CN116254437A - Alloy for positive grid of maintenance-free lead-acid storage battery and preparation method of alloy - Google Patents
Alloy for positive grid of maintenance-free lead-acid storage battery and preparation method of alloy Download PDFInfo
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- CN116254437A CN116254437A CN202210745851.3A CN202210745851A CN116254437A CN 116254437 A CN116254437 A CN 116254437A CN 202210745851 A CN202210745851 A CN 202210745851A CN 116254437 A CN116254437 A CN 116254437A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- 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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- 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 provides a novel alloy for a positive plate grid of a maintenance-free lead-acid storage battery and a preparation method thereof, wherein the alloy comprises the following components in percentage by weight: 0.02-0.2% of Ca, 0.5-0.8% of Sn, 0.005-0.05% of Al, 0.002-0.3% of Ag, 0.002-0.4% of Ba, 0.001-0.08% of Si and the balance Pb, and is prepared by adding silicon-aluminum alloy, cooling and barium, cooling and silver, cooling and calcium, cooling and tin and ingot casting after the temperature of electrolytic lead is raised. The alloy for the positive grid of the storage battery provided by the invention has higher creep resistance, corrosion resistance and good mechanical property through the synergistic effect of different elements, fundamentally overcomes the defects of poor corrosion resistance, easy growth of the grid and the like of the positive grid made of the traditional lead alloy under a high-temperature environment, and prolongs the high-temperature service life of the storage battery. Compared with the traditional lead alloy, the cost of the positive grid manufactured by the alloy is obviously reduced, meanwhile, the corrosion resistance, the hardness and the tensile strength are effectively improved, and the market competitiveness of the product is greatly improved.
Description
Technical Field
The invention belongs to the technical field of lead alloy, and particularly relates to an alloy for a positive grid of a maintenance-free lead-acid storage battery and a preparation method thereof.
Background
With the continuous development of the lead-acid storage battery technology and the impact of the lithium battery industry, the requirements on the performance of the lead-acid storage battery are higher and higher, and the improvement of the corrosion resistance, deep circulation, charge receiving capacity and the like of the battery has become the main research direction of the industry. Wherein, grid alloy is used as a framework structure of a lead-acid storage battery, and the improvement of the performance of the grid alloy is an important direction.
At present, the most widely used grid material is lead-calcium alloy, in order to realize the maintenance-free requirement of a storage battery, the oxygen evolution reaction of a positive grid is required to be small, the corrosion resistance is excellent, the corrosion resistance is improved, and the gas evolution reaction is reduced.
In order to solve the problems of passivation films and corrosion growth, many alloy additive researches have been made by many people in recent years, and Chinese patent No. 109518017A discloses a lead alloy for a positive plate grid of a maintenance-free lead-acid storage battery and a preparation method thereof. Chinese patent No. CN 107881356A discloses a silver alloy positive grid for lead-acid battery and its preparation method. The storage battery made of the lead alloy can solve the problems of serious intergranular corrosion and large impedance of a passivation film, and improves the corrosion resistance of the grid alloy. Although the alloys prepared by the above patent have advantages, the alloy has low cost, high creep resistance, high corrosion resistance, high mechanical properties and other comprehensive cost and performance aspects.
Thus, there is an urgent need to develop an alloy having high creep resistance, corrosion resistance and good mechanical properties at low cost for improving the comprehensive market competitiveness of lead acid battery products.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and solve the problems in the prior art, and provides an alloy for a positive grid of a maintenance-free lead-acid storage battery, which has the advantages of low cost, high creep resistance, high corrosion resistance and high mechanical property.
The technical scheme adopted by the invention is as follows: the alloy for the positive grid of the maintenance-free lead-acid storage battery comprises the following components in percentage by weight: 0.02-0.2% of Ca, 0.5-0.8% of Sn, 0.005-0.05% of Al, 0.002-0.3% of Ag, 0.002-0.4% of Ba, 0.001-0.08% of Si and the balance Pb.
Preferably, the weight percentages of the components are as follows: 0.01-0.15% of Ca, 0.55-0.75% of Sn, 0.01-0.015% of Al, 0.01-0.2% of Ag, 0.01-0.3% of Ba, 0.001-0.05% of Si and the balance Pb.
Preferably, the weight percentages of the components are as follows: 0.04-0.05% of Ca, 0.6-0.7% of Sn, 0.012-0.13% of Al, 0.04-0.05% of Ag, 0.08-0.1% of Ba, 0.002-0.003% of Si and the balance of Pb.
The invention also aims at a preparation method of the alloy for the positive grid of the maintenance-free lead-acid storage battery, which is characterized by comprising the following steps of: the process comprises the following steps: adding electrolytic lead, heating, adding silicon-aluminum alloy (Si 20% and Al 80%) → cooling and adding barium→ cooling and adding silver→ cooling and adding calcium→ cooling and adding tin→ casting ingot.
The preparation method of the alloy for the positive grid of the maintenance-free lead-acid storage battery specifically comprises the following process steps:
s1: adding the electrolytic lead into a lead melting pot, heating, starting stirring, adding the silicon-aluminum alloy, stirring for 3-8min, and stopping stirring after the silicon-aluminum alloy is completely melted;
s2: cooling, then stirring, adding barium, stirring for 3-8min, and stopping stirring after the barium is completely melted;
s3: cooling, stirring, adding silver, stirring for 3-6min, and stopping stirring after the silver is completely melted;
s4: cooling, stirring, adding calcium, stirring for 2-5min, and stopping stirring after calcium is completely melted;
s5: cooling, then stirring, adding tin, stirring for 2-5min, and stopping stirring after the tin is completely melted;
s6: sampling for component testing, and casting lead ingot after the components are qualified.
Preferably, in the step S1, electrolytic lead is added into a lead melting pot, and after the temperature is increased to 900-1000 ℃, silicon aluminum alloy is added and stirring is started; in the step S2, when the temperature is reduced to 750-800 ℃, adding barium and starting stirring; in the step S3, when the temperature is reduced to 550-600 ℃, adding silver and starting stirring; in the step S4, when the temperature is reduced to 530-550 ℃, adding calcium and starting stirring; in step S5, tin is added and stirring is started when the temperature is reduced to 450-480 ℃.
Preferentially, in the step S1, electrolytic lead is added into a lead melting pot, and after the temperature is increased to 940-960 ℃, silicon aluminum alloy is added and stirring is started; in the step S2, when the temperature is reduced to 750-760 ℃, adding barium and starting stirring; in the step S3, when the temperature is reduced to 570-590 ℃, adding silver and starting stirring; in the step S4, when the temperature is reduced to 540-550 ℃, adding calcium and starting stirring; in step S5, tin is added and stirring is started when the temperature is reduced to 470-480 ℃.
Preferably, in the step S1, stirring is carried out for 5-7min; in the step S2, stirring for 3-5min; in the step S3, stirring for 3-4min; in the step S4, stirring for 2-4min; in step S5, stirring for 2-3min.
In the novel alloy for the storage battery positive grid, the addition of Ba ensures that the alloy keeps higher mechanical property and reduces the growth of the grid, because the barium reacts with lead to generate hard and brittle phase Pb 3 Ba intermetallic compound, which has a certain solid solubility in lead-base alloy, causes solid solution strengthening and is due toThe existence of the intermetallic compound not only ensures that the matrix has metal bonds but also has covalent bonds, and the existence of the covalent bonds also provides additional binding force, so that the intermolecular binding is more compact; the addition of Ag reduces the corrosion current density of the alloy, enhances the corrosion resistance of the alloy and reduces the growth of a grid; the addition of Si increases the mechanical property of the grid, improves the yield strength of the grid, and reduces the growth of the grid.
The beneficial effects of the invention are as follows: the novel alloy for the positive grid of the maintenance-free lead-acid storage battery provided by the invention has higher creep resistance, corrosion resistance and good mechanical property through the synergistic effect of different elements, fundamentally solves the problems of poor corrosion resistance, easy growth of the grid and the like of the positive grid prepared from the traditional lead alloy in a high-temperature environment, prolongs the high-temperature service life of the storage battery, greatly reduces the Sn consumption and obviously reduces the cost. Compared with the traditional lead alloy, the cost of the positive grid made of the novel alloy can be reduced by 373 yuan per t, the corrosion resistance can be improved by 12.62 percent, the hardness can be improved by 13.85 percent, the tensile strength can be improved by 5.72 percent, and the market competitiveness of the product is greatly improved.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by one of ordinary skill in the art without undue burden on the person of ordinary skill in the art based on embodiments of the present invention, are within the scope of the present invention.
Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate.
Example 1
The novel alloy for the storage battery comprises the following components in percentage by weight: 0.04% of Ca, 0.6% of Sn, 0.012% of Al, 0.05% of Ag, 0.08% of Ba, 0.002% of Si and the balance of Pb.
The novel alloy for the storage battery is prepared by the following method: adding electrolytic lead into a lead melting pot, heating to 950 ℃, starting stirring, adding the silicon-aluminum alloy, stirring for 6min, and stopping stirring after the silicon-aluminum alloy is completely melted; after the temperature is reduced to 750 ℃, stirring is started, barium is added, and stirring is stopped after the barium is completely melted after stirring for 5min; after the temperature is reduced to 580 ℃, stirring is started, silver is added, and stirring is stopped after the silver is completely melted after stirring for 4min; after the temperature is reduced to 550 ℃, stirring is started, calcium is added, stirring is carried out for 3min, and stirring is stopped after the calcium is completely melted; after the temperature is reduced to 480 ℃, stirring is started, tin is added, stirring is stopped after the tin is stirred for 2min to be completely melted, finally, sampling is carried out for component testing, and a lead ingot is cast after the components are qualified.
Example 2
The novel alloy for the storage battery comprises the following components in percentage by weight: 0.05% of Ca, 0.7% of Sn, 0.013% of Al, 0.03% of Ag, 0.1% of Ba, 0.003% of Si and the balance of Pb.
The novel alloy for the storage battery is prepared by the following method: adding electrolytic lead into a lead melting pot, heating to 945 ℃, starting stirring, adding the silicon-aluminum alloy, stirring for 6min, and stopping stirring after the silicon-aluminum alloy is completely melted; after the temperature is reduced to 755 ℃, stirring is started, barium is added, stirring is stopped after the barium is completely melted for 3 min; after the temperature is reduced to 570 ℃, stirring is started, silver is added, stirring is stopped after 3 minutes of complete melting of the silver; after the temperature is reduced to 550 ℃, stirring is started, calcium is added, stirring is stopped after the calcium is completely melted for 3 min; and cooling to 470 ℃, starting stirring, adding tin, stirring for 2min, stopping stirring after the tin is completely melted, finally sampling, performing component test, and casting a lead ingot after the components are qualified.
Example 3
The novel alloy for the storage battery comprises the following components in percentage by weight: 0.06% of Ca, 0.75% of Sn, 0.01% of Al, 0.035% of Ag, 0.09% of Ba, 0.003% of Si and the balance of Pb.
The novel alloy for the storage battery is prepared by the following method: adding electrolytic lead into a lead melting pot, heating to 940 ℃, starting stirring, adding the silicon-aluminum alloy, stirring for 6min, and stopping stirring after the silicon-aluminum alloy is completely melted; after the temperature is reduced to 760 ℃, stirring is started, barium is added, stirring is stopped after the barium is completely melted for 3 min; after the temperature is reduced to 575 ℃, stirring is started, silver is added, stirring is stopped after the silver is completely melted for 3 min; after the temperature is reduced to 550 ℃, stirring is started, calcium is added, stirring is stopped after the calcium is completely melted for 3 min; after the temperature is reduced to 475 ℃, stirring is started, tin is added, stirring is stopped after the tin is stirred for 2min to be completely melted, finally, sampling is carried out for component testing, and a lead ingot is cast after the components are qualified.
Example 4
The novel alloy for the storage battery comprises the following components in percentage by weight: 0.05% of Ca, 0.65% of Sn, 0.015% of Al, 0.04% of Ag, 0.07% of Ba, 0.0015% of Si and the balance of Pb.
The novel alloy for the storage battery is prepared by the following method: adding electrolytic lead into a lead melting pot, heating to 945 ℃, starting stirring, adding the silicon-aluminum alloy, stirring for 6min, and stopping stirring after the silicon-aluminum alloy is completely melted; after the temperature is reduced to 760 ℃, stirring is started, barium is added, stirring is stopped after the barium is completely melted for 3 min; after the temperature is reduced to 590 ℃, stirring is started to add silver, and stirring is stopped after the silver is completely melted after stirring for 3 min; cooling to 540 ℃, starting stirring, adding calcium, stirring for 3min, and stopping stirring after the calcium is completely melted; and cooling to 470 ℃, starting stirring, adding tin, stirring for 2min, stopping stirring after the tin is completely melted, finally sampling, performing component test, and casting a lead ingot after the components are qualified.
Example 5
The novel alloy for the storage battery comprises the following components in percentage by weight: 0.05% of Ca, 0.55% of Sn, 0.013% of Al, 0.045% of Ag, 0.11% of Ba, 0.002% of Si and the balance of Pb.
The novel alloy for the storage battery is prepared by the following method: adding electrolytic lead into a lead melting pot, heating to 960 ℃, starting stirring, adding the silicon-aluminum alloy, stirring for 6min, and stopping stirring after the silicon-aluminum alloy is completely melted; after the temperature is reduced to 760 ℃, stirring is started, barium is added, stirring is stopped after the barium is completely melted for 3 min; after the temperature is reduced to 585 ℃, stirring is started, silver is added, stirring is stopped after 3 minutes of complete melting of the silver; cooling to 540 ℃, starting stirring, adding calcium, stirring for 3min, and stopping stirring after the calcium is completely melted; after the temperature is reduced to 475 ℃, stirring is started, tin is added, stirring is stopped after the tin is stirred for 2min to be completely melted, finally, sampling is carried out for component testing, and a lead ingot is cast after the components are qualified.
Comparative example
The comparative example adopts the existing lead alloy, and the weight percentages of the components are as follows: 0.06% of Ca, 1.2% of Sn, 0.15% of Al, 0.006% of Ag and the balance of Pb.
The alloys used in examples 1-5 and comparative examples were subjected to physical and chemical characterization and battery performance testing as follows:
| performance of | Corrosion Rate (mg/cm) 2 /h） | Tensile strength (Mpa) | Hardness (HV) | National standard cycle endurance I life (secondary) | SAEJ2801 lifetime (Unit) | Cost reduction (Yuan/t) compared to comparative examples |
| Example 1 | 0.284 | 54.7 | 13.48 | 236 | 12 | 373 |
| Example 2 | 0.298 | 54.18 | 13.22 | 230 | 11 | 367 |
| Example 3 | 0.295 | 54.3 | 13.07 | 228 | 12 | 369 |
| Example 4 | 0.286 | 54.1 | 12.48 | 232 | 11 | 350 |
| Example 5 | 0.292 | 54.6 | 13.18 | 224 | 12 | 342 |
| Comparative example | 0.325 | 51.74 | 11.84 | 220 | 11 | / |
Wherein: the corrosion resistance test adopts a constant current weightlessness method, and the experimental conditions are as follows: carrying out water bath at 40 ℃ and constant current charging for 400 hours at 2A (3+4-), and calculating the corrosion rate of unit area in unit time; tensile strength test is referred to GB/T228-2002; hardness testing was performed using a vickers hardness tester.
Meanwhile, the service life of the storage battery made of the novel alloy is tested, and the service life of the cycle endurance I and the service life of the high-temperature SAEJ2801 are not lower than those of the storage battery made of the common lead alloy by adopting national standards GB5008.1-2013 and SAEJ 2801.
In conclusion, the cost of the positive grid made of the novel alloy provided by the invention is reduced by 373 yuan per t compared with that of the conventional lead alloy, meanwhile, the corrosion resistance can be improved by 12.62%, the hardness can be improved by 13.85%, the tensile strength can be improved by 5.72%, the comprehensive cost performance of the battery is greatly improved, and the market competitiveness of the product can be greatly improved.
The foregoing description of the exemplary embodiments of the invention is not intended to limit the invention to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (8)
1. An alloy for a positive grid of a maintenance-free lead-acid storage battery is characterized in that: the composite material consists of the following components in percentage by weight: 0.02-0.2% of Ca, 0.5-0.8% of Sn, 0.005-0.05% of Al, 0.002-0.3% of Ag, 0.002-0.4% of Ba, 0.001-0.08% of Si and the balance Pb.
2. The maintenance-free alloy for positive grids of lead-acid storage batteries according to claim 1, wherein: the weight percentages of the components are as follows: 0.01-0.15% of Ca, 0.55-0.75% of Sn, 0.01-0.015% of Al, 0.01-0.2% of Ag, 0.01-0.3% of Ba, 0.001-0.05% of Si and the balance Pb.
3. The maintenance-free alloy for positive grids of lead-acid storage batteries according to claim 1, wherein: the weight percentages of the components are as follows: 0.04-0.05% of Ca, 0.6-0.7% of Sn, 0.012-0.13% of Al, 0.04-0.05% of Ag, 0.08-0.1% of Ba, 0.002-0.003% of Si and the balance of Pb.
4. A method for preparing the alloy for the positive grid of the maintenance-free lead-acid storage battery as claimed in any one of claims 1 to 3, which is characterized in that: the process comprises the following steps: adding silicon-aluminum alloy, cooling and adding barium, cooling and adding silver, cooling and adding calcium, cooling and adding tin after the temperature of the electrolytic lead is increased, and casting ingot.
5. The method for preparing the alloy for the positive grid of the maintenance-free lead-acid storage battery, which is characterized in that: the method specifically comprises the following process steps:
s1: adding the electrolytic lead into a lead melting pot, heating, starting stirring, adding the silicon-aluminum alloy, stirring for 3-8min, and stopping stirring after the silicon-aluminum alloy is completely melted;
s2: cooling, then stirring, adding barium, stirring for 3-8min, and stopping stirring after the barium is completely melted;
s3: cooling, stirring, adding silver, stirring for 3-6min, and stopping stirring after the silver is completely melted;
s4: cooling, stirring, adding calcium, stirring for 2-5min, and stopping stirring after calcium is completely melted;
s5: cooling, then stirring, adding tin, stirring for 2-5min, and stopping stirring after the tin is completely melted;
s6: sampling for component testing, and casting lead ingot after the components are qualified.
6. The method for preparing the alloy for the positive grid of the maintenance-free lead-acid storage battery, which is characterized in that:
in the step S1, electrolytic lead is added into a lead melting pot, and after the temperature is increased to 900-1000 ℃, silicon aluminum alloy is added and stirring is started;
in the step S2, when the temperature is reduced to 750-800 ℃, adding barium and starting stirring;
in the step S3, when the temperature is reduced to 550-600 ℃, adding silver and starting stirring;
in the step S4, when the temperature is reduced to 530-550 ℃, adding calcium and starting stirring;
in step S5, tin is added and stirring is started when the temperature is reduced to 450-480 ℃.
7. The method for preparing the alloy for the positive grid of the maintenance-free lead-acid storage battery, which is characterized in that:
in the step S1, electrolytic lead is added into a lead melting pot, and after the temperature is increased to 940-960 ℃, silicon aluminum alloy is added and stirring is started;
in the step S2, when the temperature is reduced to 750-760 ℃, adding barium and starting stirring;
in the step S3, when the temperature is reduced to 570-590 ℃, adding silver and starting stirring;
in the step S4, when the temperature is reduced to 540-550 ℃, adding calcium and starting stirring;
in step S5, tin is added and stirring is started when the temperature is reduced to 470-480 ℃.
8. The method for preparing the alloy for the positive grid of the maintenance-free lead-acid storage battery, which is characterized in that: in the step S1, stirring for 5-7min; in the step S2, stirring for 3-5min; in the step S3, stirring for 3-4min; in the step S4, stirring for 2-4min; in step S5, stirring for 2-3min.
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| CN202210745851.3A CN116254437A (en) | 2022-06-29 | 2022-06-29 | Alloy for positive grid of maintenance-free lead-acid storage battery and preparation method of alloy |
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