjected to capacity detection after acid charging and finishing. The single cell was left to stand for 10 hours at 25.+ -. 1 ℃ 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 is extremely 3.5min.
In example 1, 50 batteries assembled by the mixed polar plates in the curing frame were subjected to capacity detection after being subjected to acid charging and finishing. The single cell was left to stand for 10 hours at 25.+ -. 1 ℃ 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 is extremely 3.5min.
In comparative example 1, 50 batteries assembled by the outer electrode plates strung on the curing frame or the electrode plates where the strung gaps are larger were subjected to capacity detection after acid charging and finishing. The single cell was left to stand for 10 hours at 25.+ -. 1 ℃ 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 is 7.0min.
In comparative example 1, 50 batteries assembled by the middle plate strung on the curing rack were subjected to capacity detection after acid charging and finishing. The single cell was left to stand for 10 hours at 25.+ -. 1 ℃ 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 is extremely poor at 4.0min.
In comparative example 1, 50 batteries assembled with a mixed electrode plate in a curing frame were subjected to capacity detection after being subjected to acid charging and finishing. The single cell was left to stand for 10 hours at 25.+ -. 1 ℃ 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 is 6.0min.
The comparison results show that:
in examples 1, 2 and 3, and in comparative examples 1, 2 and 3, light-transmitting crack inspection and drop weight loss detection are carried out, the crack improvement of the plates at the positions with larger string hanging outer side plates or string hanging gaps is obvious, and the drop average weight loss is reduced by more than 50%. Compared with the battery capacity test of the battery assembled by the serial hanging outer side polar plate or the polar plate with larger serial hanging gap, the serial hanging middle polar plate and the mixed polar plate of the embodiment 1, the battery assembled at different positions of the embodiment 1 has small discharge time difference value, and is superior to the battery assembled at different positions of the embodiment 1, and the discharge consistency is obviously improved.
In the above-described embodiments 1 to 3,
the emulsion mixture is prepared by the following steps:
stp1; weighing fumed silica, polyacrylamide and pure water for standby, wherein the fumed silica and the polyacrylamide account for 0.5 weight percent and 0.05 weight percent of the total raw materials respectively, and the balance is the pure water;
stp2 and pure water are placed into a body of the high-speed stirring and strong shearing nano material mixing all-in-one machine;
stp3, starting a vacuum high-speed stirring and strong shearing nano material mixing integrated machine, starting a vacuum system to suck the required fumed silica and polyacrylamide powder, and stirring at a high speed;
after Stp4 and stirring, the emulsion is subjected to positive and negative strong shearing in a mixing integrated machine, the forward shearing rotating speed is 3000r/min, the reverse shearing rotating speed is 1500r/min, and the shearing time is 10-15 min, so that the emulsion mixture completely and uniformly containing silicon dioxide is prepared.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, 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 present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. 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 only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form 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 understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (7)
1. A lead storage battery plate curing method is characterized in that: the method comprises spraying silicon dioxide emulsion mixture on the surface of the polar plate by circulating air in the solidification stage;
a first curing stage carried out before the second curing stage; the first stage of curing is to place the polar plate under the conditions that the relative humidity is 98-100% and the set proportion of wind speed and wind quantity is 0-30%, firstly raising the curing temperature to 65-80 ℃ gradually, and keeping the temperature for 3-5 hours;
when the curing phase is adopted, 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 air quantity setting proportion is gradually increased to 40%;
then the wind speed and the wind quantity are adjusted to 70 percent, and emulsion mixed liquid of high-speed stirred silicon dioxide is sprayed into a curing chamber through a spraying device and is brought to the surface of the polar plate through circulating wind;
then the relative humidity is gradually reduced to 60% in 25 hours at the temperature of 45-65 ℃, and the wind speed and the wind quantity set proportion is gradually increased to 80%;
the method also comprises a three-stage curing after the two-stage curing, wherein the three-stage curing comprises the steps of putting the polar plate into a condition that the temperature is 80 ℃, the relative humidity is 0, and the circulating wind speed is 100 percent and drying for 10 hours;
the amount of the emulsion mixture adhering to silica is large in the region where the circulation air volume is large, while the amount of the emulsion mixture adhering to silica is small in the region where the circulation air volume is small.
2. The method for curing a lead storage battery plate according to claim 1, wherein the emulsion mixture is prepared by the following steps:
stp1; weighing fumed silica, polyacrylamide and pure water for later use;
stp2 and pure water are placed into a body of the high-speed stirring and strong shearing nano material mixing all-in-one machine;
stp3, starting a vacuum high-speed stirring and strong shearing nano material mixing integrated machine, starting a vacuum system to suck the required fumed silica and polyacrylamide powder, and stirring at a high speed;
and after Stp4 is stirred, the emulsion is subjected to positive and negative strong shearing in a mixing integrated machine, and the emulsion mixture completely and uniformly containing silicon dioxide is prepared.
3. The method for curing a lead storage battery plate according to claim 2, wherein in the stp1, the fumed silica and the polyacrylamide are present in an amount of 0.4 to 0.5wt% and 0.05 to 0.06wt%, respectively, based on the total raw material.
4. A method of curing a lead storage battery plate according to claim 3, wherein in the stp1, the fumed silica and the polyacrylamide are present in an amount of 0.5wt% and 0.05wt%, respectively, based on the total raw material.
5. The method for curing a lead storage battery plate according to any one of claims 2 to 4, wherein in the Stp4, the forward shearing rotational speed is 3000r/min, the reverse shearing rotational speed is 1500r/min, and the shearing time is 10 to 15min.
6. The method for curing the lead storage battery plate according to claim 1, wherein the spraying amount of the mixed liquid is 0.3-0.5L/min per cubic meter of the curing chamber, and the time is controlled to be 8-10min continuously.
7. The method for curing a lead storage battery plate according to claim 1, wherein the step of curing is preceded by a step of starting a curing chamber program, heating the curing chamber to humidify the curing chamber to 98-100% relative humidity and 38-40 ℃ by steam, and sequentially placing the smear and the wet green plate which is hung on a curing frame after surface drying 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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