A negative electrode lead paste for a vehicle high-temperature start-stop battery and a preparation method thereof

Abstract

The present invention discloses a negative electrode lead paste for a vehicle high-temperature start-stop battery and a preparation method thereof, which relates to the technical field of battery materials. Specifically, a high-temperature additive is added to the negative electrode lead paste of the present invention, and the high-temperature additive is obtained by carrying out a sulfonamide reaction between polyaniline and 9H-carbazole-3-sulfonyl chloride and coordinating with indium acetate. In the present invention, the acylation reaction of polyaniline with 9H-carbazole-3-sulfonyl chloride and indium acetate not only successfully introduces a carbazole ring and an organoindium complex, but also significantly improves the high-temperature resistance, electrical conductivity (the internal resistance is reduced by half), cycle life (the maximum increase is about 61%), rate performance (the maximum increase is 11%), energy density and structural stability of the material. These technical effects are of great significance for the application of the negative electrode lead paste of the vehicle high-temperature start-stop battery.

Description

Technical Field

[0001] The present invention relates to the technical field of battery materials, and particularly to a negative electrode lead paste for a vehicle high-temperature start-stop battery and a preparation method thereof. Background Art

[0002] Due to its low cost, good stability and reliability, lead-acid batteries play an irreplaceable role in many fields such as automotive starting, backup power systems, and new energy energy storage solutions. However, with the progress of technology and the change of market demand, the performance bottlenecks of traditional lead-acid batteries have gradually emerged, especially in the preparation and optimization of negative electrode materials, facing many challenges.

[0003] The negative electrode of a traditional lead-acid battery usually uses a lead paste prepared by directly mixing lead powder and dilute sulfuric acid as the active material. Although this preparation method is simple and direct, it has obvious performance limitations. First of all, the insufficient conductivity of the lead paste is a key issue. Due to the lack of effective conductive additives, the electron conduction ability inside the lead paste is limited, resulting in low reaction efficiency of the active material, which in turn affects the discharge capacity and power output of the battery. This defect is particularly prominent in application scenarios that require high-power discharge or fast charge and discharge, restricting the application potential of lead-acid batteries in emerging fields such as electric vehicles and smart grids.

[0004] Secondly, the structural stability of the traditional negative electrode lead paste is poor, and phenomena such as paste expansion, cracking, and even peeling are likely to occur during the recycling process. This not only significantly reduces the effective utilization rate of the active material, but also accelerates the decline of battery performance and shortens the cycle life. Especially after experiencing deep discharge or large-current charge and discharge cycles, the structure of the negative electrode lead paste is more severely damaged, and the battery performance deteriorates more significantly, making it difficult to meet the requirements of long life and high reliability.

[0005] In response to the above problems, scientific researchers have actively explored new ways to improve the negative electrode materials of lead-acid batteries. Among them, adding conductive aids to the lead paste to enhance its conductivity and structural stability has become one of the research hotspots. Carbon materials, such as carbon black, graphite, carbon nanotubes, etc., are regarded as ideal choices for improving the conductivity of lead paste due to their excellent conductivity and good chemical stability. These carbon materials can form a conductive network, improve the electron transfer rate in the lead paste, and thus enhance the reaction efficiency of the active material. However, the addition of carbon materials is not the more the better, and factors such as their particle size, distribution uniformity, and interaction with lead powder will all affect the final effect. Therefore, how to optimize the addition strategy of carbon materials and achieve their uniform dispersion in the lead paste has become an urgent technical problem to be solved.

[0006] In addition, in order to improve the mechanical strength and structural stability of the lead paste, researchers have also tried to introduce organic additives and inorganic fillers. For example, ultrafine barium sulfate as a filler can increase the density and hardness of the lead paste, reducing the deformation and shedding of the paste during cycling; organic additives such as polyester staple fibers can enhance the toughness of the lead paste and improve its ability to withstand cyclic stress. The rational use of these additives helps to improve the overall performance of the negative electrode lead paste and extend the service life of the battery.

[0007] In summary, in the face of the deficiencies of traditional negative electrode materials for lead-acid batteries in terms of conductivity, structural stability, and cycle life, developing an improved negative electrode lead paste containing multiple additives is of great significance for enhancing the comprehensive performance of lead-acid batteries and broadening their application fields. Summary of the Invention

[0008] To address the above technical problems, this method optimizes the composition and preparation process of the lead paste to further improve the electrochemical performance, cycle life, and energy density of lead-acid batteries, thereby meeting the requirements of high-performance application scenarios.

[0009] To achieve the above object, the present invention provides the following technical solutions:

[0010] A negative electrode lead paste for a vehicle high-temperature start-stop battery, comprising lead powder, sulfuric acid solution, water, and additives. Based on 100 parts by weight of the lead powder, the additives contain the following raw materials in parts by weight:

[0011] Polyester staple fiber 0.5 - 1 part, nanoscale barium sulfate 0.5 - 2 parts, nanoscale sodium sulfate 0.2 - 1 part, high-temperature resistant additive 0.1 - 1 part, carbon material additive 0.2 - 1 part;

[0012] The high-temperature resistant additive is obtained by reacting polyaniline with 9H-carbazole-3-sulfonyl chloride to undergo sulfonamide reaction and coordinating with indium acetate.

[0013] Preferably, the carbon material additive is selected from one or a combination of carbon black, carbon nanotubes, graphene, acetylene black, and carbon fibers.

[0014] Specifically, the high-temperature resistant additive is modified polyaniline, and its preparation method is as follows:

[0015] Disperse 100 - 120 parts of polyaniline in 1000 - 1200 parts of 1,2-dichloroethane, add 14 - 20 parts of 9H-carbazole-3-sulfonyl chloride, 0.03 - 0.3 parts of indium acetate, and 3 - 6 parts of aluminum trichloride, and heat to 70 - 80 °C, react for 2 - 4 h, distill off 1,2-dichloroethane, and dry to obtain the high-temperature resistant additive.

[0016] Beneficial effects of the above high-temperature resistant additive:

[0017] 1) Improve high-temperature resistance: The carbazole ring has good thermal stability. Introducing it into polyaniline can significantly improve the high-temperature resistance of the material, which is crucial for the negative lead paste of vehicle high-temperature start-stop batteries as these batteries need to start and stop frequently in high-temperature environments.

[0018] 2) Enhance electrochemical performance: The formation of organic indium complexes helps improve the electrochemical performance of the material, such as increasing conductivity and reducing resistance, which has a positive impact on the charge-discharge performance and cycle life of the battery.

[0019] 3) Improve structural stability: The introduction of the carbazole ring can also increase the intermolecular forces of the material, thereby improving its structural stability, which is of great significance for maintaining the performance of the battery during long-term use.

[0020] Specifically, based on 100 parts by weight of lead powder, 10 - 20 parts of the sulfuric acid solution with a volume ratio concentration of 5% - 10% and 30 - 50 parts of water are used. The oxidation degree of the lead powder can be 60% - 80%.

[0021] The present invention provides a method for preparing the negative lead paste of the vehicle high-temperature start-stop battery, comprising the following steps:

[0022] Step 1: Add polyester staple fiber, nano-scale sodium sulfate and nano-scale barium sulfate into water, conduct wet mixing and mix evenly to obtain a mixed solution; at the same time, dry-mix the high-temperature resistant additive, carbon material additive and lead powder to obtain a mixed powder.

[0023] Step 2: Mix the above-mentioned mixed solution and mixed powder evenly, then keep the mixed state and add the sulfuric acid solution to obtain the negative lead paste of the vehicle high-temperature start-stop battery.

[0024] Preferably, in Step 1, the wet mixing is carried out by stirring, the stirring speed is 300 - 600 rpm, and the stirring time is 10 - 20 minutes.

[0025] The dry mixing method is ball milling, the ball milling speed is 100 - 300 rpm, the ball milling time is 10 - 25 minutes, and the ball-to-material ratio is 8 - 12∶1.

[0026] Preferably, in Step 2, during the paste-making process of adding the sulfuric acid solution, the temperature is controlled at 50 - 70°C.

[0027] Preferably, in Step 2, the apparent density of the prepared negative lead paste is 3.5 - 4.5 g / cm 3 , and the penetration is 15 - 25 mm.

[0028] Preferably, in step two, after adding the sulfuric acid solution, pasting is completed, and the lead paste is cured and dried. The curing temperature is 35 - 45 °C, the humidity is controlled at 75% - 95% during the curing process, and the curing time is 24 - 36 hours.

[0029] Preferably, the drying temperature is 50 - 65 °C, and the drying time is 18 - 24 hours.

[0030] Compared with the prior art solutions, the present invention has the following beneficial effects:

[0031] In the present invention, the acylation reaction of polyaniline with 9H-carbazole-3-sulfonyl chloride and indium acetate not only successfully introduces a carbazole ring and an organoindium complex, but also significantly improves the high-temperature resistance, electrical conductivity (the internal resistance is reduced by half), cycle life (the highest increase is about 61%), rate performance (the highest increase is 11%), energy density, and structural stability of the material. These technical effects are of great significance for the application of the negative electrode lead paste of vehicle high-temperature start-stop batteries. Specific Embodiments

[0032] Example 1

[0033] The preparation method of the high-temperature resistant additive used in this example is as follows:

[0034] Disperse 100 g of polyaniline in 1000 g of 1,2-dichloroethane, add 14 g of 9H-carbazole-3-sulfonyl chloride, 0.03 g of indium acetate, and 3 g of aluminum trichloride, and heat to 70 °C. React for 4 h, distill off 1,2-dichloroethane, and dry to obtain the high-temperature resistant additive.

[0035] A preparation method of a negative electrode lead paste for a vehicle high-temperature start-stop battery includes the following steps:

[0036] Step one: Add 0.5 g of polyester staple fiber, 0.5 g of nanoscale barium sulfate, and 0.2 g of nanoscale sodium sulfate to 30 g of deionized water, stir at a stirring speed of 300 rpm for 10 minutes to obtain a mixed solution; at the same time, place 0.1 g of high-temperature resistant additive, 0.2 g of carbon black, and 100 g of lead powder (oxidation degree 60%) in a ball mill tank, and use a ball mill for ball milling and mixing. The ball milling speed is 100 rpm, the ball milling time is 10 minutes, and the ball-to-material ratio is 8:1 to obtain a mixed powder;

[0037] Step 2: Mix the above-mentioned mixed solution and mixed powder, continuously stir for 10 minutes during the mixing process, then slowly pour 10 g of dilute sulfuric acid (volume ratio concentration of 5%) while maintaining stirring, continue stirring for 10 minutes, use deionized water to adjust the apparent density of the lead paste to 3.5 g / cm³ and the penetration to 15 mm to complete paste mixing. Control the temperature during the paste mixing process at 50°C, then cure the lead paste at a curing temperature of 35°C with the humidity controlled at 75% for 24 hours; then dry at a drying temperature of 50°C for 24 hours to obtain the negative electrode lead paste described in this method.

[0038] Example 2

[0039] The preparation method of the high-temperature resistant additive used in this example is as follows:

[0040] Disperse 110 g of polyaniline in 1100 g of 1,2-dichloroethane, add 16 g of 9H-carbazole-3-sulfonyl chloride, 0.1 g of indium acetate and 4 g of aluminum trichloride, and heat to 75°C, react for 3 h, distill off 1,2-dichloroethane, and dry to obtain the high-temperature resistant additive.

[0041] A preparation method for the negative electrode lead paste of a vehicle high-temperature start-stop battery includes the following steps:

[0042] Step 1: Add 0.75 g of polyester staple fiber, 1 g of nanoscale barium sulfate and 0.5 g of nanoscale sodium sulfate to 40 g of deionized water, stir at a stirring speed of 400 rpm for 15 minutes to obtain a mixed solution; at the same time, place 0.4 g of high-temperature resistant additive, 0.8 g of carbon nanotubes and 100 g of lead powder (oxidation degree of 70%) in a ball mill tank, use a ball mill for ball milling and mixing, with a ball milling speed of 200 rpm, a ball milling time of 15 minutes, and a ball-to-material ratio of 10:1 to obtain a mixed powder;

[0043] Step 2: Mix the above-mentioned mixed solution and mixed powder, continuously stir for 15 minutes during the mixing process, then slowly pour 15 g of dilute sulfuric acid (volume ratio concentration of 7%) while maintaining stirring, continue stirring for 12 minutes, use deionized water to adjust the apparent density of the lead paste to 4 g / cm³ and the penetration to 20 mm to complete paste mixing. Control the temperature during the paste mixing process at 60°C, then cure the lead paste at a curing temperature of 40°C with the humidity controlled at 85% for 28 hours; then dry at a drying temperature of 55°C for 22 hours to obtain the negative electrode lead paste described in this method.

[0044] Example 3

[0045] The preparation method of the high-temperature resistant additive used in this example is as follows:

[0046] Disperse 110 g of polyaniline in 1100 g of 1,2-dichloroethane, add 18 g of 9H-carbazole-3-sulfonyl chloride, 0.2 g of indium acetate and 5 g of aluminum trichloride, and heat to 75 °C. React for 3 h, distill off 1,2-dichloroethane, and dry to obtain a high-temperature resistant additive.

[0047] A method for preparing the negative electrode lead paste of a vehicle high-temperature start-stop battery, comprising the following steps:

[0048] Step 1: Add 0.8 g of polyester staple fiber, 1.5 g of nano-barium sulfate and 0.8 g of nano-sodium sulfate to 40 g of deionized water, and stir for 15 minutes at a stirring speed of 500 rpm to obtain a mixed solution; at the same time, place 0.8 g of high-temperature resistant additive, 0.8 g of graphene and 100 g of lead powder (oxidation degree 70%) in a ball mill tank, and use a ball mill for ball milling and mixing. The ball milling speed is 200 rpm, the ball milling time is 20 minutes, and the ball-to-material ratio is 10:1 to obtain a mixed powder;

[0049] Step 2: Mix the above mixed solution and mixed powder, continuously stir for 15 minutes during the mixing process, then slowly pour 15 g of dilute sulfuric acid (volume ratio concentration 8%) while stirring, continue to stir for 13 minutes, and use deionized water to adjust the apparent density of the lead paste to 4 g / cm³ and the penetration to 20 mm to complete the paste mixing. The temperature during the paste mixing process is controlled at 60 °C, and then the lead paste is cured at a curing temperature of 40 °C with the humidity controlled at 85% during the curing process for 28 hours; then dried at a drying temperature of 60 °C for 20 hours to obtain the negative electrode lead paste described in this method.

[0050] Example 4

[0051] The preparation method of the high-temperature resistant additive used in this example is as follows:

[0052] Disperse 120 g of polyaniline in 1200 g of 1,2-dichloroethane, add 20 g of 9H-carbazole-3-sulfonyl chloride, 0.3 g of indium acetate and 6 g of aluminum trichloride, and heat to 80 °C. React for 2 h, distill off 1,2-dichloroethane, and dry to obtain a high-temperature resistant additive.

[0053] A method for preparing the negative electrode lead paste of a vehicle high-temperature start-stop battery, comprising the following steps:

[0054] Step 1: Add 1 g of polyester staple fiber, 2 g of nano-barium sulfate and 1 g of nano-sodium sulfate to 50 g of deionized water, and stir for 20 minutes at a stirring speed of 600 rpm to obtain a mixed solution; at the same time, place 1 g of high-temperature resistant additive, 1 g of acetylene carbon black and 100 g of lead powder (oxidation degree 80%) in a ball mill tank, and use a ball mill for ball milling and mixing. The ball milling speed is 300 rpm, the ball milling time is 25 minutes, and the ball-to-material ratio is 12:1 to obtain a mixed powder;

[0055] Step 2: Mix the above mixed solution and mixed powder, continuously stir for 20 minutes during the mixing process, then slowly pour 20 g of dilute sulfuric acid (volume ratio concentration of 10%) while maintaining stirring, continue to stir for 15 minutes, use deionized water to adjust the apparent density of the lead paste to 4.5 g / cm³ and the penetration to 25 mm, complete the paste mixing, control the temperature during the paste mixing process at 70 °C, then cure the lead paste at a curing temperature of 45 °C, control the humidity during the curing process at 95%, and cure for 36 hours; then dry at a drying temperature of 65 °C for 18 hours to obtain the negative electrode lead paste described in this method.

[0056] Comparative Example 1

[0057] A method for preparing a negative electrode lead paste for a vehicle high-temperature start-stop battery includes the following steps:

[0058] Step 1: Add 0.5 g of polyester staple fiber, 0.5 g of nanoscale barium sulfate, and 0.2 g of nanoscale sodium sulfate to 30 g of deionized water, stir for 10 minutes at a stirring speed of 300 rpm to obtain a mixed solution; at the same time, place 0.2 g of carbon black and 100 g of lead powder (oxidation degree of 60%) in a ball mill tank, use a ball mill for ball milling and mixing, with a ball milling speed of 100 rpm, a ball milling time of 10 minutes, and a ball-to-material ratio of 8:1 to obtain a mixed powder;

[0059] Step 2: Mix the above mixed solution and mixed powder, continuously stir for 10 minutes during the mixing process, then slowly pour 10 g of dilute sulfuric acid (volume ratio concentration of 5%) while maintaining stirring, continue to stir for 10 minutes, use deionized water to adjust the apparent density of the lead paste to 3.5 g / cm³ and the penetration to 15 mm, complete the paste mixing, control the temperature during the paste mixing process at 50 °C, then cure the lead paste at a curing temperature of 35 °C, control the humidity during the curing process at 75%, and cure for 24 hours; then dry at a drying temperature of 50 °C for 24 hours to obtain the negative electrode lead paste described in this method.

[0060] Comparative Example 2

[0061] The additive used in this comparative example is modified polyaniline, and its preparation method is as follows:

[0062] Disperse 100 g of polyaniline in 1000 g of 1,2-dichloroethane, add 14 g of 9H-carbazole-3-sulfonyl chloride and 3 g of aluminum trichloride, heat to 70 °C, react for 4 h, distill off 1,2-dichloroethane, and dry to obtain the additive.

[0063] A method for preparing a negative electrode lead paste for a vehicle high-temperature start-stop battery includes the following steps:

[0064] Step 1: Add 0.5 g of polyester staple fiber, 0.5 g of nanoscale barium sulfate, and 0.2 g of nanoscale sodium sulfate into 30 g of deionized water, and stir for 10 minutes at a stirring speed of 300 rpm to obtain a mixed solution; at the same time, place 0.1 g of additive, 0.2 g of carbon black, and 100 g of lead powder (oxidation degree of 60%) in a ball milling tank, and use a ball mill for ball milling and mixing. The ball milling speed is 100 rpm, the ball milling time is 10 minutes, and the ball-to-material ratio is 8:1 to obtain a mixed powder;

[0065] Step 2: Mix the above-mentioned mixed solution and mixed powder, continuously stir during the mixing process for 10 minutes, then slowly pour 10 g of dilute sulfuric acid (volume ratio concentration of 5%) while maintaining stirring, and continue to stir for 10 minutes. Use deionized water to adjust the apparent density of the lead paste to 3.5 g / cm³ and the penetration to 15 mm to complete paste mixing. The temperature during the paste mixing process is controlled at 50°C. Subsequently, cure the lead paste at a curing temperature of 35°C, control the humidity at 75% during the curing process, and cure for 24 hours; then dry at a drying temperature of 50°C for 24 hours to obtain the negative electrode lead paste described in this method.

[0066] Comparative Example 3

[0067] The additive used in this comparative example is modified polyaniline, and its preparation method is as follows:

[0068] Disperse 100 g of polyaniline in 1000 g of 1,2-dichloroethane, add 0.03 g of indium acetate and 3 g of aluminum trichloride, and heat to 70°C, react for 4 h, distill off 1,2-dichloroethane, and dry to obtain the additive.

[0069] A preparation method for the negative electrode lead paste of a vehicle high-temperature start-stop battery, comprising the following steps:

[0070] Step 1: Add 0.5 g of polyester staple fiber, 0.5 g of nanoscale barium sulfate, and 0.2 g of nanoscale sodium sulfate into 30 g of deionized water, and stir for 10 minutes at a stirring speed of 300 rpm to obtain a mixed solution; at the same time, place 0.1 g of additive, 0.2 g of carbon black, and 100 g of lead powder (oxidation degree of 60%) in a ball milling tank, and use a ball mill for ball milling and mixing. The ball milling speed is 100 rpm, the ball milling time is 10 minutes, and the ball-to-material ratio is 8:1 to obtain a mixed powder;

[0071] Step 2: Mix the above-mentioned mixed solution and mixed powder, continuously stir for 10 minutes during the mixing process, then slowly pour 10 g of dilute sulfuric acid (volume ratio concentration is 5%) while maintaining stirring, continue to stir for 10 minutes, use deionized water to adjust the apparent density of the lead paste to 3.5 g / cm³ and the penetration to 15 mm to complete paste mixing. The temperature during the paste mixing process is controlled at 50°C. Subsequently, cure the lead paste at a curing temperature of 35°C with the humidity controlled at 75% during the curing process for 24 hours; then dry at a drying temperature of 50°C for 24 hours to obtain the negative electrode lead paste described in this method.

[0072] Test Example 1

[0073] 1. Test method (applicable to two-wheel and three-wheel vehicle batteries):

[0074] 1. Conductivity test: Use electrochemical impedance spectroscopy (EIS) to test the internal resistance of the electrode, with the frequency range from 10 -2 Hz to 10 6 Hz, and measure the minimum value of the AC impedance.

[0075] 2. Cycle life test: Under the condition of 25°C, conduct cyclic charge and discharge tests on the lead-acid battery according to the standards of the International Battery Association (IEC). Cycling conditions: Constant current charging current is 0.2C, and constant current discharge is terminated at 1.8 V, and count the number of cycles.

[0076] 3. Energy density test: Under the condition of 0.1C rate, measure the discharge capacity of the battery and calculate the mass energy density (Wh / kg) of the battery.

[0077] 4. Rate performance test: Under the 0.5C discharge rate, measure the discharge capacity of the battery and calculate the rate retention rate.

[0078] 2. Test method (applicable to automotive batteries)

[0079] Fully charged storage batteries are tested in a water bath at 75°C ± 3°C according to the following test cycle:

[0080] a) Discharge at 25 A for 18 s;

[0081] b) Constant voltage 14.2 V, current limited to 25 A for charging for 30 min;

[0082] c) Discharge at 3 A for 15 min;

[0083] d) Constant voltage 14.2 V, current limited to 25 A for charging for 30 min;

[0084] e) Discharge at 25 A for 18 s;

[0085] f) Constant voltage 14.2 V, current limited to 25 A for charging for 30 min;

[0086] g) Discharge at 3 A for 15 min;

[0087] h) Charge at a constant voltage of 14.2 V with a current limit of 25 A for 30 min;

[0088] i) Discharge at 3 A for 15 min;

[0089] j) Charge at a constant voltage of 14.2 V with a current limit of 25 A for 29 min 24 s;

[0090] The battery is subjected to 6 cycles according to steps a) - j), and each cycle takes 3.25 h;

[0091] k) After 6 cycles are completed, first discharge at 10 A for 15 min, and then charge at a constant voltage of 14.2 V with a current limit of 25 A for 255 min;

[0092] l) Repeat a) - k) 4 times;

[0093] m) Repeat a) - j) 4 times;

[0094] n) Discharge at 10 A for 15 min;

[0095] o) Charge at a constant voltage of 14.2 V with a current limit of 25 A for 120 min;

[0096] The above tests include 34 cycles.

[0097] p) The storage battery is placed open - circuit in an environment temperature of 75℃ ± 2℃ for 28 h - 33 h;

[0098] q) Then discharge with a current of 200 A for 10 s, and it is required that the voltage is greater than 7.2 V at 10 s, otherwise the test is terminated;

[0099] r) a) - f) is one unit;

[0100] s) If one or more of the following situations occur, it means the test is terminated:

[0101] —— At the end of any charging step, the current is higher than 15 A;

[0102] —— At the end of any discharging step, the voltage is lower than 7.2 V;

[0103] —— When in a static state, the voltage is lower than 12 V.

[0104] The test results applicable to batteries for two - wheel and three - wheel vehicles are shown in Table 1.

[0105] Table 1 Test Results

[0106]

[0107] The 75°C high-temperature test results for automotive batteries are shown in Table 2 as follows.

[0108] Table 2 Test Results

[0109]

[0110] The above test results show that the negative electrode lead paste prepared by the present invention has significantly improved electrical conductivity, cycle life, rate performance, energy density, and high-temperature resistance compared to the sample of the comparative example, verifying the effectiveness and superiority of the technical solution of the present invention.

Claims

1. A negative electrode lead paste for a vehicle high-temperature start-stop battery, comprising lead powder, sulfuric acid solution, water and additives, characterized in that, Based on 100 parts by weight of lead powder, the additive contains the following raw materials in parts by weight: 0.5 - 1 part of polyester staple fiber, 0.5 - 2 parts of nano - barium sulfate, 0.2 - 1 part of nano - sodium sulfate, 0.1 - 1 part of high - temperature resistant additive, 0.2 - 1 part of carbon material additive; The high - temperature resistant additive is obtained by the sulfonamide reaction of polyaniline with 9H - carbazole - 3 - sulfonyl chloride and the coordination reaction with indium acetate.

2. The negative electrode lead paste of the vehicle high-temperature start-stop battery according to claim 1, characterized in that, The carbon material additive is selected from one or a combination of carbon black, carbon nanotubes, graphene, acetylene black, and carbon fiber.

3. The negative electrode lead paste of the vehicle high-temperature start-stop battery according to claim 1, characterized in that, The high - temperature resistant additive is modified polyaniline, and its preparation method is as follows: Disperse 100 - 120 parts of polyaniline in 1000 - 1200 parts of 1,2 - dichloroethane, add 14 - 20 parts of 9H - carbazole - 3 - sulfonyl chloride, 0.03 - 0.3 parts of indium acetate, and 3 - 6 parts of aluminum trichloride, and heat to 70 - 80 °C, react for 2 - 4 h, distill off 1,2 - dichloroethane, and dry to obtain the high - temperature resistant additive.

4. The negative electrode lead paste of the vehicle high-temperature start-stop battery according to claim 1, characterized in that, Based on 100 parts by weight of lead powder, 10 - 20 parts of the sulfuric acid solution, with a volume ratio concentration of 5% - 10%; 30 - 50 parts of water.

5. The preparation method of the negative electrode lead paste of the vehicle high-temperature start-stop battery according to any one of claims 1-4, characterized in that, It includes the following steps: Step 1: Add polyester staple fiber, nano - barium sulfate, and nano - sodium sulfate to water, carry out wet mixing and mix evenly to obtain a mixed solution; at the same time, dry - mix the high - temperature resistant additive, carbon material additive, and lead powder to obtain a mixed powder; Step 2: Mix the above - mentioned mixed solution and mixed powder evenly, then keep the mixed state and add the sulfuric acid solution to obtain the negative lead paste for vehicle high - temperature start - stop battery.

6. The preparation method of the negative electrode lead paste of the vehicle high-temperature start-stop battery according to claim 5, wherein, In Step 1, the wet mixing is carried out by stirring, the stirring speed is 300 - 600 rpm, and the stirring time is 10 - 20 minutes; The dry - mixing method is ball - milling, the rotation speed of the ball - milling is 100 - 300 rpm, the ball - milling time is 10 - 25 minutes, and the ball - to - material ratio is 8 - 12∶1.

7. The preparation method of the negative electrode lead paste for the vehicle high-temperature start-stop battery according to claim 5, characterized in that, In Step 2, during the paste - making process of adding the sulfuric acid solution, the temperature is controlled at 50 - 70 °C.

8. The preparation method of the negative electrode lead paste of the vehicle high-temperature start-stop battery according to claim 5, characterized in that, In Step 2, the apparent density of the prepared negative electrode lead paste is 3.5 - 4.5 g / cm 3 , and the penetration is 15 - 25 mm.

9. The preparation method of the negative electrode lead paste for a vehicle high-temperature start-stop battery according to claim 5, characterized in that, In Step 2, after adding the sulfuric acid solution, complete the paste - making, cure and dry the lead paste. The curing temperature is 35 - 45 °C, the humidity during the curing process is controlled at 75% - 95%, and the curing time is 24 - 36 hours.

10. The preparation method of the negative electrode lead paste of the vehicle high-temperature start-stop battery according to claim 9, characterized in that, The drying temperature is 50 - 65 °C, and the drying time is 18 - 24 hours.

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