CN114790523A - Lead-calcium-tin-aluminum-silver-bismuth positive grid alloy and preparation method thereof - Google Patents
Lead-calcium-tin-aluminum-silver-bismuth positive grid alloy and preparation method thereof Download PDFInfo
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- CN114790523A CN114790523A CN202210223285.XA CN202210223285A CN114790523A CN 114790523 A CN114790523 A CN 114790523A CN 202210223285 A CN202210223285 A CN 202210223285A CN 114790523 A CN114790523 A CN 114790523A
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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
- C22C11/06—Alloys based on lead with tin as the next major constituent
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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
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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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
Abstract
The invention provides a lead-calcium-tin-aluminum-silver-bismuth positive grid alloy which comprises the following chemical components in percentage by mass: 0.02-0.04% of calcium, 0.95-1.15% of tin, 0.015-0.035% of aluminum, 0.02-0.03% of silver, 0.015-0.025% of bismuth and the balance of lead. The invention has the advantages that: the alloy can greatly improve the corrosion resistance and creep resistance of a grid, and compared with a battery made of common lead-calcium-tin-aluminum, the water loss rate of the battery in the using process is greatly reduced.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a lead-calcium-tin-aluminum-silver-bismuth positive grid alloy and a preparation method thereof.
Background
The grid is formed from a lead-based alloy by casting or die casting. The role of the grid in the battery has two aspects: firstly, the carrier as an active substance plays a role of supporting a skeleton; and the other is the current collecting and transmitting function as a current conductor.
The alloy material used as the grid should have good corrosion resistance, and its structure and structure should be resistant to corrosion by the electrolyte during charging or standing. However, the corrosion resistance of the common lead-calcium alloy is unsatisfactory. In addition, the power battery is designed in a lean liquid mode, one of failure modes of the battery is electrolyte drying, and the water loss rate of the battery in the using process is also an index which needs to be focused.
Disclosure of Invention
The invention provides a lead-calcium-tin-aluminum-silver-bismuth positive grid alloy and a preparation method thereof, aiming at the defects of the prior art.
The invention solves the technical problems through the following technical means:
a lead-calcium-tin-aluminum-silver-bismuth positive grid alloy comprises the following chemical components in percentage by mass: 0.02-0.04% of calcium, 0.95-1.15% of tin, 0.015-0.035% of aluminum, 0.02-0.03% of silver, 0.015-0.025% of bismuth and the balance of lead.
A preparation method of a lead-calcium-tin-aluminum-silver-bismuth positive grid alloy comprises the following steps:
s1, dissolving lead: adding 90% of lead ingots into a lead pan, heating to 640 ℃, adding a slag reducing agent, stirring for 10min, and fishing lead slag;
s2, preparing a master alloy I: keeping the temperature of the lead liquid at 640 ℃, wrapping the silver-bismuth alloy by using lead foil, pressing the silver-bismuth alloy into the bottom of a lead pan, and stirring the silver-bismuth alloy uniformly after the silver-bismuth alloy is melted;
s3, preparing intermediate alloy II: when the temperature of the intermediate alloy I is reduced to 620-630 ℃, pressing the calcium-aluminum alloy into the bottom of the lead pot, and after the calcium-aluminum alloy is melted, uniformly stirring;
s4, preparing a grid alloy: adding the rest 10% of lead into a lead pot, cooling to about 550 ℃, adding tin blocks, melting and uniformly stirring.
Preferably, the stirring mode for preparing the master alloy I is as follows: forward stirring for 5-10min, and reverse stirring for 3-5 min.
Preferably, the stirring mode for preparing the intermediate alloy II is as follows: forward stirring for 3-5min, and backward stirring for 2-3 min.
Preferably, the stirring mode for preparing the grid alloy is as follows: forward stirring for 4-6min, and reverse stirring for 3-4 min.
Preferably, the annual calcium-aluminum ratio in the calcium-aluminum alloy is 3: 1.
The invention has the advantages that: the alloy can greatly improve the corrosion resistance and creep resistance of the grid, and compared with the battery made of the common lead-calcium-tin-aluminum, the water loss rate of the battery in the using process is greatly reduced.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A lead-calcium-tin-aluminum-silver-bismuth positive grid alloy comprises the following components in parts by weight: 2kg of calcium, 95kg of tin, 1.5kg of aluminum, 2kg of silver, 1.5kg of bismuth and the balance of lead.
A preparation method of a lead-calcium-tin-aluminum-silver-bismuth positive grid alloy comprises the following steps:
s1, lead block dissolution: adding 90% of lead ingots into a lead pan, heating to 640 ℃, adding a slag reducing agent, stirring for 10min, and fishing lead slag;
s2, preparing a master alloy I: keeping the temperature of the lead liquid at 640 ℃, wrapping the silver-bismuth alloy by using lead foil, pressing the silver-bismuth alloy into the bottom of a lead pot, and stirring uniformly after the silver-bismuth alloy is melted;
s3, preparing an intermediate alloy II: when the temperature of the intermediate alloy I is reduced to 620-630 ℃, pressing the calcium-aluminum alloy into the bottom of the lead pot, and after the calcium-aluminum alloy is melted, uniformly stirring;
s4, preparing a grid alloy: adding the rest 10% of lead into a lead pan, adding tin blocks when the temperature is reduced to about 550 ℃, melting and uniformly stirring.
The stirring mode for preparing the intermediate alloy I is as follows: forward stirring for 5-10min, and reverse stirring for 3-5 min.
The stirring mode for preparing the intermediate alloy II is as follows: forward stirring for 3-5min, and backward stirring for 2-3 min.
The preparation and stirring modes of the grid alloy are as follows: forward stirring for 4-6min, and backward stirring for 3-4 min.
The ratio of the medium-aged calcium to the aluminum in the calcium-aluminum alloy is 3: 1.
Example 2
A lead-calcium-tin-aluminum-silver-bismuth positive grid alloy comprises the following components in parts by weight: 4kg of calcium, 115kg of tin, 3.5kg of aluminum, 3kg of silver, 2.5kg of bismuth and the balance of lead.
A preparation method of a lead-calcium-tin-aluminum-silver-bismuth positive grid alloy comprises the following steps:
s1, lead block dissolution: adding 90% of lead ingots into a lead pan, heating to 640 ℃, adding a slag reducing agent, stirring for 10min, and fishing lead slag;
s2, preparing an intermediate alloy I: keeping the temperature of the lead liquid at 640 ℃, wrapping the silver-bismuth alloy by using lead foil, pressing the silver-bismuth alloy into the bottom of a lead pan, and stirring the silver-bismuth alloy uniformly after the silver-bismuth alloy is melted;
s3, preparing intermediate alloy II: when the temperature of the intermediate alloy I is reduced to 620-630 ℃, pressing the calcium-aluminum alloy into the bottom of the lead pot, and after the calcium-aluminum alloy is melted, uniformly stirring;
s4, preparing a grid alloy: adding the rest 10% of lead into a lead pan, adding tin blocks when the temperature is reduced to about 550 ℃, melting and uniformly stirring.
The stirring mode for preparing the intermediate alloy I is as follows: forward stirring for 5-10min, and backward stirring for 3-5 min.
The stirring mode for preparing the intermediate alloy II is as follows: forward stirring for 3-5min, and backward stirring for 2-3 min.
The preparation and stirring modes of the grid alloy are as follows: forward stirring for 4-6min, and backward stirring for 3-4 min.
The ratio of the medium-aged calcium to the aluminum in the calcium-aluminum alloy is 3: 1.
Example 3
A lead-calcium-tin-aluminum-silver-bismuth positive grid alloy comprises the following components in parts by weight: 3kg of calcium, 105kg of tin, 2.5kg of aluminum, 2.5kg of silver, 2kg of bismuth and the balance of lead.
A preparation method of a lead-calcium-tin-aluminum-silver-bismuth positive grid alloy comprises the following steps:
s1, lead block dissolution: adding 90% of lead ingots into a lead pan, heating to 640 ℃, adding a slag reducing agent, stirring for 10min, and fishing lead slag;
s2, preparing a master alloy I: keeping the temperature of the lead liquid at 640 ℃, wrapping the silver-bismuth alloy by using lead foil, pressing the silver-bismuth alloy into the bottom of a lead pan, and stirring the silver-bismuth alloy uniformly after the silver-bismuth alloy is melted;
s3, preparing an intermediate alloy II: when the temperature of the intermediate alloy I is reduced to 620-630 ℃, pressing the calcium-aluminum alloy into the bottom of the lead pot, and after the calcium-aluminum alloy is melted, uniformly stirring;
s4, preparing a grid alloy: adding the rest 10% of lead into a lead pot, cooling to about 550 ℃, adding tin blocks, melting and uniformly stirring.
The stirring mode for preparing the intermediate alloy I is as follows: forward stirring for 5-10min, and backward stirring for 3-5 min.
The stirring mode for preparing the intermediate alloy II is as follows: forward stirring for 3-5min, and reverse stirring for 2-3 min.
The preparation and stirring mode of the grid alloy is as follows: forward stirring for 4-6min, and backward stirring for 3-4 min.
The ratio of the medium-aged calcium to the aluminum in the calcium-aluminum alloy is 3: 1.
The addition of the silver element can thin the grain boundary, reduce the grain boundary corrosion and reduce the grain boundary cracks;
the addition of bismuth can improve the casting performance of the alloy, refine crystal grains and improve the corrosion resistance of the alloy;
meanwhile, the corrosion resistance of the alloy is improved by the ultralow calcium content;
the alloy not only has excellent corrosion resistance, but also has lower water loss rate compared with the common lead-calcium-tin-aluminum alloy.
The lead-calcium-tin-aluminum-silver-bismuth alloy can be obtained through a constant current corrosion experiment: the corrosion resistance of the grid is greatly improved;
the experimental method is to select the prepared lead-calcium-tin-aluminum-silver-bismuth alloy grid for experiment. The mass of the alloy is first weighed on an electronic balance and recorded, and the alloy tested is then used as positive electrode, pure lead as negative electrode and 1.28 g-And using the mL sulfuric acid solution as an electrolyte, and then connecting positive and negative grids by using a lead. Connected with a constant-current constant-voltage power supply, and the current density is set at 10mA/cm 2 The constant temperature water bath temperature was set at 60 ℃.
The grid is used for assembling a power battery, 100% DOD cycle test is carried out on the battery, the weight of the battery is recorded 100 times per cycle, and the weight is converted into the water loss rate of the battery.
The test method comprises the following steps: 4 6-DZF-20 batteries using a common lead-calcium-tin-aluminum alloy and a novel lead-calcium-tin-aluminum-silver-bismuth alloy were manufactured according to the same process, and 100% DOD discharge cycle test (25 ℃) was performed in the following manner:
1. standing for 2 h;
2. the discharge was terminated at 10A to 42V;
3. charging for 4h at constant voltage 59.2V current limit 10A;
4. repeating the steps 1-3 until the discharge time is reduced to below 1h36 min.
Description of the attached tables:
table 1 results of constant current corrosion experiments
TABLE 2 Water loss test results
Note: the common alloy is lead-calcium-tin-aluminum alloy; the novel alloy is a lead-calcium-tin-aluminum-silver-bismuth alloy;
it is noted that, in this document, relational terms such as first and second, and the like, if any, are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (6)
1. A lead-calcium-tin-aluminum-silver-bismuth positive grid alloy is characterized in that: according to the mass percentage of chemical components: 0.02-0.04% of calcium, 0.95-1.15% of tin, 0.015-0.035% of aluminum, 0.02-0.03% of silver, 0.015-0.025% of bismuth and the balance of lead.
2. The preparation method of the lead-calcium-tin-aluminum-silver-bismuth positive grid alloy according to claim 1, which is characterized by comprising the following steps of: the method comprises the following steps:
s1, lead block dissolution: adding 90% of lead ingots into a lead pan, heating to 640 ℃, adding a slag reducing agent, stirring for 10min, and fishing lead slag;
s2, preparing an intermediate alloy I: keeping the temperature of the lead liquid at 640 ℃, wrapping the silver-bismuth alloy by using lead foil, pressing the silver-bismuth alloy into the bottom of a lead pan, and stirring the silver-bismuth alloy uniformly after the silver-bismuth alloy is melted;
s3, preparing an intermediate alloy II: when the temperature of the intermediate alloy I is reduced to 620-630 ℃, pressing the calcium-aluminum alloy into the bottom of the lead pot, and after the calcium-aluminum alloy is melted, uniformly stirring;
s4, preparing a grid alloy: adding the rest 10% of lead into a lead pan, adding tin blocks when the temperature is reduced to about 550 ℃, melting and uniformly stirring.
3. The preparation method of the lead-calcium-tin-aluminum-silver-bismuth positive grid alloy according to claim 1, which is characterized by comprising the following steps of: the stirring mode for preparing the intermediate alloy I is as follows: forward stirring for 5-10min, and backward stirring for 3-5 min.
4. The preparation method of the lead-calcium-tin-aluminum-silver-bismuth positive grid alloy according to claim 1, which is characterized by comprising the following steps of: the stirring mode for preparing the intermediate alloy II is as follows: forward stirring for 3-5min, and reverse stirring for 2-3 min.
5. The preparation method of the lead-calcium-tin-aluminum-silver-bismuth positive grid alloy according to claim 1, which is characterized by comprising the following steps of: the preparation and stirring modes of the grid alloy are as follows: forward stirring for 4-6min, and backward stirring for 3-4 min.
6. The preparation method of the lead-calcium-tin-aluminum-silver-bismuth positive grid alloy according to claim 2, which is characterized by comprising the following steps of: the ratio of the medium-aged calcium to the aluminum in the calcium-aluminum alloy is 3: 1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115772614A (en) * | 2022-11-01 | 2023-03-10 | 天能集团贵州能源科技有限公司 | Storage battery positive grid alloy and preparation method thereof |
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| CN115772614A (en) * | 2022-11-01 | 2023-03-10 | 天能集团贵州能源科技有限公司 | Storage battery positive grid alloy and preparation method thereof |
| CN115772614B (en) * | 2022-11-01 | 2024-03-29 | 天能集团贵州能源科技有限公司 | Positive grid alloy of storage battery and preparation method thereof |
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