CN112002877B - Optimization process of grid and active material interface - Google Patents

Optimization process of grid and active material interface Download PDF

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Publication number
CN112002877B
CN112002877B CN202010720188.2A CN202010720188A CN112002877B CN 112002877 B CN112002877 B CN 112002877B CN 202010720188 A CN202010720188 A CN 202010720188A CN 112002877 B CN112002877 B CN 112002877B
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grid
temperature
curing
active material
sulfuric acid
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CN112002877A (en
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姚秋实
张峰博
王娟
许宝云
周贤机
李桂发
李进兴
张开红
田庆山
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Tianneng Battery Group Co Ltd
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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
    • 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
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/68—Selection of materials for use in lead-acid accumulators
    • H01M4/685—Lead alloys
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/73—Grids for lead-acid accumulators, e.g. frame plates
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses an optimization process of a grid and active material interface, which comprises the following steps: (1) soaking the grid in water, and then placing the grid in an oxygen-enriched environment for 12-48 h; (2) dipping the grid obtained in the step (1) in a sulfuric acid solution for 1-24 h; then, cleaning sulfuric acid on the surface of the grid, and drying; (3) filling lead plaster on the dried grid, and then sending the grid into a curing chamber for curing; the curing comprises the following steps: keeping at temperature above 50 deg.C and humidity above 80% for 2-8 hr, and dehydrating and drying. The process can accurately control the thickness of the grid and active material interface corrosion layer, can form a completely covered corrosion layer on the surface of the grid, is beneficial to keeping the discharge capacity of the battery, and prolongs the service life of the battery.

Description

Optimization process of grid and active material interface
Technical Field
The invention relates to the technical field of lead storage battery manufacturing, in particular to an optimization process of a grid and active material interface.
Background
The grid is used as a lead storage battery framework, plays a role in supporting positive and negative active substances in the battery, and also plays a role in outputting and inputting current to each part of the polar plate. The valve-regulated lead-acid grid storage battery grid generally adopts a lead-calcium-tin-aluminum alloy grid, and under the condition of deep cycle use, a passivation layer is easily formed on the interface between the grid and an active matter, so that the capacity of the battery is rapidly reduced.
The formation of the passivation layer is believed to be related to the thickness of the corrosion layer formed at the interface between the grid and the active material. And no corrosion layer is formed at the interface of the grid and the active material or the formed corrosion layer is thin, so that the capacity of the battery is easy to attenuate. The analysis is carried out on batteries with attenuated or laggard market feedback capacity, a layer of white substance or offwhite substance is arranged on the surface of a considerable part of battery grids, and the surface of a normal battery grid is free of the white substance or the offwhite substance. The grid and the active substance are separated by the white substance, so that part of the active substance can not be effectively utilized. In order to form a good corrosion layer between the grid and the active material, a long curing time is generally adopted in production, but the phenomenon of uneven oxidation still exists on the surface of the grid, and an extremely small gap exists between the grid and the active material, so that the capacity of the battery is quickly reduced in subsequent use. The good connection between the battery grid and the active material is of great significance to the battery capacity maintenance.
Chinese patent publication No. CN107190303A discloses a lead storage battery grid with a composite coating and a preparation method thereof. A lead alloy grid is used as a matrix, a compact lead dioxide oxide film is formed on the surface of the lead alloy by adopting an electrochemical oxidation method, and titanium suboxide is deposited on the surface of the lead dioxide oxide film by utilizing a cathode electrodeposition method. The composite coating prepared on the surface of the lead alloy grid by the method greatly improves the corrosion resistance of the grid and prolongs the service life of the grid on the premise of ensuring the conductivity of the grid. The method has complex operation and high cost.
Chinese patent publication No. CN104485460A discloses a grid caustic soda treatment solution and a caustic soda process, which are composed of the following components in percentage by mass: 1-4% of phosphorous acid, 92-94% of pure water and 4-5% of caustic soda flakes. After cooling the lead-calcium-tin-aluminum grid to room temperature, putting the grid into the prepared treatment liquid, soaking for 20-40min, taking out the grid, air-drying, and observing the color of the grid after age hardening at room temperature, wherein the color of the grid is determined by the appearance of a light red substance; and (3) normally pasting, and adopting a 75 ℃ high-temperature curing process to manufacture the long-life positive plate.
Chinese patent publication No. CN101515643 discloses an oxidation method for a grid of a lead-acid storage battery. And (3) oxidizing the grid for 5-25 hours in an environment with the temperature of 30-55 ℃ and the relative humidity of 80-98%. The oxidation is accelerated, lead oxide is formed on the surface of the grid, the oxide layer on the surface of the grid is thickened, the compact oxide layer formed in the air on the surface of the grid is damaged, a loose oxide layer structure is formed, and the corrosion is irregular on the interface of the grid and the oxide layer, so that the bonding capacity of the grid and the active substance is improved, and the interface resistance of the grid and the active substance is smaller. In the method, after the surface of the grid is oxidized, the thickness of an oxide layer is increased, the binding force between the grid and the lead plaster after coating is only provided by a hydration layer, PbO on the surface of the grid does not react with the lead plaster, a new phase cannot be formed, and the binding force is weak.
Disclosure of Invention
The invention provides an optimization process of a grid and an active material interface, which can accurately control the thickness of a grid and active material interface corrosion layer, can form a completely covered corrosion layer on the surface of the grid, is beneficial to maintaining the discharge capacity of a battery and prolonging the service life of the battery.
The specific technical scheme is as follows:
an optimization process of an interface between a grid and an active material comprises the following steps:
(1) soaking the grid in water, and then placing the grid in an oxygen-enriched environment for 12-48 h;
(2) dipping the grid obtained in the step (1) in a sulfuric acid solution for 1-24 h; then, cleaning sulfuric acid on the surface of the grid, and drying;
(3) filling lead plaster on the dried grid, and then sending the grid into a curing chamber for curing; the curing comprises the following steps: keeping at temperature above 50 deg.C and humidity above 80% for 2-8 hr, and dehydrating and drying.
The method is suitable for lead matrix alloy grids such as lead-calcium alloy and lead-antimony alloy grids.
The common process is to directly fill and coat the grid with lead plaster, because oxygen is needed for the reaction of grid alloy and the lead plaster, and the generation reaction of the corrosion layer on the surface of the grid after the grid is coated by the lead plaster is controlled by the diffusion of the oxygen, the reaction rate is slow, a thicker corrosion layer is difficult to form, and the formation of the corrosion layer needs a longer time. In addition, partial positions on the surface of the grid are oxidized to form lead oxide on the surface, the lead oxide and lead paste do not react in the subsequent curing process, gray black spots are formed on the surface of the grid after curing, and the contact between the spot areas and the lead paste is poor, so that the subsequent capacity of the battery is attenuated.
According to the invention, a lead sulfate layer is formed on the surface of the grid through treatment, the lead sulfate layer and the lead plaster filled subsequently react with each other to generate a new phase and form a corrosion layer completely wrapping the grid, the grid and the lead plaster form a whole, the corrosion layer is firmly combined with active substances in the lead plaster and is not easy to fall off, and the cycle life of the battery is further prolonged.
In the step (1), the oxygen-enriched environment refers to an environment with an oxygen concentration of 10-100%.
In the step (1), the grid is immersed in water at 0-45 ℃ for 3-30 s.
The thickness and the density of the lead sulfate layer formed on the surface of the grid can be adjusted by changing the thickness of the lead oxide layer and the pickling condition.
The thickness of the oxidation layer can be adjusted by changing the temperature, the air humidity and the oxidation time under the oxygen-enriched environment.
Preferably, in the step (1), the grid is put into water with the temperature of 0-45 ℃ for 3-30 s; further preferably, the grid is put into water with the temperature of 0-45 ℃ for 10-30 s.
Preferably, in the step (1), the temperature of the oxygen-enriched environment is 0-45 ℃, and the relative humidity is 50-85%.
The density of the lead sulfate layer can be adjusted by changing the pickling temperature, the pickling density and the pickling time.
Preferably, the temperature of the sulfuric acid solution is 0-45 ℃, and the density is 1.05-1.50g/cm3。
Preferably, in the step (3), the water content of the lead paste is 5-13%.
After the treatment of the step (1), generating an oxide layer with the thickness of 1-10um on the surface of the grid; after the treatment of the step (2), generating a lead sulfate layer with the thickness of 1-10um on the surface of the grid, and tightly wrapping the lead sulfate layer on the surface of the grid; and (4) forming a completely covered corrosion layer on the surface of the grid after the solidification treatment in the step (3). If the grid surface is not treated in the steps (1) and (2), a thick corrosion layer cannot be formed on the grid surface, a gap exists between the grid and the active substance at a local point position, and the grid surface can be found to be grey or black by knocking off the lead paste.
One preferred technical scheme is as follows:
an optimization process of an interface between a grid and an active material comprises the following steps:
(1) immersing a grid into water, taking out the grid and placing the grid in an oxygen-enriched environment with the temperature of 0 ℃ and the relative humidity of 50% for 12 hours;
(2) immersing the grid obtained in the step (1) at the temperature of 0 ℃ and the density of 1.50g/cm3The dipping time is 1h in the sulfuric acid solution; cleaning sulfuric acid on the surface of the grid, and drying;
(3) filling the dried grid with lead plaster, then sending the grid into a curing chamber, keeping the grid at the temperature of more than 50 ℃ and the humidity of more than 80% for 3 hours, and then dehydrating and drying the grid.
Another preferred technical scheme is as follows:
an optimization process of an interface between a grid and an active material comprises the following steps:
(1) immersing the grid into water, taking out the grid and placing the grid in an oxygen-enriched environment with the temperature of 45 ℃ and the relative humidity of 80% for 48 hours;
(2) immersing the grid obtained in the step (1) at the temperature of 45 ℃ and the density of 1.05g/cm3The dipping time is 24 hours in the sulfuric acid solution; cleaning sulfuric acid on the surface of the grid, and drying;
(3) filling the dried grid with lead paste, then sending the grid into a curing chamber, keeping the grid at the temperature of more than 50 ℃ and the humidity of more than 80% for 8 hours, and then dehydrating and drying the grid.
Compared with the prior art, the beneficial effect of this application is:
(1) the thickness of the oxidation layer can be adjusted by changing the temperature, the air humidity and the oxidation time in the oxygen-enriched environment, and the density of the lead sulfate layer can be adjusted by changing the pickling temperature, the pickling density and the pickling time. The thickness and the density of the lead sulfate layer formed on the surface of the grid can be adjusted by changing the thickness of the lead oxide layer and the pickling condition. The thickness of the corrosion layer of the present invention is thus controllable.
(2) The lead sulfate layer formed on the surface of the grid is completely covered on the surface of the grid, and the lead sulfate layer is completely covered even in a microscopic scale, so that the formed corrosion layer is also completely covered.
(3) The lead sulfate layer formed on the surface of the grid can continuously react with the lead plaster to produce a new phase, and the grid and the lead plaster form a whole, so that the binding force between the grid and the active substance is strong.
Drawings
Fig. 1 is a scanning electron micrograph of a grid surface, wherein (a) is an untreated grid and (b) is a grid treated according to steps (1) - (3) of example 1;
fig. 2 is a scanning electron micrograph of a cross section of a grid wherein (a) is the grid made in comparative example 1 and (b) is the grid made in example 1;
fig. 3 is a cycle life chart of lead-acid batteries manufactured by the grids manufactured in examples 1 and 2 and comparative examples 1 and 2.
Detailed Description
Example 1
(1) Immersing the grid into water at 0 ℃ for 10s, taking out the grid and putting the grid in an oxygen-enriched environment with the relative humidity of 50 percent at 0 ℃ (the oxygen concentration is 10-100 percent) for 12h, and forming an oxide layer with the thickness of 1-10 mu m on the surface of the grid.
(2) Immersing the oxidized grid at 0 deg.C and density of 1.50g/cm3The dipping time in the sulfuric acid solution of (2) is 1 h. A lead sulfate layer of 1-10um is formed on the surface of the grid and tightly wraps the grid.
(3) And taking out the grid soaked with the acid, putting the grid into water with the temperature of 45 ℃ to clean sulfuric acid on the surface, taking out and airing.
(4) And (3) carrying out plate coating operation on the dried grid, then sending the grid filled with the lead plaster into a curing chamber for curing, keeping the temperature above 50 ℃ and the humidity above 80% for 3h, and then entering a dehydration and drying stage.
In this embodiment, the grid surface has a fully covered corrosion layer.
Example 2
(1) Immersing the grid into water at 45 ℃ for 3s, taking out the grid and placing the grid in an oxygen-enriched environment at 45 ℃ and with the relative humidity of 80% for 48h to form an oxide layer of 1-10um on the surface of the grid.
(2) And immersing the oxidized grid into a sulfuric acid solution with the temperature of 45 ℃ and the density of 1.05g/cm3 for 24 hours. A lead sulfate layer of 1-10um is formed on the surface of the grid and tightly wraps the grid.
(3) And taking out the grid soaked with the acid, putting the grid into water at the temperature of 0 ℃ to clean sulfuric acid on the surface, taking out the grid and airing the grid in a ventilated place.
(4) And (2) carrying out plate coating operation on the dried grid (the scanning electron microscope image of which is shown in (a) in fig. 2), then sending the grid filled with the lead plaster into a curing chamber for curing, keeping the grid at the temperature of more than 50 ℃ and the humidity of more than 80% for 8h, and then entering the dehydration and drying stages. A scanning electron microscope image of the cross section of the cured grid is shown in fig. 2 (b).
In this embodiment, the grid surface has a fully covered corrosion layer.
Comparative example 1
Coating the untreated grid (the scanning electron microscope image of which is shown in figure 1), then sending the grid filled with the lead paste into a curing chamber for curing, keeping the grid at the temperature of more than 50 ℃ and the humidity of more than 80% for 3 hours, and then entering a drying and dehydrating stage. Through visual observation, a small part of yellow lead plaster is adhered to the surface of the grid, namely a small part of the yellow lead plaster forms an etching layer and is adhered to the etching layer; most of the sites appeared gray or black, i.e. no corrosion layer was formed and no yellow lead paste was attached.
A scanning electron microscope image of the cross section of the cured grid is shown in fig. 1 (b).
Comparative example 2
And (3) coating the untreated grid, then sending the grid filled with the lead plaster into a curing chamber for curing, and curing by adopting a conventional curing process. Most of the surface of the grid is adhered with yellow lead plaster, namely, a corrosion layer is formed, and a small part of the surface of the grid is gray or black and is not adhered with the yellow lead plaster.
The conventional curing process is as follows:
keeping the temperature at 85 ℃ and the humidity at 95% for 8 h;
keeping the temperature at 55 ℃ and the humidity at 95% for 3 h;
keeping the temperature at 55 ℃ and the humidity at 85% for 3 h;
keeping the temperature at 55 ℃ and the humidity at 75% for 6 h;
keeping the temperature at 55 ℃ and the humidity at 65% for 3 h;
keeping the temperature at 50 ℃ and the humidity at 50% for 3 h;
keeping the temperature at 50 ℃ and the humidity at 30% for 3 h;
keeping the temperature at 85 ℃ and the humidity at 10% for 2 h;
keeping the temperature at 85 ℃ and the humidity at 0% for 6 h;
the temperature is 50 ℃, the humidity is 0%, and the temperature is kept for 1 h.
Comparing the original grid surface with the grid surface treated in example 1 (fig. 2 (a)), it can be seen that there is a layer of more lead sulfate particles on the grid surface after treatment, which are tightly bound with the grid and grow on the grid surface. Comparing the cured cross section of the original grid (fig. 1 (b)) with the cured cross section of the grid in example 1 (fig. 2 (b)), it can be seen that there is a small gap (circled in the figure) between the original grid and the active, resulting in easy peeling of the cured corrosion layer from the grid surface. However, there is almost no gap between the grid treated in example 1 and the active material, and the cured corrosion layer is firmly bonded to the active material and is not easily peeled off.
Lead storage batteries were prepared from the grids obtained in examples 1, 2, 1 and 2 by a conventional process, and the discharge time was measured for 2hr and the discharge time at a low temperature of-18 ℃ according to the standard GB/T22199-2017, and the results are shown in Table 1. The cycle life of the lead storage battery was tested and the results are shown in fig. 3. The cycle life detection method comprises the following steps: at 25 ℃, discharging to I2Discharging current to 10.5V/current, charging to 14.8V/current limit 0.512And charging for 8 h.
TABLE 1 test results of conventional Battery Performance
Discharge time of 2hr Low temperature discharge at-18 deg.C
Example 1 128.5min 93min
Example 2 127.3min 94min
Comparative example 1 127.7min 91min
Comparative example 2 128.2min 92min
As can be seen from the test results in Table 1 and FIG. 3, the batteries of examples and comparative examples had a small difference in 2hr discharge time, and the batteries of examples had a discharge time at a low temperature of-18 ℃ which was about 2min longer than that of comparative examples. But as the number of cycles increased, the comparative example 1 cell rapidly exhibited a capacity fade, ending in about 200 battery lives. The grid treated by the conventional process in comparative example 2 had a certain decline in battery capacity with increasing cycles, but the capacity was still significantly higher than that of comparative example 1. The capacity of the battery in the embodiment 1 and the battery in the embodiment 2 at the early stage of the cycle does not obviously attenuate, the cycle life can reach about 380 times, and is prolonged by about 90 percent compared with the cycle life of the battery in the comparative example 1.
The above-mentioned embodiments 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, equivalents, etc. made within the scope of the principles of the present invention should be included in the scope of the present invention.

Claims (5)

1. An optimization process of an interface between a grid and an active material is characterized by comprising the following steps:
(1) soaking the grid in water, and then placing the grid in an oxygen-enriched environment for 12-48 h; the oxygen-enriched environment refers to an environment with the oxygen concentration of 10-100%; the temperature of the oxygen-enriched environment is 0-45 ℃, and the relative humidity is 50-85%;
(2) dipping the grid obtained in the step (1) in a sulfuric acid solution for 1-24 h; then, cleaning sulfuric acid on the surface of the grid, and drying; the temperature of the sulfuric acid solution is 0-45 ℃, and the density is 1.05-1.50g/cm3；
(3) Filling lead plaster on the dried grid, and then sending the grid into a curing chamber for curing; the curing comprises the following steps: keeping at temperature above 50 deg.C and humidity above 80% for 2-8 hr, and dehydrating and drying.
2. The process for optimizing the interface between the grid and the active material according to claim 1, wherein in the step (1), the grid is immersed in water at 0-45 ℃ for 3-30 s.
3. The process for optimizing the interface between the grid and the active material according to claim 1, wherein in step (3), the lead paste has a water content of 5-13%.
4. The process for optimizing the interface between a grid and an active material according to claim 1, comprising the steps of:
(1) immersing a grid into water, taking out the grid and placing the grid in an oxygen-enriched environment with the temperature of 0 ℃ and the relative humidity of 50% for 12 hours;
(2) immersing the grid obtained in the step (1) at the temperature of 0 ℃ and the density of 1.50g/cm3The dipping time is 1h in the sulfuric acid solution; cleaning sulfuric acid on the surface of the grid, and drying;
(3) filling lead plaster on the dried grid, and then sending the grid into a curing chamber for curing; the curing comprises the following steps: keeping at temperature above 50 deg.C and humidity above 80% for 3 hr, and dehydrating and drying.
5. The process for optimizing the interface between a grid and an active material according to claim 1, comprising the steps of:
(1) immersing the grid into water, taking out the grid and placing the grid in an oxygen-enriched environment with the temperature of 45 ℃ and the relative humidity of 80% for 48 hours;
(2) immersing the grid obtained in the step (1) at the temperature of 45 ℃ and the density of 1.05g/cm3The dipping time is 24 hours in the sulfuric acid solution; cleaning sulfuric acid on the surface of the grid, and drying;
(3) filling lead plaster on the dried grid, and then sending the grid into a curing chamber for curing; the curing comprises the following steps: keeping at temperature above 50 deg.C and humidity above 80% for 3 hr, and dehydrating and drying.
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CN103137947A (en) * 2013-03-05 2013-06-05 江苏苏中电池科技发展有限公司 Curing process of polar plate used for lead-acid battery pack
CN103490043A (en) * 2013-07-22 2014-01-01 理士电池私人有限公司 Manufacturing method of battery plate
CN110880583A (en) * 2019-11-29 2020-03-13 天能电池(芜湖)有限公司 Production process for improving paste grid combination
CN111129438A (en) * 2019-12-12 2020-05-08 双登集团股份有限公司 Preparation method of polar plate for improving binding force between positive plate grid and lead paste

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Publication number Priority date Publication date Assignee Title
JPS56168370A (en) * 1980-05-30 1981-12-24 Shin Kobe Electric Mach Co Ltd Lead acid battery
WO2013122132A1 (en) * 2012-02-14 2013-08-22 新神戸電機株式会社 Positive electrode plate for lead acid battery, method for producing said electrode plate, and lead acid battery using said positive electrode plate
CN108987678B (en) * 2018-07-31 2020-09-04 哈尔滨工业大学 Preparation method of lead-acid storage battery electrode containing lead-tin/graphene composite coating
CN110690454B (en) * 2019-09-16 2022-04-19 界首市南都华宇电源有限公司 Production process of positive plate of storage battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103137947A (en) * 2013-03-05 2013-06-05 江苏苏中电池科技发展有限公司 Curing process of polar plate used for lead-acid battery pack
CN103490043A (en) * 2013-07-22 2014-01-01 理士电池私人有限公司 Manufacturing method of battery plate
CN110880583A (en) * 2019-11-29 2020-03-13 天能电池(芜湖)有限公司 Production process for improving paste grid combination
CN111129438A (en) * 2019-12-12 2020-05-08 双登集团股份有限公司 Preparation method of polar plate for improving binding force between positive plate grid and lead paste

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