A lead calcium tin copper alloy, a preparation method, a positive plate grid and a lead-acid storage battery

Abstract

The application discloses a lead-calcium-tin-copper alloy, a preparation method, a positive plate grid and a lead-acid storage battery. The lead-calcium-tin-copper alloy is prepared from the following components: 0.01-0.02 parts of sodium, 0.1-0.12 parts of calcium, 0.4-0.6 parts of tin, 0.03-0.04 parts of copper and 100 parts of lead. The application sets the added components sodium and copper, and sets the proportion of the components in the alloy, so that the prepared alloy has strong corrosion resistance, and the cycle number and the floating life of the lead-acid storage battery are obviously improved when the alloy is applied to the positive plate grid of the lead-acid storage battery.

Description

Technical Field

[0001] This application relates to the field of alloy technology for positive plate grids of lead-acid batteries, and in particular to a lead-calcium-tin-copper alloy grid, its preparation method, and a lead-acid battery. Background Technology

[0002] Lead-acid batteries mainly consist of three parts: the container, plates, and separators. The grid is the most important inactive material in a lead-acid battery, and since its invention, Pb-Sb alloy has been the primary material used for the grid. However, with the advent of maintenance-free lead-acid batteries, Pb-Sb alloy can no longer meet the performance requirements for maintenance-free operation and has been gradually replaced by other alloys. Research has found that Pb-Ca alloy has excellent maintenance-free performance, but its intergranular corrosion is severe, and the calcium content is difficult to control. In particular, the high-resistance passivation film formed on the surface of the battery grid severely hinders the charging and discharging process, exacerbating early capacity loss (PCL) and significantly shortening the float life of the lead-acid battery.

[0003] Besides lead-calcium alloys, lead-antimony alloys are also widely used in batteries. Lead-antimony alloys have a low melting point, good fluidity in the molten state, and are easy to cast. However, the gas evolution overpotential of the grid is low, resulting in a shorter service life. Summary of the Invention

[0004] In order to solve at least one of the above-mentioned technical problems and develop an alloy with good corrosion resistance to improve the cycle life and float charge life of lead-acid batteries made therefrom, this application provides a lead-calcium-tin-copper alloy, a preparation method, a positive electrode grid, and a lead-acid battery.

[0005] On the one hand, the lead-calcium-tin-copper alloy provided in this application is prepared from the following components: 0.01-0.02 parts sodium, 0.1-0.12 parts calcium, 0.4-0.6 parts tin, 0.03-0.04 parts copper, and 100 parts lead.

[0006] By adopting the above technical solutions, the corrosion resistance of the alloy is improved, and the cycle life and float charge life of the prepared lead-acid battery are significantly increased.

[0007] Optionally, it is prepared from the following components: 0.01-0.02 parts sodium, 0.1-0.12 parts calcium, 0.4-0.6 parts tin, 0.03-0.04 parts copper, 0.0015-0.0025 parts silver, and 100 parts lead.

[0008] By adopting the above technical solutions, the cycle life of lead-acid batteries can be significantly increased, extending their service life; and corrosion resistance can be improved to a certain extent, thus increasing the float charge service life of lead-acid batteries.

[0009] Optionally, it is prepared from the following components: 0.01-0.02 parts sodium, 0.1-0.12 parts calcium, 0.4-0.6 parts tin, 0.03-0.04 parts copper, 0.01-0.02 parts lanthanum, and 100 parts lead.

[0010] By adopting the above technical solutions, the corrosion resistance of the alloy is significantly improved, the float life of lead-acid batteries is increased, and the number of cycles is also improved to a certain extent.

[0011] Optionally, it is prepared from the following components: 0.01-0.02 parts sodium, 0.1-0.12 parts calcium, 0.4-0.6 parts tin, 0.03-0.04 parts copper, 0.0015-0.0025 parts silver, 0.01-0.02 parts lanthanum, and 100 parts lead.

[0012] By adopting the above technical solution, the corrosion resistance can be significantly improved by adding silver or lanthanum alone, resulting in a higher cycle life and float life of the prepared lead-acid battery.

[0013] Optionally, the mass ratio of silver to lanthanum is set at 1:8-10.

[0014] By adopting the above technical solution, the cycle life of the prepared lead-acid battery can be effectively increased, resulting in a longer service life.

[0015] Secondly, this application provides a method for preparing the aforementioned lead-calcium-tin-copper alloy, comprising the following steps:

[0016] S1. Melt 35wt% of lead in the formula into liquid lead, heat up, add metals other than lead, sodium, calcium and tin in the formula according to the formula amount, and stir until eutectic state is reached; add 15wt% of lead in the formula and stir until completely melted, cool down to cast ingot, and cool to obtain lead ingot.

[0017] S2. Melt 35 wt% of lead into liquid lead, add sodium, calcium and lead ingots obtained in S1 according to the formula, and stir until eutectic state is reached; add 15 wt% of lead according to the formula, cool down and then add tin, and stir until eutectic state is reached; after cooling down, lead-calcium-tin-copper alloy is obtained.

[0018] Optionally, in step S1, lead is melted at 400–500°C; after heating to 1100–1150°C, metals other than lead, sodium, calcium, and tin in the formula are added; and the temperature is lowered to 600–700°C to cast ingots.

[0019] Optionally, in step S2, lead is melted at 400–500°C; sodium, calcium, and the lead ingot obtained in step S1 are added at 700–800°C; and tin is added at 550–600°C.

[0020] Thirdly, this application provides a positive electrode grid prepared from the aforementioned lead-calcium-tin-copper alloy.

[0021] Fourthly, this application provides a lead-acid battery including the aforementioned positive electrode grid.

[0022] In summary, the present invention has at least one of the following beneficial technical effects:

[0023] This application, by adding sodium and copper components and setting the proportions of each component in the alloy, produces an alloy with strong corrosion resistance. When applied to the positive grid of a lead-acid battery, it significantly improves the cycle life and float life of the lead-acid battery. Detailed Implementation

[0024] The present application will be further described in detail below with reference to the embodiments.

[0025] The components and weight fractions in Examples 1-22 and Comparative Examples 1-3 of this application are shown in the table below:

[0026]

[0027]

[0028] Example 1

[0029] This embodiment provides a lead-calcium-tin-copper alloy, prepared from the following components: 0.01 parts sodium, 0.11 parts calcium, 0.6 parts tin, 0.03 parts copper, and 100 parts lead; specifically prepared according to the following method:

[0030] Add 35 kg of lead to an intermediate frequency furnace, heat to 400°C to melt into molten lead, heat to 1100°C, add 30 g of copper, and stir until eutectic state is reached; add 15 kg of lead and stir until completely melted, cool to 700°C to cast ingots, and cool to obtain lead ingots.

[0031] Add 35 kg of lead to a medium-frequency furnace, heat to 400°C to melt it into liquid lead, heat to 700°C, add 10 g of sodium, 110 g of calcium and the lead ingots prepared above, and stir until a eutectic state is reached; add 15 kg of lead, cool to 550°C and add 600 g of tin, and stir until a eutectic state is reached; after cooling, a lead-calcium-tin-copper alloy is obtained.

[0032] This embodiment also provides a positive electrode grid, which is made of the lead-calcium-tin-copper alloy prepared above.

[0033] This embodiment also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0034] Example 2

[0035] This embodiment provides a lead-calcium-tin-copper alloy, prepared from the following components: 0.015 parts sodium, 0.12 parts calcium, 0.4 parts tin, 0.035 parts copper, and 100 parts lead; specifically prepared according to the following method:

[0036] Add 35 kg of lead to an intermediate frequency furnace, heat to 500°C to melt into molten lead, heat to 1100°C, add 30 g of copper, and stir until eutectic state is reached; add 15 kg of lead and stir until completely melted, cool to 600°C to cast ingots, and cool to obtain lead ingots.

[0037] Add 35 kg of lead to a medium-frequency furnace, heat to 450°C to melt into molten lead, heat to 750°C, add 10 g of sodium, 110 g of calcium and the lead ingots prepared above, and stir until a eutectic state is reached; add 15 kg of lead, cool to 600°C and add 600 g of tin, and stir until a eutectic state is reached; after cooling, a lead-calcium-tin-copper alloy is obtained.

[0038] This embodiment also provides a positive electrode grid, which is made of the lead-calcium-tin-copper alloy prepared above.

[0039] This embodiment also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0040] Example 3

[0041] This embodiment provides a lead-calcium-tin-copper alloy, prepared from the following components: 0.02 parts sodium, 0.1 parts calcium, 0.5 parts tin, 0.04 parts copper, and 100 parts lead; specifically prepared according to the following method:

[0042] Add 35 kg of lead to an intermediate frequency furnace, heat to 450°C to melt into lead liquid, heat to 1150°C, add 30 g of copper, and stir until eutectic state is reached; add 15 kg of lead and stir until completely melted, cool to 650°C to cast ingots, and cool to obtain lead ingots.

[0043] Add 35 kg of lead to a medium-frequency furnace, heat to 500°C to melt into molten lead, heat to 800°C, add 10 g of sodium, 110 g of calcium and the lead ingots prepared above, and stir until a eutectic state is reached; add 15 kg of lead, cool to 600°C and add 600 g of tin, and stir until a eutectic state is reached; after cooling, a lead-calcium-tin-copper alloy is obtained.

[0044] This embodiment also provides a positive electrode grid, which is made of the lead-calcium-tin-copper alloy prepared above.

[0045] This embodiment also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0046] Comparative Example 1

[0047] This comparative example provides a lead-calcium-tin alloy, prepared from the following components: 0.01 parts sodium, 0.11 parts calcium, 0.6 parts tin, and 100 parts lead; specifically prepared according to the following method:

[0048] 70 kg of lead was added to an intermediate frequency furnace and heated to 400°C to melt it into liquid lead. The temperature was then raised to 700°C, and 10 g of sodium and 110 g of calcium were added. The mixture was stirred until it reached a eutectic state. 30 kg of lead was added, and the temperature was lowered to 550°C. 600 g of tin was added and stirred until it reached a eutectic state. After cooling, a lead-calcium-tin alloy was obtained.

[0049] This comparative example also provides a positive electrode grid, which is made of the lead-calcium-tin alloy prepared above.

[0050] This comparative example also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0051] Comparative Example 2

[0052] This comparative example provides a lead-calcium-tin-copper alloy, prepared from the following components: 0.12 parts calcium, 0.4 parts tin, 0.035 parts copper, and 100 parts lead; specifically prepared according to the following method:

[0053] Add 35 kg of lead to an intermediate frequency furnace, heat to 500°C to melt into molten lead, heat to 1100°C, add 30 g of copper, and stir until eutectic state is reached; add 15 kg of lead and stir until completely melted, cool to 600°C to cast ingots, and cool to obtain lead ingots.

[0054] Add 35 kg of lead to a medium-frequency furnace, heat to 450°C to melt into molten lead, heat to 750°C, add 110 g of calcium and the lead ingots prepared above, and stir until a eutectic state is reached; add 15 kg of lead, cool to 600°C, add 600 g of tin, and stir until a eutectic state is reached; after cooling, a lead-calcium-tin-copper alloy is obtained.

[0055] This comparative example also provides a positive electrode grid, which is made of the lead-calcium-tin-copper alloy prepared above.

[0056] This comparative example also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0057] Comparative Example 3

[0058] This comparative example provides a lead-calcium-tin-copper alloy, prepared from the following components: 0.1 parts calcium, 0.5 parts tin, and 100 parts lead; specifically prepared according to the following method:

[0059] 70 kg of lead was added to an intermediate frequency furnace and heated to 400°C to melt it into liquid lead. The temperature was then raised to 700°C, and 110 g of calcium was added. The mixture was stirred until it reached a eutectic state. 30 kg of lead was added, and the temperature was lowered to 550°C. 600 g of tin was added and stirred until it reached a eutectic state. After cooling, a lead-calcium-tin alloy was obtained.

[0060] This comparative example also provides a positive electrode grid, which is made of the lead-calcium-tin alloy prepared above.

[0061] This comparative example also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0062] Cycle test: Four lead-acid batteries from Examples 1-3 and Comparative Examples 1-3 were taken and fully charged. The four lead-acid batteries in the same group were connected in series and discharged at 11A current in an environment of 25±2℃ until the battery pack terminal voltage reached 42V. The voltage was kept constant at 59.2V and the current was limited to 11A for 4 hours. This constitutes one cycle. The above cycle steps were repeated until the discharge time was less than 1.6 hours for three consecutive times, at which point the experiment was terminated. The cycle test results for the lead-acid batteries in Examples 1-3 and Comparative Examples 1-3 are shown in Table 1.

[0063] High-temperature accelerated float charge life test: The lead-acid batteries in Examples 1-3 and Comparative Examples 1-3 were continuously charged at 2.27V / cell for 30 days in an environment of 60℃±2℃. The batteries were then removed and placed for 24h~36h. A 3h rate (150A discharge to 1.80V) capacity test was then conducted in an environment of 25℃±5℃. This constituted one test cycle, equivalent to one year of life. The above steps were repeated until the battery capacity was lower than 80% of the rated capacity at the 3h rate, and the test was conducted again. The test was terminated when it was confirmed that the capacity was still lower than 80%. The high-temperature accelerated float charge life test results of the lead-acid batteries in Examples 1-3 and Comparative Examples 1-3 are shown in Table 1.

[0064] Table 1 Performance test results of lead-acid batteries in Examples 1-3 and Comparative Examples 1-3

[0065] Loop count High temperatures accelerate float charge lifespan Example 1 356 9 Example 2 387 10 Example 3 395 10 Comparative Example 1 327 7 Comparative Example 2 298 8 Comparative Example 3 282 6

[0066] As can be seen from Examples 1-3, Comparative Examples 1-3 and Table 1, when sodium and copper are added simultaneously and the positive electrode grid is fabricated according to the component weight ratio of this application (0.01-0.02 parts sodium, 0.1-0.12 parts calcium, 0.4-0.6 parts tin, 0.03-0.04 parts copper, and 100 parts lead) using the same preparation process, and applied to lead-acid batteries of the same specifications, the cycle life and float life of the lead-acid batteries are significantly improved.

[0067] Example 4

[0068] This embodiment provides a lead-calcium-tin-copper alloy, prepared from the following components: 0.01 parts sodium, 0.11 parts calcium, 0.6 parts tin, 0.03 parts copper, 0.0015 parts silver, and 100 parts lead; specifically prepared according to the following method:

[0069] Add 35 kg of lead to an intermediate frequency furnace, heat to 400°C to melt into molten lead, heat to 1100°C, add 30 g of copper and 1.5 g of silver, stir until eutectic state is reached; add 15 kg of lead and stir until completely melted, cool to 700°C to cast ingots, and cool to obtain lead ingots.

[0070] Add 35 kg of lead to a medium-frequency furnace, heat to 400°C to melt it into liquid lead, heat to 700°C, add 10 g of sodium, 110 g of calcium and the lead ingots prepared above, and stir until a eutectic state is reached; add 15 kg of lead, cool to 550°C and add 600 g of tin, and stir until a eutectic state is reached; after cooling, a lead-calcium-tin-copper alloy is obtained.

[0071] This embodiment also provides a positive electrode grid, which is made of the lead-calcium-tin-copper alloy prepared above.

[0072] This embodiment also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0073] Example 5

[0074] This embodiment provides a lead-calcium-tin-copper alloy, prepared from the following components: 0.01 parts sodium, 0.11 parts calcium, 0.6 parts tin, 0.03 parts copper, 0.002 parts silver, and 100 parts lead; specifically prepared according to the following method:

[0075] Add 35 kg of lead to an intermediate frequency furnace, heat to 400°C to melt into molten lead, heat to 1100°C, add 30 g of copper and 2 g of silver, stir until eutectic state is reached; add 15 kg of lead and stir until completely melted, cool to 700°C to cast ingots, and cool to obtain lead ingots.

[0076] Add 35 kg of lead to a medium-frequency furnace, heat to 400°C to melt it into liquid lead, heat to 700°C, add 10 g of sodium, 110 g of calcium and the lead ingots prepared above, and stir until a eutectic state is reached; add 15 kg of lead, cool to 550°C and add 600 g of tin, and stir until a eutectic state is reached; after cooling, a lead-calcium-tin-copper alloy is obtained.

[0077] This embodiment also provides a positive electrode grid, which is made of the lead-calcium-tin-copper alloy prepared above.

[0078] This embodiment also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0079] Example 6

[0080] This embodiment provides a lead-calcium-tin-copper alloy, prepared from the following components: 0.01 parts sodium, 0.11 parts calcium, 0.6 parts tin, 0.03 parts copper, 0.0025 parts silver, and 100 parts lead; specifically prepared according to the following method:

[0081] Add 35 kg of lead to an intermediate frequency furnace, heat to 400°C to melt into molten lead, heat to 1100°C, add 30 g of copper and 2.5 g of silver, stir until eutectic state is reached; add 15 kg of lead and stir until completely melted, cool to 700°C to cast ingots, and cool to obtain lead ingots.

[0082] Add 35 kg of lead to a medium-frequency furnace, heat to 400°C to melt it into liquid lead, heat to 700°C, add 10 g of sodium, 110 g of calcium and the lead ingots prepared above, and stir until a eutectic state is reached; add 15 kg of lead, cool to 550°C and add 600 g of tin, and stir until a eutectic state is reached; after cooling, a lead-calcium-tin-copper alloy is obtained.

[0083] This embodiment also provides a positive electrode grid, which is made of the lead-calcium-tin-copper alloy prepared above.

[0084] This embodiment also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0085] Example 7

[0086] This embodiment provides a lead-calcium-tin-copper alloy, prepared from the following components: 0.015 parts sodium, 0.12 parts calcium, 0.4 parts tin, 0.035 parts copper, 0.002 parts silver, and 100 parts lead; specifically prepared according to the following method:

[0087] Add 35 kg of lead to an intermediate frequency furnace, heat to 500°C to melt into molten lead, heat to 1100°C, add 30 g of copper and 2 g of silver, stir until eutectic state is reached; add 15 kg of lead and stir until completely melted, cool to 600°C to cast ingots, and cool to obtain lead ingots.

[0088] Add 35 kg of lead to a medium-frequency furnace, heat to 450°C to melt into molten lead, heat to 750°C, add 10 g of sodium, 110 g of calcium and the lead ingots prepared above, and stir until a eutectic state is reached; add 15 kg of lead, cool to 600°C and add 600 g of tin, and stir until a eutectic state is reached; after cooling, a lead-calcium-tin-copper alloy is obtained.

[0089] This embodiment also provides a positive electrode grid, which is made of the lead-calcium-tin-copper alloy prepared above.

[0090] This embodiment also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0091] Example 8

[0092] This embodiment provides a lead-calcium-tin-copper alloy, prepared from the following components: 0.02 parts sodium, 0.1 parts calcium, 0.5 parts tin, 0.04 parts copper, 0.0025 parts silver, and 100 parts lead; specifically prepared according to the following method:

[0093] Add 35 kg of lead to an intermediate frequency furnace, heat to 450°C to melt it into molten lead, heat to 1150°C, add 30 g of copper and 2.5 g of silver, stir until eutectic state is reached; add 15 kg of lead and stir until completely melted, cool to 650°C to cast ingots, and cool to obtain lead ingots.

[0094] Add 35 kg of lead to a medium-frequency furnace, heat to 500°C to melt into molten lead, heat to 800°C, add 10 g of sodium, 110 g of calcium and the lead ingots prepared above, and stir until a eutectic state is reached; add 15 kg of lead, cool to 600°C and add 600 g of tin, and stir until a eutectic state is reached; after cooling, a lead-calcium-tin-copper alloy is obtained.

[0095] This embodiment also provides a positive electrode grid, which is made of the lead-calcium-tin-copper alloy prepared above.

[0096] This embodiment also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0097] The lead-acid batteries in Examples 4-8 were subjected to cycle number tests and high-temperature accelerated float charge life tests according to the above test methods; the test results are shown in Table 2.

[0098] Table 2 Performance test results of lead-acid batteries in Examples 4-8

[0099]

[0100]

[0101] As shown in Examples 4-8 and Table 2, this application, by adding lead, sodium, calcium, tin, and copper components without changing the original component ratio, and then adding silver, can effectively improve the quality of the active material and enhance the corrosion resistance of the alloy. However, as shown in Examples 4-6 and Table 2, when the weight percentage of silver added is 0.0015, the cycle life of the lead-acid battery increases significantly, but the float life does not improve significantly. When the weight percentage of silver increases from 0.0015 to 0.002, the increase in the cycle life of the lead-acid battery slows down, but the improvement in float life is more significant. When the weight percentage of silver increases from 0.002 to 0.0025, the cycle life of the lead-acid battery does not improve significantly, and the float life does not change significantly either.

[0102] As can be seen from Examples 4 and 7-8, changing the amount of lead, sodium, calcium, tin, and copper components while keeping the amount of silver added constant has a certain impact on the cycle life and float life of lead-acid batteries. The cycle life of the lead-acid battery in Example 7 is slightly improved compared to Example 5, and the float life increases significantly from 10 to 11 cycles. Example 8 shows a similar improvement in cycle life as Example 6 and Example 7 shows a similar improvement as Example 5, but the float life increases considerably from 10 to 12 cycles.

[0103] Example 9

[0104] This embodiment provides a lead-calcium-tin-copper alloy, prepared from the following components: 0.01 parts sodium, 0.11 parts calcium, 0.6 parts tin, 0.03 parts copper, 0.01 parts lanthanum, and 100 parts lead; specifically prepared according to the following method:

[0105] Add 35 kg of lead to an intermediate frequency furnace, heat to 400°C to melt into molten lead, heat to 1100°C, add 30 g of copper and 10 g of lanthanum, stir until eutectic state is reached; add 15 kg of lead and stir until completely melted, cool to 700°C to cast ingots, and cool to obtain lead ingots.

[0106] Add 35 kg of lead to a medium-frequency furnace, heat to 400°C to melt it into liquid lead, heat to 700°C, add 10 g of sodium, 110 g of calcium and the lead ingots prepared above, and stir until a eutectic state is reached; add 15 kg of lead, cool to 550°C and add 600 g of tin, and stir until a eutectic state is reached; after cooling, a lead-calcium-tin-copper alloy is obtained.

[0107] This embodiment also provides a positive electrode grid, which is made of the lead-calcium-tin-copper alloy prepared above.

[0108] This embodiment also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0109] Example 10

[0110] This embodiment provides a lead-calcium-tin-copper alloy, prepared from the following components: 0.01 parts sodium, 0.11 parts calcium, 0.6 parts tin, 0.03 parts copper, 0.015 parts lanthanum, and 100 parts lead; specifically prepared according to the following method:

[0111] Add 35 kg of lead to an intermediate frequency furnace, heat to 400°C to melt into molten lead, heat to 1100°C, add 30 g of copper and 15 g of lanthanum, stir until eutectic state is reached; add 15 kg of lead and stir until completely melted, cool to 700°C to cast ingots, and cool to obtain lead ingots.

[0112] Add 35 kg of lead to a medium-frequency furnace, heat to 400°C to melt it into liquid lead, heat to 700°C, add 10 g of sodium, 110 g of calcium and the lead ingots prepared above, and stir until a eutectic state is reached; add 15 kg of lead, cool to 550°C and add 600 g of tin, and stir until a eutectic state is reached; after cooling, a lead-calcium-tin-copper alloy is obtained.

[0113] This embodiment also provides a positive electrode grid, which is made of the lead-calcium-tin-copper alloy prepared above.

[0114] This embodiment also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0115] Example 11

[0116] This embodiment provides a lead-calcium-tin-copper alloy, prepared from the following components: 0.01 parts sodium, 0.11 parts calcium, 0.6 parts tin, 0.03 parts copper, 0.02 parts lanthanum, and 100 parts lead; specifically prepared according to the following method:

[0117] Add 35 kg of lead to an intermediate frequency furnace, heat to 400°C to melt into molten lead, heat to 1100°C, add 30 g of copper and 20 g of lanthanum, stir until eutectic state is reached; add 15 kg of lead and stir until completely melted, cool to 700°C to cast ingots, and cool to obtain lead ingots.

[0118] Add 35 kg of lead to a medium-frequency furnace, heat to 400°C to melt it into liquid lead, heat to 700°C, add 10 g of sodium, 110 g of calcium and the lead ingots prepared above, and stir until a eutectic state is reached; add 15 kg of lead, cool to 550°C and add 600 g of tin, and stir until a eutectic state is reached; after cooling, a lead-calcium-tin-copper alloy is obtained.

[0119] This embodiment also provides a positive electrode grid, which is made of the lead-calcium-tin-copper alloy prepared above.

[0120] This embodiment also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0121] Example 12

[0122] This embodiment provides a lead-calcium-tin-copper alloy, prepared from the following components: 0.015 parts sodium, 0.12 parts calcium, 0.4 parts tin, 0.035 parts copper, 0.015 parts lanthanum, and 100 parts lead; specifically prepared according to the following method:

[0123] Add 35 kg of lead to an intermediate frequency furnace, heat to 500°C to melt into molten lead, heat to 1100°C, add 30 g of copper and 15 g of lanthanum, stir until eutectic state is reached; add 15 kg of lead and stir until completely melted, cool to 600°C to cast ingots, and cool to obtain lead ingots.

[0124] Add 35 kg of lead to a medium-frequency furnace, heat to 450°C to melt into molten lead, heat to 750°C, add 10 g of sodium, 110 g of calcium and the lead ingots prepared above, and stir until a eutectic state is reached; add 15 kg of lead, cool to 600°C and add 600 g of tin, and stir until a eutectic state is reached; after cooling, a lead-calcium-tin-copper alloy is obtained.

[0125] This embodiment also provides a positive electrode grid, which is made of the lead-calcium-tin-copper alloy prepared above.

[0126] This embodiment also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0127] Example 13

[0128] This embodiment provides a lead-calcium-tin-copper alloy, prepared from the following components: 0.02 parts sodium, 0.1 parts calcium, 0.5 parts tin, 0.04 parts copper, 0.02 parts lanthanum, and 100 parts lead; specifically prepared according to the following method:

[0129] Add 35 kg of lead to an intermediate frequency furnace, heat to 450°C to melt into molten lead, heat to 1150°C, add 30 g of copper and 20 g of lanthanum, stir until eutectic state is reached; add 15 kg of lead and stir until completely melted, cool to 650°C to cast ingots, and cool to obtain lead ingots.

[0130] Add 35 kg of lead to a medium-frequency furnace, heat to 500°C to melt into molten lead, heat to 800°C, add 10 g of sodium, 110 g of calcium and the lead ingots prepared above, and stir until a eutectic state is reached; add 15 kg of lead, cool to 600°C and add 600 g of tin, and stir until a eutectic state is reached; after cooling, a lead-calcium-tin-copper alloy is obtained.

[0131] This embodiment also provides a positive electrode grid, which is made of the lead-calcium-tin-copper alloy prepared above.

[0132] This embodiment also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0133] The lead-acid batteries in Examples 9-13 were subjected to cycle life tests and high-temperature accelerated float charge life tests according to the above test methods; the test results are shown in Table 3.

[0134] Table 3 Performance test results of lead-acid batteries in Examples 9-13

[0135]

[0136]

[0137] As can be seen from Examples 9-11 and Table 3, the addition of rare earth metal lanthanum, based on Example 1, can effectively improve the float charge life of lead-acid batteries. Furthermore, when the weight component addition of lanthanum is increased from 0.01 to 0.015, the improvement in the corrosion resistance of the alloy is particularly significant, and the float charge life increases from 9 times to 12 times. When the weight component addition of lanthanum is further increased from 0.015, the improvement in corrosion resistance is not significant, and the float charge life remains at 12 times.

[0138] A comparison of Examples 10 and 12, and Examples 11 and 13, shows that when the amount of lanthanum added remains unchanged, changing the weight composition of lead, sodium, calcium, tin, and copper components does not significantly improve the corrosion resistance of the alloy, nor does it significantly improve the cycle life or float charge life of the battery.

[0139] Example 14

[0140] This embodiment provides a lead-calcium-tin-copper alloy, prepared from the following components: 0.01 parts sodium, 0.11 parts calcium, 0.6 parts tin, 0.03 parts copper, 0.0015 parts silver, 0.01 parts lanthanum, and 100 parts lead; specifically prepared according to the following method:

[0141] Add 35 kg of lead to an intermediate frequency furnace, heat to 400°C to melt it into liquid lead, heat to 1100°C, add 30 g of copper, 1.5 g of silver and 10 g of lanthanum, and stir until it reaches a eutectic state; add 15 kg of lead and stir until it is completely melted, cool to 700°C to cast ingots, and cool to obtain lead ingots.

[0142] Add 35 kg of lead to a medium-frequency furnace, heat to 400°C to melt it into liquid lead, heat to 700°C, add 10 g of sodium, 110 g of calcium and the lead ingots prepared above, and stir until a eutectic state is reached; add 15 kg of lead, cool to 550°C and add 600 g of tin, and stir until a eutectic state is reached; after cooling, a lead-calcium-tin-copper alloy is obtained.

[0143] This embodiment also provides a positive electrode grid, which is made of the lead-calcium-tin-copper alloy prepared above.

[0144] This embodiment also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0145] Example 15

[0146] This embodiment provides a lead-calcium-tin-copper alloy, prepared from the following components: 0.015 parts sodium, 0.12 parts calcium, 0.4 parts tin, 0.035 parts copper, 0.002 parts silver, 0.015 parts lanthanum, and 100 parts lead; specifically prepared according to the following method:

[0147] Add 35 kg of lead to an intermediate frequency furnace, heat to 500°C to melt into molten lead, heat to 1100°C, add 30 g of copper, 2 g of silver and 15 g of lanthanum, stir until eutectic state is reached; add 15 kg of lead and stir until completely melted, cool to 600°C to cast ingots, and cool to obtain lead ingots.

[0148] Add 35 kg of lead to a medium-frequency furnace, heat to 450°C to melt into molten lead, heat to 750°C, add 10 g of sodium, 110 g of calcium and the lead ingots prepared above, and stir until a eutectic state is reached; add 15 kg of lead, cool to 600°C and add 600 g of tin, and stir until a eutectic state is reached; after cooling, a lead-calcium-tin-copper alloy is obtained.

[0149] This embodiment also provides a positive electrode grid, which is made of the lead-calcium-tin-copper alloy prepared above.

[0150] This embodiment also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0151] Example 16

[0152] This embodiment provides a lead-calcium-tin-copper alloy, prepared from the following components: 0.02 parts sodium, 0.1 parts calcium, 0.5 parts tin, 0.04 parts copper, 0.0025 parts silver, 0.02 parts lanthanum, and 100 parts lead; specifically prepared according to the following method:

[0153] Add 35 kg of lead to an intermediate frequency furnace, heat to 450°C to melt it into molten lead, heat to 1150°C, add 30 g of copper, 2.5 g of silver and 20 g of lanthanum, and stir until they reach a eutectic state; add 15 kg of lead and stir until completely melted, cool to 650°C to cast ingots, and cool to obtain lead ingots.

[0154] Add 35 kg of lead to a medium-frequency furnace, heat to 500°C to melt into molten lead, heat to 800°C, add 10 g of sodium, 110 g of calcium and the lead ingots prepared above, and stir until a eutectic state is reached; add 15 kg of lead, cool to 600°C and add 600 g of tin, and stir until a eutectic state is reached; after cooling, a lead-calcium-tin-copper alloy is obtained.

[0155] This embodiment also provides a positive electrode grid, which is made of the lead-calcium-tin-copper alloy prepared above.

[0156] This embodiment also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0157] The lead-acid batteries in Examples 14-16 were subjected to cycle life tests and high-temperature accelerated float charge life tests according to the above test methods; the test results are shown in Table 4.

[0158] Table 4 Performance test results of lead-acid batteries in Examples 14-16

[0159] Loop count High temperatures accelerate float charge lifespan Example 14 486 11 Example 15 538 12 Example 16 574 13

[0160] As can be seen from Examples 14-16 and Table 4, the addition of silver and lanthanum to Examples 1-3 significantly improves the active material and corrosion resistance, resulting in a greater increase in the number of battery cycles compared to adding silver or lanthanum alone.

[0161] By comparing Example 14 with Examples 4 and 9, Example 15 with Examples 5 and 10, and Example 16 with Examples 6 and 11, Example 14 shows a significant improvement in corrosion resistance compared to Examples 4 and 9, reflected in an increase in float charge life from 9-10 to 11.

[0162] Meanwhile, compared to Examples 6 and 11, Example 16 shows a more significant improvement in the number of cycle times for the lead-acid battery; while Example 14 shows a smaller improvement in the number of cycle times compared to Examples 4 and 9, Example 15 shows a smaller improvement compared to Examples 5 and 10, and Example 16 shows a smaller improvement compared to Examples 6 and 11. Therefore, the applicant infers that, with other components and their amounts fixed, the simultaneous addition of silver and lanthanum significantly improves the number of cycle times and float life of the battery; and the magnitude of this improvement is correlated with the amount of silver and lanthanum added. Therefore, based on the above, the applicant conducted research experiments and produced Examples 17-22.

[0163] Example 17

[0164] This embodiment provides a lead-calcium-tin-copper alloy, prepared from the following components: 0.01 parts sodium, 0.11 parts calcium, 0.6 parts tin, 0.03 parts copper, 0.0015 parts silver, 0.015 parts lanthanum, and 100 parts lead; specifically prepared according to the following method:

[0165] Add 35 kg of lead to an intermediate frequency furnace, heat to 400°C to melt it into liquid lead, heat to 1100°C, add 30 g of copper, 1.5 g of silver and 15 g of lanthanum, and stir until it reaches a eutectic state; add 15 kg of lead and stir until it is completely melted, cool to 700°C to cast ingots, and cool to obtain lead ingots.

[0166] Add 35 kg of lead to a medium-frequency furnace, heat to 400°C to melt it into liquid lead, heat to 700°C, add 10 g of sodium, 110 g of calcium and the lead ingots prepared above, and stir until a eutectic state is reached; add 15 kg of lead, cool to 550°C and add 600 g of tin, and stir until a eutectic state is reached; after cooling, a lead-calcium-tin-copper alloy is obtained.

[0167] This embodiment also provides a positive electrode grid, which is made of the lead-calcium-tin-copper alloy prepared above.

[0168] This embodiment also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0169] Example 18

[0170] This embodiment provides a lead-calcium-tin-copper alloy, prepared from the following components: 0.01 parts sodium, 0.11 parts calcium, 0.6 parts tin, 0.03 parts copper, 0.0015 parts silver, 0.02 parts lanthanum, and 100 parts lead; specifically prepared according to the following method:

[0171] Add 35 kg of lead to an intermediate frequency furnace, heat to 400°C to melt into molten lead, heat to 1100°C, add 30 g of copper, 1.5 g of silver and 20 g of lanthanum, and stir until eutectic state is reached; add 15 kg of lead and stir until completely melted, cool to 700°C to cast ingots, and cool to obtain lead ingots;

[0172] Add 35 kg of lead to a medium-frequency furnace, heat to 400°C to melt it into liquid lead, heat to 700°C, add 10 g of sodium, 110 g of calcium and the lead ingots prepared above, and stir until a eutectic state is reached; add 15 kg of lead, cool to 550°C and add 600 g of tin, and stir until a eutectic state is reached; after cooling, a lead-calcium-tin-copper alloy is obtained.

[0173] This embodiment also provides a positive electrode grid, which is made of the lead-calcium-tin-copper alloy prepared above.

[0174] This embodiment also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0175] The lead-acid batteries in Examples 17-18 were subjected to cycle life tests and high-temperature accelerated float charge life tests according to the above test methods; the test results are shown in Table 5.

[0176] Table 5 Performance test results of lead-acid batteries in Examples 17-18

[0177] Loop count High temperatures accelerate float charge lifespan Example 14 486 11 Example 17 546 11 Example 18 510 11

[0178] As can be seen from Examples 14, Examples 17-18 and Table 5, when the weight ratio of lanthanum to silver in Example 17 was adjusted to 10:1, the improvement in the number of cycles of the lead-acid battery was greater than that in Example 14 (6.7:1) and Example 18 (13.3:1); however, the improvement in the corrosion resistance of the alloy and the float life of the lead-acid battery was not significant.

[0179] Example 19

[0180] This embodiment provides a lead-calcium-tin-copper alloy, prepared from the following components: 0.015 parts sodium, 0.12 parts calcium, 0.4 parts tin, 0.035 parts copper, 0.0015 parts silver, 0.015 parts lanthanum, and 100 parts lead; specifically prepared according to the following method:

[0181] Add 35 kg of lead to an intermediate frequency furnace, heat to 500°C to melt into molten lead, heat to 1100°C, add 30 g of copper, 1.5 g of silver and 15 g of lanthanum, and stir until eutectic state is reached; add 15 kg of lead and stir until completely melted, cool to 600°C to cast ingots, and cool to obtain lead ingots;

[0182] Add 35 kg of lead to a medium-frequency furnace, heat to 450°C to melt into molten lead, heat to 750°C, add 10 g of sodium, 110 g of calcium and the lead ingots prepared above, and stir until a eutectic state is reached; add 15 kg of lead, cool to 600°C and add 600 g of tin, and stir until a eutectic state is reached; after cooling, a lead-calcium-tin-copper alloy is obtained.

[0183] This embodiment also provides a positive electrode grid, which is made of the lead-calcium-tin-copper alloy prepared above.

[0184] This embodiment also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0185] Example 20

[0186] This embodiment provides a lead-calcium-tin-copper alloy, prepared from the following components: 0.015 parts sodium, 0.12 parts calcium, 0.4 parts tin, 0.035 parts copper, 0.0015 parts silver, 0.02 parts lanthanum, and 100 parts lead; specifically prepared according to the following method:

[0187] Add 35 kg of lead to an intermediate frequency furnace, heat to 500°C to melt it into molten lead, heat to 1100°C, add 30 g of copper, 1.5 g of silver and 20 g of lanthanum, and stir until it reaches a eutectic state; add 15 kg of lead and stir until it is completely melted, cool to 600°C to cast ingots, and cool to obtain lead ingots.

[0188] Add 35 kg of lead to a medium-frequency furnace, heat to 450°C to melt into molten lead, heat to 750°C, add 10 g of sodium, 110 g of calcium and the lead ingots prepared above, and stir until a eutectic state is reached; add 15 kg of lead, cool to 600°C and add 600 g of tin, and stir until a eutectic state is reached; after cooling, a lead-calcium-tin-copper alloy is obtained.

[0189] This embodiment also provides a positive electrode grid, which is made of the lead-calcium-tin-copper alloy prepared above.

[0190] This embodiment also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0191] The lead-acid batteries in Examples 19-20 were subjected to cycle life tests and high-temperature accelerated float charge life tests according to the above test methods; the test results are shown in Table 6.

[0192] Table 6 Performance test results of lead-acid batteries in Examples 19-20

[0193] Loop count High temperatures accelerate float charge lifespan Example 15 538 12 Example 19 581 12 Example 20 515 12

[0194] As can be seen from Examples 15, Examples 19-20 and Table 6, when the weight ratio of lanthanum to silver in Example 19 was adjusted to 10:1, compared with the weight ratio in Example 15 (7.5:1) and Example 20 (13.3:1), the improvement in the number of cycles of the lead-acid battery was greater; however, the improvement in the corrosion resistance of the alloy and the float life of the lead-acid battery was not significant.

[0195] Example 21

[0196] This embodiment provides a lead-calcium-tin-copper alloy, prepared from the following components: 0.02 parts sodium, 0.1 parts calcium, 0.5 parts tin, 0.04 parts copper, 0.002 parts silver, 0.015 parts lanthanum, and 100 parts lead; specifically prepared according to the following method:

[0197] Add 35 kg of lead to an intermediate frequency furnace, heat to 450°C to melt into molten lead, heat to 1150°C, add 30 g of copper, 2 g of silver and 15 g of lanthanum, stir until eutectic state is reached; add 15 kg of lead and stir until completely melted, cool to 650°C to cast ingots, and cool to obtain lead ingots.

[0198] Add 35 kg of lead to a medium-frequency furnace, heat to 500°C to melt into molten lead, heat to 800°C, add 10 g of sodium, 110 g of calcium and the lead ingots prepared above, and stir until a eutectic state is reached; add 15 kg of lead, cool to 600°C and add 600 g of tin, and stir until a eutectic state is reached; after cooling, a lead-calcium-tin-copper alloy is obtained.

[0199] This embodiment also provides a positive electrode grid, which is made of the lead-calcium-tin-copper alloy prepared above.

[0200] This embodiment also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0201] Example 22

[0202] This embodiment provides a lead-calcium-tin-copper alloy, prepared from the following components: 0.02 parts sodium, 0.1 parts calcium, 0.5 parts tin, 0.04 parts copper, 0.0015 parts silver, 0.02 parts lanthanum, and 100 parts lead; specifically prepared according to the following method:

[0203] Add 35 kg of lead to an intermediate frequency furnace, heat to 450°C to melt into molten lead, heat to 1150°C, add 30 g of copper, 1.5 g of silver and 20 g of lanthanum, and stir until eutectic state is reached; add 15 kg of lead and stir until completely melted, cool to 650°C to cast ingots, and cool to obtain lead ingots.

[0204] Add 35 kg of lead to a medium-frequency furnace, heat to 500°C to melt into molten lead, heat to 800°C, add 10 g of sodium, 110 g of calcium and the lead ingots prepared above, and stir until a eutectic state is reached; add 15 kg of lead, cool to 600°C and add 600 g of tin, and stir until a eutectic state is reached; after cooling, a lead-calcium-tin-copper alloy is obtained.

[0205] This embodiment also provides a positive electrode grid, which is made of the lead-calcium-tin-copper alloy prepared above.

[0206] This embodiment also provides a lead-acid battery, including the positive electrode grid prepared as described above.

[0207] The lead-acid batteries in Examples 21-22 were subjected to cycle number tests and high-temperature accelerated float charge life tests according to the above test methods; the test results are shown in Table 7.

[0208] Table 7 Performance test results of lead-acid batteries in Examples 21-22

[0209] Loop count High temperatures accelerate float charge lifespan Example 16 574 13 Example 21 542 13 Example 22 512 13

[0210] As can be seen from Examples 16, Examples 21-22 and Table 7, when the weight ratio of lanthanum to silver in Example 16 was adjusted to 8:1, the improvement in the number of cycles of the lead-acid battery was greater than that in Example 21 (7.5:1) and Example 22 (13.3:1); however, the improvement in the corrosion resistance of the alloy and the float life of the lead-acid battery was not significant.

[0211] As can be seen from Examples 14-22, setting the weight ratio of lanthanum to silver in the range of 8-10:1 results in a greater increase in the cycle life of lead-acid batteries.

[0212] The above are all preferred embodiments of this application, and are not intended to limit the scope of protection of this application. Therefore, all equivalent changes made in accordance with the structure, shape and principle of this application should be covered within the scope of protection of this application.

Claims

1. A lead calcium tin copper alloy characterized by, The alloy is prepared from the following components by weight: sodium 0.01-0.02 parts, calcium 0.1-0.12 parts, tin 0.4-0.6 parts, copper 0.03-0.04 parts, silver 0.0015-0.0025 parts, lanthanum 0.01-0.02 parts, and lead 100 parts; the mass ratio of silver to lanthanum is set at 1:8-10.

2. A method of producing the lead calcium tin copper alloy as claimed in claim 1, characterized in that, The method comprises the following steps: S1, melting lead with a formula amount of 35wt% into lead liquid, heating, adding metals other than lead, sodium, calcium and tin according to the formula amount, and stirring to reach a eutectic state; adding lead with a formula amount of 15wt% and stirring until completely melted, cooling to cast ingot, and cooling to obtain lead ingot; S2, melting lead with a formula amount of 35wt% into lead liquid, adding sodium, calcium and the lead ingot prepared in S1 according to the formula amount, and stirring to reach a eutectic state; adding lead with a formula amount of 15wt%, adding tin after cooling, and stirring to reach a eutectic state; and cooling to obtain lead calcium tin copper alloy. In S1, lead is melted at 400-500℃; after heating to 1100-1150℃, metals other than lead, sodium, calcium and tin are added; and the temperature is lowered to 600-700℃ to cast ingot.

3. The production method according to claim 2, characterized by, In S2, lead is melted at 400-500℃; after heating to 700-800℃, sodium, calcium and the lead ingot prepared in S1 are added; and the temperature is lowered to 550-600℃ to add tin.

4. The production method according to claim 2, characterized by, The alloy is prepared from the following components by weight: sodium 0.01-0.02 parts, calcium 0.1-0.12 parts, tin 0.4-0.6 parts, copper 0.03-0.04 parts, silver 0.0015-0.0025 parts, lanthanum 0.01-0.02 parts, and lead 100 parts; the mass ratio of silver to lanthanum is set at 1:8-10.

5. A positive plate grid characterized by, The method comprises the following steps: S1, melting lead with a formula amount of 35wt% into lead liquid, heating, adding metals other than lead, sodium, calcium and tin according to the formula amount, and stirring to reach a eutectic state; adding lead with a formula amount of 15wt% and stirring until completely melted, cooling to cast ingot, and cooling to obtain lead ingot; S2, melting lead with a formula amount of 35wt% into lead liquid, adding sodium, calcium and the lead ingot prepared in S1 according to the formula amount, and stirring to reach a eutectic state; adding lead with a formula amount of 15wt%, adding tin after cooling, and stirring to reach a eutectic state; and cooling to obtain lead calcium tin copper alloy.

6. A lead-acid battery characterised in that, ​

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