CN111349812A - Energy-saving environment-friendly lead-based alloy - Google Patents
Energy-saving environment-friendly lead-based alloy Download PDFInfo
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- CN111349812A CN111349812A CN202010104271.7A CN202010104271A CN111349812A CN 111349812 A CN111349812 A CN 111349812A CN 202010104271 A CN202010104271 A CN 202010104271A CN 111349812 A CN111349812 A CN 111349812A
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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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Abstract
An energy-saving environment-friendly lead-based alloy is prepared from electrolytic lead and a lead-based master alloy according to a mass ratio of 9:1, wherein the lead-based master alloy comprises the following components in percentage by mass: 0.3 to 0.5 percent of aluminum, 1.2 to 2.0 percent of calcium, 8 to 15 percent of tin, 0.01 to 0.025 percent of silver, 1.5 to 4 percent of antimony, 0.02 to 0.08 percent of lanthanum and the balance of lead. In the invention, the addition of aluminum, calcium, tin, silver, antimony and lanthanum can improve the characteristics of the lead-based alloy; meanwhile, the invention has the characteristics of good consistency, good fluidity, high strength, good corrosion resistance, energy conservation, environmental protection and the like.
Description
Technical Field
The invention relates to the field of battery material manufacturing, in particular to an energy-saving and environment-friendly lead-based alloy.
Background
Lead-acid battery grid materials which are commercially produced at present are basically lead-based alloys, and particularly, lead-based alloys are adopted for positive grids. The positive grid mainly plays a role in supporting active substances and conducting electricity in the storage battery, does not participate in storage and release of electric energy, and accounts for about 12% of the small-sized power battery in weight and is higher. In addition, the current lead-based alloy preparation method is to directly mix lead and various formula auxiliary materials to prepare a finished alloy, the finished alloy is secondarily melted to prepare the grid, and the lead is melted for 2 times in the preparation process, so that a proper technology capable of reducing most of electrolytic lead for secondary melting is urgently needed. Meanwhile, the temperature is high, the energy consumption is high, the burning loss is serious, and the corresponding lead-containing tail gas and lead-containing solid waste are generated.
Therefore, a new technical solution is needed to solve the above technical problems.
Disclosure of Invention
In order to solve the problems, the invention provides an energy-saving and environment-friendly lead-based alloy.
The technical scheme adopted by the invention is as follows:
an energy-saving environment-friendly lead-based alloy is prepared from electrolytic lead and a lead-based master alloy according to a mass ratio of 9:1, wherein the lead-based master alloy comprises the following components in percentage by mass: 0.3 to 0.5 percent of aluminum, 1.2 to 2.0 percent of calcium, 8 to 15 percent of tin, 0.01 to 0.025 percent of silver, 1.5 to 4 percent of antimony, 0.02 to 0.08 percent of lanthanum and the balance of lead.
Further, the lead-based master alloy preferably comprises the following components in percentage by mass: 0.45% of aluminum, 1.35% of calcium, 13% of tin, 0.02% of silver, 1.8% of antimony, 0.03% of lanthanum and the balance of lead.
Further, the preparation of the lead-based master alloy adopts electrolytic lead as a lead source, and the preparation process of the lead-based master alloy comprises the following steps: adding electrolytic lead with the formula amount into a high-temperature furnace with a stirrer, heating to 400-450 ℃, adding a certain amount of activated carbon and caustic soda flakes after the lead is completely melted, starting the stirrer to stir, fully mixing and reacting until the lead slag is powdery, fishing up the lead slag floating on the surface of lead liquid by using a special tool, then heating to 480-520 ℃, adding antimony with the formula amount, starting stirring, controlling the stirring speed of the stirrer to be 40-50 r/min, adding tin with the formula amount after the antimony blocks are completely melted, and stirring until the antimony blocks are completely melted; continuously heating to 580-620 ℃, adding silver with the formula amount, stirring for 10min, stopping stirring, continuously heating to 650-680 ℃, adding aluminum and calcium with the formula amount, stirring at the stirring speed of 40-50 r/min, simultaneously continuously heating to 950-980 ℃, adding lanthanum with the formula amount, continuously stirring in the temperature range until the lanthanum is completely melted, continuously stirring for 10min, uniformly mixing all components of the lead alloy, and testing that the components of the lead-based master alloy meet the requirement of the formula content range by using a spectrometer; stirring at a stirring speed of 10-15 r/min, starting a cooling program, cooling the alloy, and casting the alloy into a lead ingot at a temperature of 600-650 ℃.
Further, the mass percentage of the activated carbon relative to the lead source is 0.029-0.031%, and preferably 0.03%; the mass percentage of the flake caustic soda relative to the activated carbon is 39.9-40.1%, and preferably 40%. The activated carbon is mainly used for reducing slag, can reduce partial lead oxide into lead, and simultaneously separates the lead from the oxidized slag; the caustic soda flakes are mainly used for removing impurities (copper, iron, calcium, tin, aluminum, antimony and the like) in lead.
An energy-saving and environment-friendly lead-based alloy application method comprises the steps of adding electrolytic lead and a lead-based master alloy into a lead pot with a stirring device according to the mass ratio of 9:1, controlling the temperature in the lead pot at 450-520 ℃, controlling the stirring speed at 5-15 r/min after the alloy is completely melted, and applying the lead-based master alloy after the alloy is uniformly stirred.
Furthermore, the capacity of the lead pot is matched with the using speed of the lead liquid, and one pot of lead liquid needs to be used up within 6 hours.
The invention has the beneficial effects that:
1. the aluminum, calcium, tin, silver, antimony and lanthanum elements can all play a role in improving the characteristics of the lead-based alloy: calcium element can effectively improve the strength of the lead alloy, tin element and antimony element can improve the binding force between the grid material and the active substance, effectively inhibit the formation of a binding layer passive film and improve the deep cycle performance of the storage battery; the silver element and the lanthanum element can effectively improve the corrosion resistance and the creep resistance of the alloy; the aluminum element in the alloy mainly has low solubility of aluminum in the alloy, and simultaneously has low density, so that an aluminum protective layer can be formed on the upper layer of the alloy to block the reaction of oxygen and water in the air with elements such as calcium, lanthanum and the like, and the protective and auxiliary effects are achieved;
2. compared with the conventional process, the method has the characteristics of good consistency, good fluidity, high strength, good corrosion resistance, energy conservation, environmental protection and the like, can reduce 90% of electrolytic lead for secondary melting by preparing the lead-based master alloy, can reduce the energy consumption of each ton of alloy by 40kWh, and simultaneously reduces over 50% of lead-containing tail gas emission and 30% of lead-containing solid waste. Due to the improvement of the corrosion resistance of the grid and the design of the same service life, the size of grid ribs can be reduced, and the lead content of the positive grid can be reduced by 35 percent through tests.
Detailed Description
For the purpose of enhancing the understanding of the present invention, the present invention will be further described in detail with reference to the following examples, which are provided for the purpose of illustration only and are not intended to limit the scope of the present invention.
Example 1:
an energy-saving environment-friendly lead-based alloy is prepared from electrolytic lead and a lead-based master alloy according to a mass ratio of 9:1, and the preparation process of the lead-based master alloy comprises the following steps: 1667kg of electrolytic lead is added into a high-temperature furnace with a stirrer, the temperature is raised to 400-450 ℃, when the lead is completely melted, 0.5kg of activated carbon and 0.2kg of flake caustic soda are added, the activated carbon is mainly used for reducing slag, can reduce partial lead oxide into lead, and simultaneously lead and oxidized slag are separated; the caustic soda flakes are mainly used for removing impurities (copper, iron, calcium, tin, aluminum, antimony and the like) in lead. Starting a stirrer to stir, fully mixing and reacting until lead slag is powdery, fishing up the lead slag floating on the surface of lead liquid by using a special tool, then heating to 480-520 ℃, adding 36kg of antimony, starting stirring, controlling the stirring speed of the stirrer to be 50 r/min, adding 260kg of tin after antimony blocks are completely melted, and stirring until the antimony blocks are completely melted; continuously heating to 580-620 ℃, adding 400g of silver, stirring for 10min, stopping stirring, continuously heating to 650-680 ℃, adding 9kg of aluminum and 27kg of calcium, stirring at a stirring speed of 50 r/min, simultaneously continuously heating to 950-980 ℃, adding 600g of lanthanum, continuously stirring in the temperature range until the lanthanum is completely melted, continuously stirring for 10min to uniformly mix the components of the lead alloy, and testing that the components of the lead-based master alloy meet the requirement of the formula content range by using a spectrometer; stirring at a stirring speed of 15 r/min, starting a cooling program, cooling the alloy, and casting the alloy into a lead ingot at the temperature of 600-650 ℃.
An energy-saving and environment-friendly lead-based alloy application method comprises the steps of adding electrolytic lead and a lead-based master alloy into a lead pot with a stirring device according to the mass ratio of 9:1, controlling the temperature in the lead pot at 450-520 ℃, controlling the stirring speed at 5-15 r/min after the alloy is completely melted, and applying the lead-based master alloy after the alloy is uniformly stirred. The capacity of the lead pot is matched with the using speed of the lead liquid, and one pot of lead liquid needs to be used up within 6 hours.
Example 2:
in the embodiment, the energy-saving environment-friendly lead-based alloy is prepared from electrolytic lead and a lead-based master alloy according to the mass ratio of 9: 1. Meanwhile, the preparation process for preparing the lead-based master alloy in the embodiment is consistent with that in the embodiment 1, and only the formula amount is inconsistent, namely: the mass of electrolytic lead was 1779.4kg, the mass of activated carbon was 534g, the mass of flake caustic soda was 214g, the mass of aluminum was 6kg, the mass of calcium was 24kg, the mass of tin was 160kg, the mass of silver was 200g, the mass of antimony was 30kg, and the mass of lanthanum was 400 g.
Similarly, the method of using the energy-saving and environment-friendly lead-based alloy in this example is the same as that in example 1.
Example 3:
in the embodiment, the energy-saving environment-friendly lead-based alloy is prepared from electrolytic lead and a lead-based master alloy according to the mass ratio of 9: 1. Meanwhile, the preparation process for preparing the lead-based master alloy in the embodiment is consistent with that in the embodiment 1, and only the formula amount is inconsistent, namely: the mass of electrolytic lead was 1567.9kg, the mass of activated carbon was 470g, the mass of flake caustic soda was 188g, the mass of aluminum was 10kg, the mass of calcium was 40kg, the mass of tin was 300kg, the mass of silver was 500g, the mass of antimony was 80kg, and the mass of lanthanum was 1.6 kg.
Similarly, the method of using the energy-saving and environment-friendly lead-based alloy in this example is the same as that in example 1.
Example 4:
in the embodiment, the energy-saving environment-friendly lead-based alloy is prepared from electrolytic lead and a lead-based master alloy according to the mass ratio of 9: 1. Meanwhile, the preparation process for preparing the lead-based master alloy in the embodiment is consistent with that in the embodiment 1, and only the formula amount is inconsistent, namely: the mass of electrolytic lead was 1678.66kg, the mass of activated carbon was 504g, the mass of flake caustic soda was 202g, the mass of aluminum was 8kg, the mass of calcium was 32kg, the mass of tin was 230kg, the mass of silver was 340g, the mass of antimony was 50kg, and the mass of lanthanum was 1 kg.
Similarly, the method of using the energy-saving and environment-friendly lead-based alloy in this example is the same as that in example 1.
Example 5:
in the embodiment, the energy-saving environment-friendly lead-based alloy is prepared from electrolytic lead and a lead-based master alloy according to the mass ratio of 9: 1. Meanwhile, the preparation process for preparing the lead-based master alloy in the embodiment is consistent with that in the embodiment 1, and only the formula amount is inconsistent, namely: the mass of electrolytic lead is 1615.5kg, the mass of activated carbon is 485g, the mass of flake caustic soda is 194g, the mass of aluminum is 7kg, the mass of calcium is 36kg, the mass of tin is 280kg, the mass of silver is 300g, the mass of antimony is 60kg, and the mass of lanthanum is 1.2 kg.
Similarly, the method of using the energy-saving and environment-friendly lead-based alloy in this example is the same as that in example 1.
Claims (6)
1. The energy-saving environment-friendly lead-based alloy is characterized by being prepared from electrolytic lead and a lead-based master alloy according to a mass ratio of 9:1, wherein the lead-based master alloy comprises the following components in percentage by mass: 0.3 to 0.5 percent of aluminum, 1.2 to 2.0 percent of calcium, 8 to 15 percent of tin, 0.01 to 0.025 percent of silver, 1.5 to 4 percent of antimony, 0.02 to 0.08 percent of lanthanum and the balance of lead.
2. The energy-saving and environment-friendly lead-based alloy as claimed in claim 1, wherein the lead-based master alloy preferably comprises the following components in percentage by mass: 0.45% of aluminum, 1.35% of calcium, 13% of tin, 0.02% of silver, 1.8% of antimony, 0.03% of lanthanum and the balance of lead.
3. The energy-saving environment-friendly lead-based alloy as claimed in claims 1 and 2, wherein the lead-based master alloy is prepared by adopting electrolytic lead as a lead source, and the preparation process of the lead-based master alloy comprises the following steps: adding electrolytic lead with the formula amount into a high-temperature furnace with a stirrer, heating to 400-450 ℃, adding a certain amount of activated carbon and caustic soda flakes after the lead is completely melted, starting the stirrer to stir, fully mixing and reacting until the lead slag is powdery, fishing up the lead slag floating on the surface of lead liquid by using a special tool, then heating to 480-520 ℃, adding antimony with the formula amount, starting stirring, controlling the stirring speed of the stirrer to be 40-50 r/min, adding tin with the formula amount after the antimony blocks are completely melted, and stirring until the antimony blocks are completely melted; continuously heating to 580-620 ℃, adding silver with the formula amount, stirring for 10min, stopping stirring, continuously heating to 650-680 ℃, adding aluminum and calcium with the formula amount, stirring at the stirring speed of 40-50 r/min, simultaneously continuously heating to 950-980 ℃, adding lanthanum with the formula amount, continuously stirring in the temperature range until the lanthanum is completely melted, continuously stirring for 10min, uniformly mixing all components of the lead alloy, and testing that the components of the lead-based master alloy meet the requirement of the formula content range by using a spectrometer; stirring at a stirring speed of 10-15 r/min, starting a cooling program, cooling the alloy, and casting the alloy into a lead ingot at a temperature of 600-650 ℃.
4. An energy-saving and environment-friendly lead-based alloy as claimed in claim 3, wherein the mass percentage of the activated carbon relative to the lead source is in the range of 0.029-0.031%, preferably 0.03%; the mass percentage of the flake caustic soda relative to the activated carbon is 39.9-40.1%, and preferably 40%.
5. An energy-saving environment-friendly lead-based alloy using method is characterized in that electrolytic lead and the lead-based master alloy described in claim 3 are added into a lead pot with a stirring device according to the mass ratio of 9:1, the temperature in the lead pot is controlled at 450-520 ℃, after the alloy is completely melted, the stirring speed is controlled at 5-15 r/min, and the lead-based alloy can be used after being uniformly stirred.
6. The use method of the energy-saving and environment-friendly lead-based alloy as claimed in claim 5, wherein the capacity of the lead pot is matched with the use speed of the molten lead, and one pot of the molten lead needs to be used up within 6 hours.
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Cited By (2)
| 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 |
| CN115233033A (en) * | 2022-07-14 | 2022-10-25 | 铅锂智行(北京)科技有限公司 | Lead-based alloy and product thereof |
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| CN107881356A (en) * | 2017-11-29 | 2018-04-06 | 河南超威电源有限公司 | A kind of lead-acid accumulator silver alloy anode plate grid and preparation method thereof |
| CN108467968A (en) * | 2018-02-06 | 2018-08-31 | 天能电池集团有限公司 | A kind of preparation method of lead accumulator grid alloy |
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Cited By (2)
| 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 |
| CN115233033A (en) * | 2022-07-14 | 2022-10-25 | 铅锂智行(北京)科技有限公司 | Lead-based alloy and product thereof |
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Address after: 226400 No. 118 Yalujiang Road, New Area of Rudong Economic Development Zone, Nantong City, Jiangsu Province Patentee after: Jiangsu Haibao New Energy Co.,Ltd. Address before: 226400 No. 118 Yalujiang Road, New Area of Rudong Economic Development Zone, Nantong City, Jiangsu Province Patentee before: Jiangsu Hairui Power Supply Co.,Ltd. |