A negative lead paste for deep cycle automotive start-stop lead-acid batteries, its preparation method and application

Abstract

The present invention discloses a negative electrode lead paste for deep cycle automotive start-stop lead-acid batteries, a preparation method thereof, and an application thereof. The grinding aid synergist of the present invention is prepared by a mercapto-ene addition reaction between ethanolamine mercaptoacetate and indium 2-vinylcyclopropane-1,1-dicarboxylate complex under alkaline conditions, and is successfully applied to the preparation of the negative electrode lead paste for deep cycle automotive start-stop lead-acid batteries. It improves the dispersion effect of ball milling, and at the same time, the indium dicarboxylate complex and ethanolamine also have a positive impact on the performance of the negative electrode lead paste by improving thermal stability, electrochemical performance, and grinding efficiency, etc. The negative electrode lead paste prepared by the method of the present invention enables the battery to maintain good electrical conductivity and chemical stability under high temperature and deep cycle conditions, greatly improving the cycle life (up to 49% improvement) and high-rate discharge performance (up to 11% improvement) of the automotive start-stop lead-acid battery, and significantly improving the overall performance of the battery.

Description

Technical Field

[0001] The present invention relates to the technical field of lead-acid battery production, and particularly to a negative lead paste for deep-cycle automotive start-stop lead-acid batteries, a preparation method thereof, and an application thereof. Background Art

[0002] With the rapid development of the automotive industry, energy conservation and environmental protection have become important technological development directions. As an effective means to address fuel consumption and emissions, automotive start-stop systems have been widely used in modern vehicles. This system can automatically shut down the engine when the vehicle stops briefly and quickly restart it when needed, thereby reducing idle fuel consumption and exhaust emissions. However, the start-stop system poses extremely high requirements on the battery, including frequent start-stop, high-rate discharge, durability, and deep-cycle life. In particular, stringent performance standards are imposed on the stability, conductivity, and high-temperature durability of the negative lead paste material.

[0003] Traditional lead-acid batteries are widely used in start-stop systems and have the advantages of low production cost and high safety. The patent application with the publication number CN101887971A discloses a lead paste formula for energy storage batteries. By weight percentage, the positive lead paste formula consists of the following raw materials: dilute sulfuric acid 6.5% - 8%, deionized water 10% - 11%, red lead 15% - 30%, colloidal graphite 0.1% - 0.3%, stannous sulfate 0.08% - 0.25%, polyester staple fiber 0.06% - 0.10%, and the balance is lead powder. The negative lead paste formula consists of the following raw materials: dilute sulfuric acid 7.5% - 8.5%, deionized water 9% - 10%, barium sulfate 0.5% - 0.8%, acetylene black 0.15% - 0.25%, humic acid 0.30% - 0.40%, polyester staple fiber 0.06% - 0.10%, and the balance is lead powder. The lead paste prepared by using the formula and the preparation method of the present invention has a very high initial capacity and cycle life after being made into a battery.

[0004] The patent application with the publication number CN108134054A discloses a high-performance start-stop negative plate lead paste and its application in lead-acid battery negative plates. It includes the following components in parts by weight: sulfuric acid 8.5 - 10 parts; nano barium sulfate A 0.13 - 0.35 parts; nano barium sulfate B 0.3 - 0.45 parts; lignin 0.10 - 0.20 parts; short fiber 0.05 - 0.15 parts; carbon material 0.10 - 0.25 parts; barium polyaspartate 0.05 - 0.15 parts; deionized water 9 - 13 parts; lead powder 74 - 80 parts. On the basis of not adding high-carbon and having a small content of organic expanding agents, the present invention increases the charging acceptance ability and low-temperature performance of the battery, thereby increasing the battery life.

[0005] However, the negative electrode lead paste is prone to the loss and shedding of active substances under deep cycle and high-temperature working conditions, resulting in the expansion of the battery plate and the decline of conductivity, ultimately affecting the discharge efficiency and life of the battery. Under deep cycle and high-temperature conditions, electrochemical polarization occurs inside the battery, manifested as an increase in the internal resistance of the battery, which further exacerbates the consumption of active substances and reduces the deep cycle performance and service life of the battery. This problem is particularly obvious under conditions of frequent start-stop and high-rate discharge, posing an important challenge to the reliability of start-stop batteries. Summary of the Invention

[0006] In view of the above technical problems, the present method proposes a preparation method for the negative electrode lead paste of a deep cycle automotive start-stop lead-acid battery. The lead-acid battery prepared by this method can maintain a low electrochemical polarization phenomenon under the frequent cycling conditions of the start-stop system, extend the deep cycle life of the battery, and thus better meet the requirements of modern automobiles for start-stop batteries.

[0007] To achieve the above object, the present invention provides the following technical solutions:

[0008] The present invention provides a preparation method for the negative electrode lead paste of a deep cycle automotive start-stop lead-acid battery, comprising the following steps:

[0009] Step 1: Dry-mix lead powder, sodium lignosulfonate, ultrafine precipitated barium sulfate (2000-4000 mesh), fiber, conductive carbon material, and grinding aid synergist, and mix evenly to obtain a mixed powder;

[0010] The grinding aid synergist is obtained by an addition reaction of ethanolamine mercaptoacetate and indium 2-vinylcyclopropane-1,1-dicarboxylate under alkaline conditions;

[0011] The indium 2-vinylcyclopropane-1,1-dicarboxylate is obtained by a coordination reaction of 2-vinylcyclopropane-1,1-dicarboxylic acid and indium nitrate;

[0012] Step 2: Add water to the mixed powder obtained in Step 1, stir evenly, pour in sulfuric acid solution, control the paste temperature, and perform pasting to obtain the negative electrode lead paste of the deep cycle automotive start-stop lead-acid battery.

[0013] Specifically, in parts by weight, 100-120 parts of lead powder, 0.5-1.5 parts of sodium lignosulfonate, 0.1-0.5 parts of ultrafine precipitated barium sulfate, 0.02-0.05 parts of fiber, 0.05-0.2 parts of conductive carbon material, 0.1-1 part of grinding aid synergist, 10-16 parts of water, and 12-15 parts of sulfuric acid solution.

[0014] Preferably, the lead powder contains 60% - 80% of PbO; the density of the sulfuric acid solution at 25°C is 1.350 - 1.450 g / cm³.

[0015] Preferably, the fiber is selected from one or a combination of polyester fiber, polyamide fiber, and acrylic fiber;

[0016] The conductive carbon material is selected from one or a combination of carbon black, acetylene black, carbon nanotubes, graphene, and carbon fiber.

[0017] Specifically, the preparation method of the grinding aid and synergist is as follows:

[0018] By mass, 25 - 32 parts of ethanolamine thioglycolate, 0.03 - 0.3 part of indium 2 - vinylcyclopropane - 1,1 - dicarboxylate complex, 300 - 400 parts of N,N - dimethylformamide (DMF), and 2 - 5 parts of triethylamine are mixed and reacted at 60 - 70 °C for 60 - 120 minutes. After the reaction, N,N - dimethylformamide is distilled off under reduced pressure to obtain the grinding aid and synergist.

[0019] The preparation method of the indium 2 - vinylcyclopropane - 1,1 - dicarboxylate complex is as follows:

[0020] By weight, 15 - 30 parts of 2 - vinylcyclopropane - 1,1 - dicarboxylic acid, 20 - 40 parts of indium nitrate, and 200 - 300 parts of water are mixed and reacted at 60 - 70 °C for 60 - 120 minutes. The water is distilled off, and then it is dried in vacuo to obtain the indium 2 - vinylcyclopropane - 1,1 - dicarboxylate complex.

[0021] The reaction mechanism of the grinding aid and synergist is as follows:

[0022] The mercapto group (-SH) has high reactivity and easily attacks the carbon - carbon double bond to form a new chemical bond. In ethanolamine thioglycolate, the mercapto group acts as a nucleophile and undergoes an addition reaction with the carbon - carbon double bond in the indium 2 - vinylcyclopropane - 1,1 - dicarboxylate complex. Due to the excess ethanolamine thioglycolate, the mercapto group and the indium 2 - vinylcyclopropane - 1,1 - dicarboxylate complex can also undergo a ring - opening addition reaction.

[0023] The technical effects of the grinding aid and synergist are as follows:

[0024] 1) The addition of the grinding aid and synergist reduces the surface tension of the lead powder, making the lead powder easier to be wetted, thereby improving its dispersibility during the ball - milling process.

[0025] 2) The polar functional groups in the grinding aid interact with the surface of the lead powder to form a stable adsorption layer, preventing the agglomeration between lead powder particles and further improving the dispersion effect. The indium dicarboxylate complex has good thermal stability and electrochemical properties, and its introduction helps to improve the stability of the negative electrode lead paste in a high-temperature environment and the cycle life of the battery. The indium dicarboxylate complex may also participate in the chemical reaction on the electrode surface, improving the interfacial properties of the electrode, thereby enhancing the charge-discharge performance of the battery. The amino functional group of ethanolamine may interact with the oxides or other impurities on the surface of the lead powder to remove these impurities, thus exposing more fresh surfaces for the ball milling process to act on.

[0026] In summary, the grinding aid is prepared by thiol-ene addition reaction and is successfully applied to the preparation of the negative electrode lead paste of a deep-cycle automotive start-stop lead-acid battery. It improves the dispersion effect of ball milling, and at the same time, the indium dicarboxylate complex and ethanolamine also have a positive impact on the performance of the negative electrode lead paste by improving thermal stability, electrochemical properties and grinding efficiency, etc.

[0027] Preferably, the dry mixing method is ball milling, and the ball milling process is as follows: the ball milling speed is 200 - 300 rpm, the ball-to-material ratio is 5 - 10∶1, and the ball milling time is 10 - 30 minutes.

[0028] Preferably, the temperature during the paste mixing process is 50 - 65 °C, and the paste mixing time is 10 - 20 minutes.

[0029] The present invention also provides a negative electrode lead paste for a deep-cycle automotive start-stop lead-acid battery prepared by the above preparation method.

[0030] The present invention also provides a deep-cycle automotive start-stop lead-acid battery, comprising a positive electrode, a negative electrode and an electrolyte, wherein the negative electrode comprises a negative electrode lead paste, and the negative electrode lead paste is the negative electrode lead paste for a deep-cycle automotive start-stop lead-acid battery.

[0031] Compared with the prior art solutions, the present invention has the following beneficial effects:

[0032] The negative electrode lead paste prepared by the method of the present invention enables the battery to maintain good electrical conductivity and chemical stability under high-temperature and deep-cycle conditions, greatly improving the cycle life (up to 49% improvement) and high-rate discharge performance (up to 11% improvement) of the automotive start-stop lead-acid battery, and significantly improving the overall performance of the battery. Specific Embodiments

[0033] To further understand the present invention, the present invention will be further described in detail below in conjunction with preferred embodiments.

[0034] Example 1

[0035] The preparation method of the grinding aid used in this example is as follows:

[0036] 1. Indium complex of 2-vinylcyclopropane-1,1-dicarboxylic acid:

[0037] Mix 15 g of 2-vinylcyclopropane-1,1-dicarboxylic acid (CAS: 57742-48-0), 20 g of indium nitrate, and 200 g of water, react at 60 °C for 60 minutes, distill off the water, and then dry in vacuo to obtain the indium complex of 2-vinylcyclopropane-1,1-dicarboxylic acid.

[0038] 2. Grinding aid synergist

[0039] Mix 25 g of ethanolamine mercaptoacetate (CAS: 126-97-6), 0.03 g of the indium complex of 2-vinylcyclopropane-1,1-dicarboxylic acid, 300 g of DMF, and 2 g of triethylamine, react at 60 °C for 60 minutes. After the reaction, distill off DMF under reduced pressure to obtain the grinding aid synergist.

[0040] A method for preparing the negative lead paste of a deep-cycle automotive start-stop lead-acid battery, comprising the following steps:

[0041] Step 1: Put 100 g of lead powder (with a PbO content of 60%), 0.5 g of sodium lignosulfonate, 0.1 g of ultrafine precipitated barium sulfate (2000 mesh), 0.02 g of polyester fiber, 0.05 g of carbon black, and 0.1 g of the grinding aid synergist into a ball mill tank, with a ball mill speed of 200 rpm; a ball-to-material ratio of 5:1; zirconia as the ball mill beads; and a ball milling time of 30 minutes, and mix evenly.

[0042] Step 2: Pour the above mixed powder into a paste mixer, add 10 g of deionized water, stir evenly, pour in 12 g of sulfuric acid solution (with a density of 1.350 g / cm³ at 25 °C), control the temperature during the paste mixing process to be 50 °C, and the paste mixing time to be 10 minutes. After completion, cool down and discharge the paste to obtain the lead paste.

[0043] Example 2

[0044] The preparation method of the grinding aid synergist used in this example is as follows:

[0045] 1. Indium complex of 2-vinylcyclopropane-1,1-dicarboxylic acid:

[0046] Mix 20 g of 2-vinylcyclopropane-1,1-dicarboxylic acid (CAS: 57742-48-0), 30 g of indium nitrate, and 250 g of water, react at 65 °C for 80 minutes, distill off the water, and then dry in vacuo to obtain the indium complex of 2-vinylcyclopropane-1,1-dicarboxylic acid.

[0047] 2. Grinding aid synergist

[0048] Mix 28 g of ethanolamine thioglycolate (CAS: 126-97-6), 0.1 g of indium complex of 2-vinylcyclopropane-1,1-dicarboxylic acid, 350 g of DMF and 3 g of triethylamine, react at 65 °C for 80 minutes. After the reaction, distill off DMF under reduced pressure to obtain the grinding aid.

[0049] A method for preparing the negative electrode lead paste of a deep-cycle automotive start-stop lead battery, comprising the following steps:

[0050] Step 1: Put 110 g of lead powder (with a PbO content of 70%), 1 g of sodium lignosulfonate, 0.25 g of ultrafine precipitated barium sulfate (3000 mesh), 0.03 g of polyamide fiber, 0.1 g of acetylene black and 0.35 g of grinding aid into a ball mill tank, with a ball mill rotation speed of 250 rpm; the ball-to-material ratio is 7:1; the ball mill beads are zirconia; the ball milling time is 20 minutes, and mix evenly;

[0051] Step 2: Pour the above mixed powder into a paste mixer, add 12 g of deionized water, stir evenly, pour in 13 g of sulfuric acid solution (with a density of 1.4 g / cm³ at 25 °C), control the temperature during the paste mixing process to be 55 °C, and the paste mixing time to be 15 minutes. After completion, cool down and take out the paste to obtain the lead paste.

[0052] Example 3

[0053] The preparation method of the grinding aid used in this example is as follows:

[0054] 1. Indium complex of 2-vinylcyclopropane-1,1-dicarboxylic acid:

[0055] Mix 25 g of 2-vinylcyclopropane-1,1-dicarboxylic acid (CAS: 57742-48-0), 30 g of indium nitrate and 250 g of water, react at 65 °C for 100 minutes, distill off the water, and then dry in vacuo to obtain the indium complex of 2-vinylcyclopropane-1,1-dicarboxylic acid.

[0056] 2. Grinding aid

[0057] Mix 30 g of ethanolamine thioglycolate (CAS: 126-97-6), 0.2 g of indium complex of 2-vinylcyclopropane-1,1-dicarboxylic acid, 350 g of DMF and 4 g of triethylamine, react at 65 °C for 100 minutes. After the reaction, distill off DMF under reduced pressure to obtain the grinding aid.

[0058] A method for preparing the negative electrode lead paste of a deep-cycle automotive start-stop lead battery, comprising the following steps:

[0059] Step 1: Put 110 g of lead powder (with a PbO content of 70%), 1 g of sodium lignosulfonate, 0.4 g of ultrafine precipitated barium sulfate (4000 mesh), 0.04 g of acrylic fiber, 0.15 g of carbon nanotubes, and 0.75 g of grinding aid into a ball mill tank. The ball mill speed is 250 rpm; the ball-to-material ratio is 8:1; the ball mill beads are zirconia; the ball milling time is 20 minutes, and mix evenly;

[0060] Step 2: Pour the above mixed powder into a paste mixer, add 14 g of deionized water, stir evenly, pour in 14 g of sulfuric acid solution (with a density of 1.4 g / cm³ at 25 °C), control the temperature during the paste mixing process to be 60 °C, and the paste mixing time is 15 minutes. After completion, cool down and discharge the paste to obtain the lead paste.

[0061] Example 4

[0062] The preparation method of the grinding aid used in this example is as follows:

[0063] 1. Indium complex of 2-vinylcyclopropane-1,1-dicarboxylic acid:

[0064] Mix 30 g of 2-vinylcyclopropane-1,1-dicarboxylic acid (CAS: 57742-48-0), 40 g of indium nitrate, and 300 g of water, react at 70 °C for 120 minutes, distill off the water, and then dry in vacuo to obtain the indium complex of 2-vinylcyclopropane-1,1-dicarboxylic acid.

[0065] 2. Grinding aid

[0066] Mix 32 g of ethanolamine thioglycolate (CAS: 126-97-6), 0.3 g of indium complex of 2-vinylcyclopropane-1,1-dicarboxylic acid, 400 g of DMF, and 5 g of triethylamine, react at 70 °C for 120 minutes. After the reaction is completed, distill off DMF under reduced pressure to obtain the grinding aid.

[0067] A preparation method of a negative lead paste for a deep-cycle automotive start-stop lead-acid battery, comprising the following steps:

[0068] Step 1: Put 120 g of lead powder (with a PbO content of 80%), 1.5 g of sodium lignosulfonate, 0.5 g of ultrafine precipitated barium sulfate (2000 mesh), 0.05 g of acrylic fiber, 0.2 g of graphene, and 1 g of grinding aid into a ball mill tank. The ball mill speed is 300 rpm; the ball-to-material ratio is 10:1; the ball mill beads are zirconia; the ball milling time is 10 minutes, and mix evenly;

[0069] Step 2: Pour the above mixed powder into a paste mixer, add 16 g of deionized water, stir evenly, pour in 15 g of sulfuric acid solution (with a density of 1.450 g / cm³ at 25 °C), control the temperature during the paste mixing process to be 65 °C, and the paste mixing time to be 20 minutes. After completion, cool down and discharge the paste to obtain the lead paste.

[0070] Comparative Example 1

[0071] A method for preparing a negative electrode lead paste of a lead-acid battery, comprising the following steps:

[0072] Step 1: Put 100 g of lead powder (with a PbO content of 60%), 0.5 g of sodium lignosulfonate, 0.1 g of ultrafine precipitated barium sulfate (2000 mesh), 0.02 g of polyester fiber, and 0.05 g of carbon black into a ball mill tank, with a ball milling speed of 200 rpm; the ball-to-material ratio is 5:1; the ball milling beads are zirconia; the ball milling time is 30 minutes, and mix evenly;

[0073] Step 2: Pour the above mixed powder into a paste mixer, add 10 g of deionized water, stir evenly, pour in 12 g of sulfuric acid solution (with a density of 1.350 g / cm³ at 25 °C), control the temperature during the paste mixing process to be 50 °C, and the paste mixing time to be 10 minutes. After completion, cool down and discharge the paste to obtain the lead paste.

[0074] Comparative Example 2

[0075] The grinding aid used in this comparative example is: ethanolamine thioglycolate (CAS: 126-97-6).

[0076] A method for preparing a negative electrode lead paste of a lead-acid battery, comprising the following steps:

[0077] Step 1: Put 100 g of lead powder (with a PbO content of 60%), 0.5 g of sodium lignosulfonate, 0.1 g of ultrafine precipitated barium sulfate (2000 mesh), 0.02 g of polyester fiber, 0.05 g of carbon black, and 0.1 g of ethanolamine thioglycolate into a ball mill tank and mix evenly;

[0078] Step 2: Pour the above mixed powder into a paste mixer, add 10 g of deionized water, stir evenly, pour in 12 g of sulfuric acid solution (with a density of 1.350 g / cm³ at 25 °C), control the temperature during the paste mixing process to be 50 °C, and the paste mixing time to be 10 minutes. After completion, cool down and discharge the paste to obtain the lead paste.

[0079] Test Example 1

[0080] To verify the performance improvement effect of the negative electrode lead paste of the present invention, the negative electrode lead paste prepared in the examples and comparative examples was applied to a start-stop lead-acid battery, and the following key performance tests were carried out:

[0081] 1. Electrochemical performance test:

[0082] Test battery: The prepared negative electrode lead paste was used to assemble a start-stop lead-acid battery (rated capacity 70 Ah), and the test objects were the examples and comparative examples of the present invention respectively.

[0083] Test conditions: Charge and discharge tests were carried out at a rate of 2C, and the change in the discharge capacity of the battery with the number of cycles was recorded until the capacity decayed to 80% of the initial capacity.

[0084] 2. High-temperature deep-cycle performance test

[0085] Test conditions: Under the environment of 55 °C, a simulated deep-cycle charge and discharge test was carried out, and the following charge and discharge mode was adopted:

[0086] Charge: Constant current charge to 14.7 V, the current is 0.1C, and constant voltage charge for 1 hour.

[0087] Discharge: Discharge at 0.2C to 10.5 V.

[0088] Cycle: 50 times is a cycle, and the capacity retention rate after 500 cycles of testing was tested.

[0089] 3. Discharge performance test

[0090] Test conditions: At room temperature of 25 °C, the discharge capacity of the battery was tested at discharge rates of 0.1C and 2C, and the high-rate discharge performance retention rate was calculated.

[0091] Formula: High-rate discharge performance retention rate = (C high rate / C low rate) × 100%.

[0092] The test results are shown in Table 1.

[0093] Table 1 Test results

[0094]

[0095] The above test results show that the negative electrode lead paste prepared by the method of the present invention significantly improves the performance of the lead-acid battery under deep-cycle and high-temperature conditions. Especially in the start-stop working conditions, the cycle life and high-rate discharge performance of the battery are significantly better than those of the negative electrode lead paste prepared by the comparative example, and the cycle life and high-rate discharge performance of the battery are respectively increased by up to 49% and 11%. This fully proves the superiority and practical value of the present invention in the application of start-stop lead-acid batteries.

Claims

1. A preparation method for the negative electrode lead paste of a deep-cycle lead-acid battery for automotive start-stop applications, characterized in that, It includes the following steps: Step 1: Dry mix 100 - 120 parts by weight of lead powder, 0.5 - 1.5 parts of sodium lignosulfonate, 0.1 - 0.5 parts of ultrafine precipitated barium sulfate, 0.02 - 0.05 parts of fiber, 0.05 - 0.2 parts of conductive carbon material, and 0.1 - 1 part of grinding aid synergist to obtain a uniformly mixed powder. The particle size of the ultrafine precipitated barium sulfate is 2000 - 4000 mesh. The preparation method of the grinding aid synergist is as follows: Mix 25 - 32 parts by mass of ethanolamine mercaptoacetate, 0.03 - 0.3 parts of indium 2 - vinylcyclopropane - 1,1 - dicarboxylate complex, 300 - 400 parts of N,N - dimethylformamide, and 2 - 5 parts of triethylamine, react at 60 - 70 °C for 60 - 120 minutes. After the reaction, distill off N,N - dimethylformamide under reduced pressure to obtain the grinding aid synergist. The preparation method of the indium 2 - vinylcyclopropane - 1,1 - dicarboxylate complex is as follows: Mix 15 - 30 parts by weight of 2 - vinylcyclopropane - 1,1 - dicarboxylic acid, 20 - 40 parts of indium nitrate, and 200 - 300 parts of water, react at 60 - 70 °C for 60 - 120 minutes, distill off the water, and then dry in vacuum to obtain the indium 2 - vinylcyclopropane - 1,1 - dicarboxylate complex. Step 2: Add 10 - 16 parts of water to the mixed powder obtained in Step 1, stir evenly, pour in 12 - 15 parts of sulfuric acid solution, control the paste - making temperature, carry out paste - making, and then the negative - electrode lead paste for deep - cycle automotive starting and stopping batteries is obtained.

2. The preparation method of the negative electrode lead paste of the deep cycle lead-acid battery for automotive start-stop use according to claim 1, wherein, The PbO content in the lead powder is 60% - 80%; the density of the sulfuric acid solution at 25 °C is 1.350 - 1.450 g / cm³.

3. The preparation method of the negative electrode lead paste of the deep cycle lead-acid battery for automotive starting and stopping according to claim 1, characterized in that, The fiber is selected from one or a combination of polyester fiber, polyamide fiber, and acrylic fiber. The conductive carbon material is selected from one or a combination of carbon black, acetylene black, carbon nanotubes, graphene, and carbon fiber.

4. The preparation method of the negative electrode lead paste of the deep cycle lead-acid battery for automotive starting and stopping according to claim 1, characterized in that, The dry - mixing method is ball - milling, and the ball - milling process is: the ball - milling speed is 200 - 300 rpm, the ball - to - material ratio is 5 - 10∶1, and the ball - milling time is 10 - 30 minutes.

5. The preparation method of the negative electrode lead paste of the deep cycle lead-acid battery for automotive start-stop use according to claim 1, characterized in that, During the paste - making process, the temperature is 50 - 65 °C and the paste - making time is 10 - 20 minutes.

6. The negative - electrode lead paste for deep - cycle automotive starting and stopping batteries prepared by the preparation method according to any one of claims 1 - 5.

7. A deep cycle lead-acid battery for automotive start-stop applications, comprising a positive electrode, a negative electrode, and an electrolyte, characterized in that, The negative electrode includes a negative - electrode lead paste, and the negative - electrode lead paste is the negative - electrode lead paste for deep - cycle automotive starting and stopping batteries according to claim 6.

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