CN113611870A - Lead-based alloy for punched grid and preparation method and application thereof - Google Patents
Lead-based alloy for punched grid and preparation method and application thereof Download PDFInfo
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- CN113611870A CN113611870A CN202110772082.1A CN202110772082A CN113611870A CN 113611870 A CN113611870 A CN 113611870A CN 202110772082 A CN202110772082 A CN 202110772082A CN 113611870 A CN113611870 A CN 113611870A
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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
- H01M4/66—Selection of materials
- H01M4/68—Selection of materials for use in lead-acid accumulators
- H01M4/685—Lead alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C11/00—Alloys based on lead
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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
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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
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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
- H01M4/82—Multi-step processes for manufacturing carriers for lead-acid accumulators
- H01M4/84—Multi-step processes for manufacturing carriers for lead-acid accumulators involving casting
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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
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- 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-based alloy for a punched grid, and a preparation method and application thereof, wherein the lead-based alloy is prepared from the following components in percentage by mass: 0.8 to 1.5 percent of manganese, 0.1 to 0.3 percent of tellurium, 0.05 to 0.1 percent of cobalt, 0.05 to 0.3 percent of selenium and the balance of electrolytic lead. The electrolytic manganese ingot is characterized in that the manganese is an electrolytic manganese sheet with the purity of more than 99.9%, the tellurium is tellurium particles with the purity of more than 99.99%, the cobalt is a cobalt sheet with the purity of more than 99.99%, the selenium is selenium particles with the purity of more than 99.99%, and the lead is an electrolytic lead ingot with the purity of more than 99.994%. The positive plate prepared by the lead-based alloy formula and the preparation method can inhibit the formation of a high-impedance layer on the surface of a grid caused in the charging and discharging processes of a storage battery, solve the problem of initial capacity attenuation of the storage battery and further prolong the deep cycle service life of the storage battery.
Description
Technical Field
The invention relates to the technical field of lead-acid storage batteries, in particular to a lead-based alloy for a screen punching plate grid and a preparation method and application thereof.
Background
At present, in order to realize cadmium-free and arsenic-free of a storage battery, a grid alloy of a positive plate of the storage battery of the electric moped is adjusted to be a lead-calcium-tin-aluminum or lead-calcium-rare earth alloy from a lead-antimony-cadmium alloy; however, when the alloy is adjusted to a new alloy, the initial capacity of some batteries is reduced, the capacity of the battery is rapidly reduced in 50 life cycles, and the phenomenon is more remarkable particularly in a high-temperature environment.
Research and analysis on the phenomenon find that the problem is caused by the fact that a layer of high-impedance substance is formed between the grid of the positive plate and the active substance, the substance is a compact oxide layer between lead oxide and lead dioxide, the oxide layer cannot be completely eliminated through normal charging and discharging, due to the existence of the oxide layer, the internal resistance of the storage battery is increased, electric energy generated by the active substance cannot be well led out through the grid, and finally the capacity of the storage battery is reduced. Meanwhile, after trying to adopt alloys such as lead-antimony-tin-silver alloy, lead-carbon alloy, lead-antimony-copper alloy and the like, the problem still cannot be solved.
Patent document No. CN109196688A discloses lead-based alloys and related methods and products, in which "a lead-based alloy comprising, in total weight percent of the alloy, 0.0030% to 0.0900% bismuth, 0.0010% to 0.0300% antimony, 0.0010% to 0.0300% arsenic and 0.0010% to 0.0100% tin, wherein the alloy contains less than 0.0010% (10ppm) in total by weight tellurium, selenium, nickel, copper, molybdenum, manganese, cobalt and chromium". The main components of the lead-based alloy in the prior art except lead still comprise arsenic, and the technical problem that the capacity of the storage battery at the initial stage is attenuated due to the fact that a high-impedance oxide layer is formed between a grid and an active substance cannot be solved.
Disclosure of Invention
The invention aims to provide a lead-based alloy for punching a grid, a preparation method and application thereof, and aims to solve the technical problems that on the basis of ensuring cadmium-free and arsenic-free of a storage battery, a layer of high-impedance substance is formed between the grid of a positive plate prepared from the lead-based alloy and an active substance, the substance is a compact oxide layer between lead oxide and lead dioxide, the oxide layer cannot be completely eliminated through normal charging and discharging, due to the existence of the oxide layer, the internal resistance of the storage battery is increased, the electric energy generated by the active substance cannot be well led out through the grid, and the capacity of the storage battery is finally reduced, and the service life is short.
In order to achieve the purpose, the invention adopts the following technical scheme:
the lead-based alloy for the screen punching plate grid is prepared from the following components in percentage by mass: 0.8 to 1.5 percent of manganese, 0.1 to 0.3 percent of tellurium, 0.05 to 0.1 percent of cobalt, 0.05 to 0.3 percent of selenium and the balance of electrolytic lead; the electrolytic manganese ingot is characterized in that the manganese is an electrolytic manganese sheet with the purity of more than 99.9%, the tellurium is tellurium particles with the purity of more than 99.99%, the cobalt is a cobalt sheet with the purity of more than 99.99%, the selenium is selenium particles with the purity of more than 99.99%, and the lead is an electrolytic lead ingot with the purity of more than 99.994%.
The lead-based alloy for punching the mesh grid comprises the following specific preparation steps:
adding electrolytic lead with the formula amount into an alloy preparation furnace, heating and melting, fishing out oxidation slag floating on the surface of the lead liquid when the temperature of the lead liquid reaches 600 ℃, continuously heating to 650-700 ℃, and starting stirring to enable the lead liquid to form a vortex; after stirring stably, adding the metal manganese sheets, tellurium particles, cobalt sheets and selenium particles in the formula ratio into an alloy preparation furnace, continuously stirring for 30-40 minutes to uniformly mix the metal manganese sheets, the tellurium particles, the cobalt sheets and the selenium particles to prepare a lead-based alloy, and casting the lead-based alloy into a lead alloy ingot after the spectrum inspection is qualified.
The invention also provides an application of the lead-based alloy for the screen punching plate grid in the preparation of a positive plate, and the specific application method is as follows:
1) adding the cast lead alloy ingot into a lead furnace, and controlling the temperature of the lead furnace to 420-500 ℃ until the lead alloy ingot is completely melted;
2) the molten lead liquid flows into continuous casting and rolling equipment, and a lead alloy belt with the thickness of 0.7-0.8mm is formed through multi-stage rolling;
3) the rolling die prepared by the sand blasting process is used for carrying out surface roughness treatment on the lead alloy strip to enable the surface roughness Ra of the lead alloy strip to reach 15-25;
4) designing a net punching die according to the structure of a grid to be prepared, processing lead alloy band-pass net punching equipment into a corresponding grid, wherein the grid comprises a grid assembly and guide rail strips symmetrically connected to the upper end and the lower end of the grid assembly, the grid assembly comprises two grid groups which are parallel to each other and staggered from top to bottom, each grid group is provided with a plurality of small grids which are arranged in parallel, the small grids are arranged along the length direction of the guide rail strips, a process lug in a Z-shaped structure is respectively connected between the two small grids which correspond to each other from top to bottom, each small grid comprises a grid, a frame arranged along the peripheral edge of the grid and a lug arranged on one side of the frame, and the small grids are connected with the adjacent guide rail strips through the lugs;
5) and uniformly filling positive active substances on the grid by using continuous plate coating equipment, and preparing the positive plate by coating, roller shearing, surface drying and pole plate lamination curing.
Compared with the prior art, the invention has the beneficial effects that:
1. the lead, manganese, tellurium, cobalt and selenium elements in the invention can all play a role in improving the characteristics of the lead-based alloy: lead is a base body of the alloy; the addition of manganese can effectively improve the chemical composition of a surface corrosion layer of the grid in the charge-discharge cycle process, and high-valence manganese ions formed by charging can promote the conversion of lead oxide to lead dioxide, so that the main chemical components of the corrosion section of the grid are converted into lead dioxide with good conductivity, and the contact resistance of an active substance and the grid is finally improved; the addition of tellurium and selenium can refine the crystal grains of the lead-based alloy, so that the lead-based alloy has better ductility and creep resistance, and is beneficial to subsequent processing and application of the lead-based alloy; the addition of cobalt can improve the electrochemical corrosion resistance of the lead-based alloy;
2. the positive plate prepared by the alloy formula and the preparation method has good electrochemical corrosion resistance, can inhibit the formation of a high-resistance layer on the surface of a grid caused in the charging and discharging processes of a storage battery, solves the problem of initial capacity attenuation of the storage battery, and further prolongs the deep cycle service life of the storage battery;
3. in the invention, the surface roughness treatment is carried out in the preparation process of the positive plate, and the contact area between the active substance and the grid can be improved by utilizing the rough surface, so that the direct bonding force between the active substance and the grid is improved, and the contact resistance between the grid and the active substance is further reduced finally;
4. the arrangement mode of the grid group and the arrangement of the guide rail bar and the process pole ear enable the subsequent cutting of the grid to be more convenient and the positioning to be more accurate.
Drawings
Fig. 1 is a schematic diagram of the structure of a grid of the present invention.
In the figure: 1. guide rail bar 2, grid group 3, small grid 31, grid 32, frame 33, tab 4, craft tab.
Detailed Description
In order to enhance the understanding of the present invention, the present invention will be described in further detail with reference to the following examples.
Example 1
Preparing a lead-based alloy: adding 980.5kg of electrolytic lead with the purity of more than 99.994% into an alloy preparation furnace, heating and melting, fishing out oxidation slag floating on the surface of the lead liquid when the temperature of the lead liquid reaches 600 ℃, continuously heating to 650-700 ℃, starting stirring to enable the lead liquid to form a vortex; after stirring stably, adding 15kg of metal manganese sheets with the purity of more than 99.9 percent, 3kg of tellurium particles with the purity of more than 99.99 percent, 1kg of cobalt sheets with the purity of more than 99.99 percent and 0.5kg of selenium particles with the purity of more than 99.99 percent into an alloy preparation furnace, continuously stirring for 30-40 minutes to uniformly mix the materials to prepare a lead-based alloy, and casting the lead-based alloy into a lead alloy ingot after the spectrum inspection is qualified;
preparing a positive plate:
1) adding the prepared lead alloy ingot into a lead furnace, and controlling the temperature of the lead furnace to 420 ℃ and 500 ℃ until the lead alloy ingot is completely melted;
2) the molten lead liquid flows into continuous casting and rolling equipment, and a lead alloy belt with the thickness of 0.7-0.8mm is formed through multi-stage rolling;
3) the rolling die prepared by the sand blasting process is used for carrying out surface roughness treatment on the lead alloy strip to enable the surface roughness Ra of the lead alloy strip to reach 15-25;
4) designing a mesh punching die according to the structure of the grid shown in the figure 1, and processing a lead alloy band-pass mesh punching device into a corresponding grid; the grid comprises a grid assembly and guide rail strips 1 symmetrically connected to the upper end and the lower end of the grid assembly, the grid assembly comprises two grid groups 2 which are parallel to each other in an up-down mode and are arranged in a staggered mode, the grid groups 2 are provided with eight small grids 3 which are arranged in parallel, the small grids 3 are arranged along the length direction of the guide rail strips 1, process lugs 4 which are in a Z-shaped structure are respectively connected between the two small grids 3 which correspond to each other in the up-down mode, each small grid 3 is composed of a grid 31, a frame 32 arranged along the circumferential edge of the grid 31 and a lug 33 arranged on one side of the frame 32, and each small grid 3 is connected with the adjacent guide rail strip 1 through the lug 33;
5) and uniformly filling positive active substances on the grid by using continuous plate coating equipment, and preparing a finished positive plate by coating, roller shearing, surface drying and pole plate lamination curing.
Example 2
The preparation method of this example is consistent with example 1, only the formula amounts are inconsistent, i.e.: the weight of the electrolytic lead is 984.5kg, the weight of the metal manganese pieces is 10 kg, the weight of the tellurium particles is 2kg, the weight of the cobalt pieces is 1.5kg, and the weight of the selenium particles is 2 kg.
Example 3
The preparation method of this example is consistent with example 1, only the formula amounts are inconsistent, i.e.: the weight of the electrolytic lead is 987.5kg, the weight of the metal manganese sheet is 8kg, the weight of the tellurium particles is 1kg, the weight of the cobalt sheet is 0.5kg, and the weight of the selenium particles is 3 kg.
Example 4
The preparation method of this example is consistent with example 1, only the formula amounts are inconsistent, i.e.: the weight of the electrolytic lead is 982.7kg, the weight of the metal manganese sheet is 13kg, the weight of the tellurium particles is 2.5 kg, the weight of the cobalt sheet is 0.8kg, and the weight of the selenium particles is 1 kg.
Example 5
The preparation method of this example is consistent with example 1, only the formula amounts are inconsistent, i.e.: the weight of the electrolytic lead is 982.3kg, the weight of the metal manganese sheet is 12kg, the weight of the tellurium particles is 1.5kg, the weight of the cobalt sheet is 1.2kg, and the weight of the selenium particles is 3 kg.
Claims (9)
1. The lead-based alloy for the screen punching plate grid is characterized by comprising the following components in percentage by mass: 0.8 to 1.5 percent of manganese, 0.1 to 0.3 percent of tellurium, 0.05 to 0.1 percent of cobalt, 0.05 to 0.3 percent of selenium and the balance of electrolytic lead.
2. The lead-based alloy for screen punching plate grid according to claim 1, wherein the manganese is electrolytic manganese flakes with a purity of 99.9% or more, the tellurium is tellurium particles with a purity of 99.99% or more, the cobalt is cobalt flakes with a purity of 99.99% or more, the selenium is selenium particles with a purity of 99.99% or more, and the lead is electrolytic lead ingot with a purity of 99.994% or more.
3. The method for preparing the lead-based alloy for the screen punching plate grid as recited in any one of claims 1-2, characterized in that the specific operation steps are as follows:
1) adding electrolytic lead with the formula amount into an alloy preparation furnace, heating and melting, fishing out oxidation slag floating on the surface of the lead liquid when the temperature of the lead liquid reaches 600 ℃, continuously heating to 650-700 ℃, and starting stirring to enable the lead liquid to form a vortex;
2) after stirring stably, adding the metal manganese sheets, tellurium particles, cobalt sheets and selenium particles in the formula ratio into an alloy preparation furnace, continuously stirring to mix uniformly to prepare a lead-based alloy, and casting the lead-based alloy into a lead alloy ingot after the spectrum inspection is qualified.
4. The method for preparing a lead-based alloy for a screen punching plate grid according to claim 3, wherein in the step 2), the stirring time is 30-40 minutes.
5. Use of a lead-based alloy for a screen punching grid according to any of claims 1-4, characterised in that the specific application method is as follows:
1) adding the lead alloy ingot into a lead furnace, and controlling the temperature of the lead furnace until the lead alloy ingot is completely melted;
2) the molten lead liquid flows into continuous casting and rolling equipment, and a lead alloy belt is formed through multi-stage rolling;
3) the rolling die prepared by the sand blasting process is used for carrying out surface roughness treatment on the lead alloy strip to enable the surface roughness Ra of the lead alloy strip to reach 15-25;
4) designing a mesh punching die according to the structure of the grid to be prepared, and processing the lead alloy strip-pass mesh punching device into a corresponding grid;
5) and uniformly filling positive active substances on the grid by using continuous plate coating equipment, and preparing the positive plate by coating, roller shearing, surface drying and pole plate lamination curing.
6. The use of the lead-based alloy for punching screen plate grid as claimed in claim 5, wherein the lead furnace temperature in step 1) is 420-500 ℃.
7. Use of a lead-based alloy for screen punching grids according to claim 5, characterized in that in step 3) the lead alloy strip has a thickness of 0.7-0.8 mm.
8. The application of the lead-based alloy for the screen punching plate grid according to claim 5, wherein in the step 4), the grid comprises a grid assembly and guide rails symmetrically connected to the upper end and the lower end of the grid assembly, the grid assembly comprises two grid groups which are parallel to each other in an up-down mode and staggered in an up-down mode, each grid group is provided with a plurality of small grids which are arranged in parallel, the small grids are arranged along the length direction of the guide rails, and process tabs in a Z-shaped structure are respectively connected between the two small grids corresponding to each other in the up-down mode.
9. The use of a lead-based alloy for screen punching grids according to claim 8, wherein the small grid comprises a grid, a frame arranged along the periphery of the grid, and a tab arranged on one side of the frame, and the small grid is connected with the adjacent guide rail strips through the tab.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115094267A (en) * | 2022-05-20 | 2022-09-23 | 江苏海瑞电源有限公司 | Lead-based bearing alloy for high-performance bearing and preparation method thereof |
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| CN104821402A (en) * | 2014-08-15 | 2015-08-05 | 骆驼集团襄阳蓄电池有限公司 | Lead-acid storage battery plate grid and forming surface treatment method |
| CN107681162A (en) * | 2017-09-22 | 2018-02-09 | 武汉亿维登科技发展有限公司 | A kind of positive grid of lead-acid accumulator low antimony alloy |
| CN110205516A (en) * | 2019-06-13 | 2019-09-06 | 骆驼集团华中蓄电池有限公司 | The ultralow water loss plate anode plate grid of lead-acid accumulator and lead acid storage battery pool preparation method |
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- 2021-07-08 CN CN202110772082.1A patent/CN113611870B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101792873A (en) * | 2010-03-26 | 2010-08-04 | 如皋市天鹏冶金有限公司 | Low-stibium multicomponent lead alloy and production technology and applications thereof |
| CN104821402A (en) * | 2014-08-15 | 2015-08-05 | 骆驼集团襄阳蓄电池有限公司 | Lead-acid storage battery plate grid and forming surface treatment method |
| CN107681162A (en) * | 2017-09-22 | 2018-02-09 | 武汉亿维登科技发展有限公司 | A kind of positive grid of lead-acid accumulator low antimony alloy |
| CN110205516A (en) * | 2019-06-13 | 2019-09-06 | 骆驼集团华中蓄电池有限公司 | The ultralow water loss plate anode plate grid of lead-acid accumulator and lead acid storage battery pool preparation method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115094267A (en) * | 2022-05-20 | 2022-09-23 | 江苏海瑞电源有限公司 | Lead-based bearing alloy for high-performance bearing and preparation method thereof |
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Address after: 226400 No.1 Yalujiang Road, Rudong Economic Development Zone, Nantong City, Jiangsu Province Patentee after: JIANGSU HAIBAO BATTERY TECHNOLOGY Co.,Ltd. Patentee after: Jiangsu Haibao New Energy Co.,Ltd. Address before: 226400 No.1 Yalujiang Road, Rudong Economic Development Zone, Nantong City, Jiangsu Province Patentee before: JIANGSU HAIBAO BATTERY TECHNOLOGY Co.,Ltd. Patentee before: Jiangsu Hairui Power Supply Co.,Ltd. |
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