CN111416128A - Preparation method of positive plate of lead storage battery - Google Patents
Preparation method of positive plate of lead storage battery Download PDFInfo
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- CN111416128A CN111416128A CN202010229196.7A CN202010229196A CN111416128A CN 111416128 A CN111416128 A CN 111416128A CN 202010229196 A CN202010229196 A CN 202010229196A CN 111416128 A CN111416128 A CN 111416128A
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- lead
- storage battery
- grid
- positive plate
- plate
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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
- H01M4/64—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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
Abstract
The invention discloses a preparation method of a positive plate of a lead storage battery, and belongs to the technical field of storage batteries. The preparation method comprises the following steps: (1) die-cutting the foamed lead material after a plurality of pressing and rolling to obtain a grid lattice body, and die-casting lead-tin alloy along one wide edge of the grid lattice body to form an upper frame and a lug so as to prepare a positive grid; (2) spraying low-acid or acid-free lead plaster on the positive grid, and then soaking in acid; (3) and taking the polar plate out of the acid liquor, covering the surface of the polar plate with coated paper, stacking the polar plate and placing the polar plate in a curing chamber for curing, and thus obtaining the positive plate of the lead storage battery. According to the invention, a foamed lead material with high porosity and large pore diameter is utilized, the thinning of the polar plate is realized through multiple rolling, meanwhile, the pore structure is richer and more complex, the spraying of low-acid low-viscosity lead paste can be realized, the current distribution of the polar plate is more uniform, and the utilization rate of active substances and the large-current charging and discharging capacity are obviously improved; the lamination is solidified, so that low-temperature and low-humidity solidification can be realized, and the energy consumption and the process control difficulty of the solidification process are reduced.
Description
Technical Field
The invention relates to the technical field of storage batteries, in particular to a preparation method of a positive plate of a lead storage battery.
Background
The lead storage battery is widely applied to the fields of communication, electric power, UPS power supply and the like because of the advantages of mature technology, low price, large monomer capacity, high safety and the like, and is the secondary battery with the largest consumption at present.
The field of traditional communication, UPS backup power supply and the like is mainly used for floating charging, and the main failure mode of the storage battery under the using condition is corrosion of a positive plate grid. The fields of power energy storage and the like are mainly recycled, and the main failure mode of the storage battery under the using condition is softening and falling of the positive lead plaster.
In recent years, with the rise and high-speed development of the internet and electronic commerce, an IDC machine room is greatly built, a storage battery is mostly powered on for a short time, the power supply time is 5-10 min generally, and the acceptance standard of a storage battery pack is 15min constant-power discharge. Meanwhile, due to the large data processing capacity, the backup power supply of the IDC machine room is basically a high-voltage system, the capacity is large, and the storage battery is required to have higher specific energy and specific power so as to reduce the occupation of an installation site, the load of a unit area of a floor and the like.
Aiming at the use characteristics and failure modes of the storage battery in the typical application scene, a storage battery with a more corrosion-resistant positive grid, a positive lead paste which is not easy to soften and fall off and a higher specific energy needs to be developed.
The slab lattice of the present lead accumulator is mainly cast slab lattice of lead-calcium alloy, which has heavy weight and results in low specific energy of the accumulator. The weight of the polar plate accounts for 70 percent of the weight of the whole battery, in order to reduce the weight of the battery and improve the utilization rate of active substances, technicians at home and abroad mainly improve the structure and the material of the plate grids, and invent a plurality of novel plate grid materials such as copper expanded grid, lead cloth and the like in succession, and the mass specific energy of the novel plate grid materials can be improved to 50 Wh/Kg.
The foamed lead has a good net-shaped porous structure, high porosity, high specific surface area and light volume density, so that when the foamed lead is used as an electrode grid of a lead storage battery, the utilization rate of an electrode active substance of the lead storage battery can be greatly improved, and the foamed lead is paid much attention. For example, patent document CN 203589138U discloses a high-performance lead-acid battery grid, which includes a tab fixed on the outer side of a frame, and a foamed lead current collector disposed inside the frame, the foamed lead current collector being connected with the frame by electrodeposition; patent document CN 110148710 a also discloses that the battery grid is made of foamed lead material to reduce the grid mass, and the three-dimensional network structure of foamed lead increases the contact area with lead paste, and improves the utilization rate of active substances.
However, in actual production, there are problems as follows: the polar plate can not be thinned (the thickness of a foam lead material is generally more than 6mm, and the thickness of a foam lead plate grid prepared by the existing method is thicker), the rate performance of the prepared battery is poor, the casting reliability of the pole lug is low (the pole lug has poor strength, and the defects of insufficient solder, air holes and the like are easy to occur), the using amount of lead and the weight of a finished battery can be greatly increased by adopting a mode of casting the pole lug and a peripheral frame, and the industrial application of the battery is seriously influenced.
Disclosure of Invention
The invention aims to provide a method for preparing a positive plate of a lead storage battery, which has low requirements on process conditions and stable and reliable performance of a finished plate.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a positive plate of a lead storage battery comprises the following steps:
(1) die-cutting the foamed lead material after a plurality of pressing and rolling to obtain a grid lattice body, and die-casting lead-tin alloy along one wide edge of the grid lattice body to form an upper frame and a lug so as to prepare a positive grid;
the porosity of the foamed lead material is 90-95%, the pore diameter is larger than or equal to 6mm, and the calendering conditions are as follows: the reduction rate of each pass is less than or equal to 10 percent, and the total reduction rate is less than or equal to 60 percent;
(2) spraying lead plaster on the positive grid, and then soaking in acid;
the lead plaster comprises lead powder, sulfuric acid solution and water, wherein the lead powder accounts for 100 parts by weight, and the concentration of the lead powder is 1.4g/cm30-5 parts of sulfuric acid solution and 18-25 parts of water;
(3) and taking the polar plate out of the acid liquor, covering the surface of the polar plate with coated paper, stacking the polar plate and placing the polar plate in a curing chamber for curing, and thus obtaining the positive plate of the lead storage battery.
In the step (1), according to the size of the existing pole plate, the foamed lead material with high porosity and large aperture is rolled to the required thickness, and is punched into the required size, so that the grid lattice body is prepared. The weight of the grid is far less than that of the traditional cast grid by adopting a foamed lead material, so that the weight of the storage battery and the consumption of lead are greatly reduced; the corrosion resistance of the lead-calcium alloy plate grid is superior to that of the traditional lead-calcium alloy plate grid.
And during calendering, the number of calendering channels and the reduction rate per time are controlled, so that the internal pores of the material are more abundant and complex, the contact area of the three-dimensional network pore structure with lead paste is increased, and the utilization rate of active substances is improved.
The thickness of the foamed lead material is 5-9 mm, the porosity is 90-95%, and the pore diameter is larger than or equal to 6 mm.
Preferably, the mixture is subjected to 4-9 rolling.
The invention adopts the die-casting technology to connect the upper frame and the lug of the lead-tin alloy on one side of the grid lattice body, and the upper frame is effectively connected with the foamed lead grid and the lug, thereby being beneficial to the concentration of current to the lug.
Preferably, the mass percent of tin in the lead-tin alloy is 1.8-30%.
The upper frame is arranged on one side of the grid daughter of the foam lead plate, so that the consumption of lead is reduced. The upper frame accounts for 1.2% -3% of the height of the positive grid. The width of the overlapping part of the upper frame and the grid lattice body is 3-4 mm.
Preferably, the pressure of the die casting is 30-40 MPa, and the temperature is 480 +/-20 ℃. The reliability and the production efficiency of the casting finished product are ensured, and the precision, the surface finish degree, the mechanical strength and the like of the pole lug size are ensured.
In the step (2), low-acid or acid-free lead paste is sprayed in the grid cavity of the positive plate by using a spray gun and then is soaked in acid.
Preferably, the lead plaster comprises the following components in parts by weight based on 100 parts by weight of lead powder: 100 parts of lead powder, 1.4g/cm32.5 to 4.2 parts of sulfuric acid, 19.3 to 20.5 parts of water and 0.05 to 0.1 part of teflon solution with the mass concentration of 15 to 30 percent.
The common short fibers are omitted in the lead plaster additive, and the low-mass-fraction teflon solution is added, so that pores of an active substance are developed, the high-rate charge and discharge performance is further improved, and meanwhile, the temperature rise of a battery is increased during high-rate charge and discharge, and the teflon is more difficult to degrade than the traditional short fibers.
The high-pressure spraying is favorable for fully filling the lead paste into the plate grid cavity, and preferably, the spraying pressure is 0.04-0.08 MPa.
The pickling adopts the density of 1.08-1.20 g/cm3The pickling time of the sulfuric acid solution is 30-60 s.
In the step (3), the lamination is solidified after the coated paperboard is coated, so that the heat generated by the reaction of the polar plate is fully utilized, the polar plate is more beneficial to moisturizing, the low-temperature and low-humidity solidification can be realized, and the energy consumption is reduced.
Preferably, the curing temperature is 35-45 ℃, the relative humidity is 30-50%, and the curing time is 48-72 h.
The invention has the following beneficial effects:
(1) according to the invention, a foam lead material with high porosity and large pore diameter is utilized, a three-dimensional network structure with richer and more complex pores is formed through calendering, the current distribution of a polar plate is more uniform, the utilization rate of active substances and the large-current charging and discharging capacity are obviously improved, and compared with a two-dimensional pore structure of a traditional cast grid, the lead plaster is more difficult to fall off.
(2) The foamed lead material is difficult to thin, the pole plate is thin through multiple rolling, meanwhile, the pore structure is rich, the low-acid low-viscosity lead paste spraying can be realized, and the utilization rate and the high-rate discharge performance of active substances are further improved through the low-acid low-viscosity lead paste.
(3) The invention adopts lamination curing, can realize low-temperature and low-humidity curing, and reduces energy consumption and the process control difficulty of the curing process.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the present invention is not limited thereto.
Example 1
1. The method is characterized in that a foamed lead material with the thickness of 5mm, the porosity of 95% and the minimum pore diameter of 6mm is adopted, the foamed lead material is subjected to 4-pass rolling and is pressed to the thickness of 3.8mm, and a grid lattice body material with the length of 234mm and the width of 141mm is punched.
The lead-tin alloy tab and the upper frame with the tin content of 1.8 percent by weight are die-cast in the width direction of the grid lattice body, the tab is 4mm thick and 18mm wide, the tab is 37.5mm away from the edge of the grid lattice body, the upper frame is 4mm thick and 4mm wide, the tab is as long as the grid lattice body, the width direction of the tab is 1mm higher than that of the grid lattice body, and the size of the finished grid frame is 141mm wide, 235mm high and 4mm thick.
2. Lead plaster component: lead powder 100kg, 1.4g/cm34.13kg of dilute sulfuric acid, 19.3kg of deionized water and 0.05kg of teflon solution with the mass concentration of 30 percent.
Spraying a polar plate, wherein the pressure of a spray gun is 0.08MPa, the size of the finished polar plate is 141mm in width, 235mm in height and 4.2mm in thickness, and pickling treatment is carried out after the plate coating is finished, and the pickling density is 1.08g/cm3The pickling time was 60 seconds.
3. Coating paper on both sides of the electrode plate after acid dipping, and performing lamination curing at the curing temperature of 40 +/-5 ℃ and the relative humidity of 40 +/-10% for 48 h.
Example 2
1. Adopting a foamed lead material with the thickness of 8.5mm, the porosity of 90 percent and the minimum aperture of 10mm, rolling for 9 times, pressing to the thickness of 3.8mm, and punching a grid body material with the length of 234mm and the width of 141 mm.
The lead-tin alloy tab and the upper frame with the tin content of 30 percent by weight are die-cast in the width direction of the grid lattice body, the tab is 4mm thick and 18mm wide, the tab is 37.5mm away from the edge of the lattice body, the upper frame is 4mm thick and 4mm wide, the tab is as long as the lattice body, the tab is 1mm higher than the lattice body in the width direction, and the size of the finished grid frame is 141mm wide, 235mm high and 4mm thick.
2. Lead plaster component: lead powder 100kg, 1.4g/cm32.56kg of dilute sulphuric acid, 20.5kg of deionized water and 0.1kg of teflon solution with the mass concentration of 15 percent.
Spraying a polar plate, wherein the pressure of a spray gun is 0.04MPa, the size of the finished polar plate is 141mm in width, 235mm in height and 4.2mm in thickness, and pickling treatment is carried out after the plate coating is finished, and the pickling density is 1.20g/cm3The pickling time was 30 seconds.
3. Coating paper on both sides of the electrode plate after acid dipping, and performing lamination curing at the curing temperature of 40 +/-5 ℃ and the relative humidity of 40 +/-10% for 72 h.
Comparative example 1
The grid is cast by adopting the traditional gravity, the alloy of the grid is Pb-0.08 Ca-1.20 Sn-0.03 Al alloy, and the size of the frame of the grid is 141mm in width, 235mm in height and 4mm in thickness.
Lead plaster component: 100kg of lead powder, 9.36kg of dilute sulfuric acid, 11.5kg of deionized water and 0.1kg of short fibers. The plate coating is carried out by adopting the existing process, the size of the finished plate is 141mm in width, 235mm in height and 4.2mm in thickness, the hanging piece is cured after the plate coating is finished, the distance between the plates is 5-10 mm, the curing temperature is 75 +/-5 ℃, the relative humidity is 95 +/-5%, and the curing time is 72 h.
Application example
The three positive plates and the existing negative plate with the same specification are assembled to manufacture a 2V300Ah sample battery with the same specification, tests such as a conventional capacity, constant power discharge performance, high-temperature accelerated floating charge life test (YD/T799-2010 standard test method), 100% DOD cycle life (middle mobile test method) and the like are carried out, and specific data are shown in table 1:
TABLE 1
As can be seen from the data in Table 1, the weight of the finished product of the battery assembled by the positive plate prepared by the preparation method is greatly reduced, the conventional capacity and the high-rate discharge performance are obviously improved, the high-temperature floating charge life and the deep cycle life are greatly superior to those of the conventional product, and the preparation method is particularly suitable for application scenes such as communication, photovoltaic energy storage and IDC data centers.
Claims (9)
1. The preparation method of the positive plate of the lead storage battery is characterized by comprising the following steps:
(1) die-cutting the foamed lead material after a plurality of pressing and rolling to obtain a grid lattice body, and die-casting lead-tin alloy along one wide edge of the grid lattice body to form an upper frame and a lug so as to prepare a positive grid;
the porosity of the foamed lead material is 90-95%, the pore diameter is larger than or equal to 6mm, and the calendering conditions are as follows: the reduction rate of each pass is less than or equal to 10 percent, and the total reduction rate is less than or equal to 60 percent;
(2) spraying lead plaster on the positive grid, and then soaking in acid;
the lead plaster comprises lead powder, sulfuric acid solution and water, wherein the lead powder accounts for 100 parts by weight, and the concentration of the lead powder is 1.4g/cm30-5 parts of sulfuric acid solution and 18-25 parts of water;
(3) and taking the polar plate out of the acid liquor, covering the surface of the polar plate with coated paper, stacking the polar plate and placing the polar plate in a curing chamber for curing, and thus obtaining the positive plate of the lead storage battery.
2. The method for preparing the positive plate of the lead storage battery according to claim 1, wherein in the step (1), 4 to 9 calendering steps are performed.
3. The method for preparing the positive plate of the lead storage battery according to claim 1, wherein in the step (1), the mass percentage of tin in the lead-tin alloy is 1.8-30%.
4. The method for preparing the positive plate of the lead storage battery as claimed in claim 3, wherein the width of the overlapping part of the upper frame and the grid lattice body is 3-4 mm.
5. The method for preparing the positive plate of the lead storage battery according to claim 4, wherein the pressure of the die casting is 30-40 MPa, and the temperature is 480 +/-20 ℃.
6. The method for preparing the positive plate of the lead storage battery according to claim 1, wherein in the step (2), the components of the lead paste, based on 100 parts by weight of lead powder, comprise: 100 parts of lead powder, 1.4g/cm32.5 to 4.2 parts of sulfuric acid, 19.3 to 20.5 parts of water and 0.05 to 0.1 part of teflon solution with the mass concentration of 15 to 30 percent.
7. The method for preparing the positive plate of the lead storage battery according to claim 1, wherein in the step (2), the spraying pressure is 0.04 to 0.08 MPa.
8. The method for preparing the positive plate of the lead storage battery according to claim 1, wherein the pickling is performed at a density of 1.08-1.20 g/cm3The pickling time of the sulfuric acid solution is 30-60 s.
9. The method for preparing the positive plate of the lead storage battery as claimed in claim 1, wherein in the step (3), the curing temperature is 35-45 ℃, the relative humidity is 30-50%, and the curing time is 48-72 h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116706262A (en) * | 2023-06-30 | 2023-09-05 | 国网浙江省电力有限公司建设分公司 | Preparation process of bipolar horizontal battery |
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| CN106450172A (en) * | 2016-11-16 | 2017-02-22 | 双登集团股份有限公司 | Method for coating lead plaster on felt plate grid |
| CN108306058A (en) * | 2017-01-12 | 2018-07-20 | 广州丰江实业有限公司 | A kind of preparation method of lead-acid accumulator |
| CN109037691A (en) * | 2018-07-25 | 2018-12-18 | 江苏永达电源股份有限公司 | A kind of battery novel anode material additive |
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| CN1501528A (en) * | 2002-11-14 | 2004-06-02 | 深圳市雄韬电源科技有限公司 | Polar plate curing technology for lead-acid storage battery |
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| CN1790796A (en) * | 2005-12-27 | 2006-06-21 | 哈尔滨工业大学 | Coiled lead-acid battery with lead foam negative electrode grid and preparing method thereof |
| CN106450172A (en) * | 2016-11-16 | 2017-02-22 | 双登集团股份有限公司 | Method for coating lead plaster on felt plate grid |
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