Preparation method and application of high-specific-capacitance lead storage battery positive electrode lead paste

Abstract

The invention provides a preparation method and application of positive electrode lead paste of a high-specific-capacitance lead storage battery. The positive electrode lead paste is prepared from the following components in parts by mass: 980 to 1040 parts of lead powder, 85 to 100 parts of dilute sulphuric acid, 105 to 120 parts of deionized water, 1.5 to 3 parts of a composite electrode material, 0.8 to 1.4 parts of an antimony compound, 0.6 to 1.2 parts of metal sulfate, 38 to 44 parts of lead oxide and 0.7 to 1.0 part of polyester fibers. By optimizing the lead paste formula, the conductivity and the specific capacitance of the lead paste are improved, and the cycle life of the battery is prolonged.

Description

Technical Field

[0001] The invention belongs to the technical field of lead-acid batteries, and in particular relates to a preparation method and application of a positive electrode lead paste for a high specific capacitance lead-acid battery. Background Art

[0002] Lead-acid batteries are widely used in automobile starting power supplies, uninterruptible power supplies (UPS), electric bicycle power sources, and various energy storage systems due to their significant advantages such as low cost, high safety, mature technology, good high and low temperature performance, and large current discharge. For example, in the automotive field, lead-acid batteries are a key component of the vehicle starting and power supply system, providing the necessary power support for the normal operation of the vehicle; in the communication field, the lead-acid batteries in UPS ensure the continuous operation of communication equipment when the city power is interrupted, ensuring the stability and reliability of communication.

[0003] The patent application with publication number CN107634209A discloses a positive lead paste for lead-acid batteries, comprising the following components, each component by weight: 75-85 parts of lead powder, 10-20 parts of sulfuric acid, 8-15 parts of deionized water, 0.5-1.5 parts of nano-carbon fibers, 0.1-1.2 parts of polyacrylic acid, and 0.05-0.15 parts of polytetrafluoroethylene. The patent application improves the cold start performance of lead-acid batteries by optimizing the combination of multiple additives.

[0004] However, with the rapid development of new energy technologies and increasingly stringent requirements for battery performance in various industries, traditional lead-acid batteries are facing severe challenges. Among them, specific capacitance, as one of the key indicators for measuring battery performance, directly affects the battery's charging and discharging efficiency and energy storage capacity. High specific capacitance means that the battery can store more charge per unit mass or volume, so that the battery can achieve faster conversion of electrical energy and chemical energy during the charging and discharging process, improving the operating efficiency and endurance of the equipment.

[0005] The positive electrode lead paste of traditional lead-acid batteries mainly adopts the lead paste material formed by the reaction of lead powder and sulfuric acid. Although the process is mature, it still has the following problems: insufficient conductivity: the microstructure of traditional lead paste is relatively dense, and the conductivity of active materials is low, which leads to limited specific capacity of the plate and reduces the energy density of the battery; limited cycle life: the lead paste is prone to structural expansion and shedding during the charge and discharge cycle, resulting in loss of active materials on the plate, which in turn affects the long-term stability of the battery; low specific capacitance: when the lead-acid battery is discharged at a high rate, the utilization rate of active materials is low, which makes it difficult to meet the needs of high-power energy storage applications.

[0006] The patent application with publication number CN117219733A discloses a positive electrode for a lead-acid battery with a long cycle life and a preparation method. The positive electrode for a lead-acid battery with a long cycle life includes the following raw materials, by weight percentage: 5% to 10% dilute sulfuric acid, 5% to 20% deionized water, 0.1% to 0.5% carbon fiber, 0.05% to 0.5% conductive additive, 0.05% to 0.5% bismuth oxide, 0.05% to 0.5% structural stabilizing additive, 0.1% to 5% seed additive, 2% to 20% red lead, and the rest is lead powder. The invention provides seeds for forming 4BS by adding seed additives to the lead paste, and the mixing is more uniform; the conductive additive is added to the lead paste, which is conducive to improving the charging acceptance; the structural stabilizing additive in the lead paste makes the lead paste stable in structure and does not soften during the cycle, thereby extending the cycle life.

[0007] Although there are many studies in the prior art on improving the conductivity and cycle stability of lead paste of lead-acid batteries by using additives, there is still room for improvement in the energy storage performance and cycle life of lead-acid batteries. Summary of the invention

[0008] In order to solve the above technical problems existing in the prior art, the present invention provides a preparation method and application of a high specific capacitance lead paste for positive electrode of a lead-acid battery, which improves the conductivity and specific capacitance of the lead paste by optimizing the lead paste formula, thereby extending the cycle life of the battery.

[0009] The present invention provides a method for preparing a positive electrode lead paste for a high specific capacitance lead-acid battery, wherein the positive electrode lead paste is prepared from the following components in parts by mass: 980-1040 parts of lead powder, 85-100 parts of dilute sulfuric acid, 105-120 parts of deionized water, 1.5-3 parts of composite electrode material, 0.8-1.4 parts of antimony compound, 0.6-1.2 parts of metal sulfate, 38-44 parts of lead oxide, and 0.7-1.0 parts of polyester fiber.

[0010] Preferably, the density of the dilute sulfuric acid is 1.3-1.6 g / mL.

[0011] Preferably, the polyester fiber is a quinoline-modified polyethylene terephthalate fiber, and the preparation method of the polyester fiber is as follows: 105-130 parts by mass of polyethylene terephthalate fiber is placed in 1200-2000 parts by mass of ethylene dichloride, and after stirring evenly, 0.2-0.66 parts by mass of zinc chloride catalyst is added; 3.5-6 parts by mass of 2,3-quinoline dicarboxylic anhydride is added, and an acylation reaction is performed to obtain quinoline-modified polyethylene terephthalate fiber. By introducing quinoline structure into polyester fiber, the polyester fiber is endowed with excellent properties such as anti-oxidation and anti-ultraviolet, and the stability and durability are improved. In addition, the surface polarity and chemical properties of the polyester fiber are changed, and the compatibility with the lead paste component is enhanced, which is conducive to dispersion.

[0012] Acylation reaction mechanism: The zinc chloride catalyst coordinates with the carbonyl oxygen of 2,3-quinolinedicarboxylic anhydride to enhance the positive charge of the carbonyl carbon; the carbonyl carbon of the activated 2,3-quinolinedicarboxylic anhydride attacks the benzene ring of the polyethylene terephthalate fiber, undergoing electrophilic substitution, and hydrogen leaves as a proton to form quinoline-modified polyethylene terephthalate fiber.

[0013] More preferably, the acylation reaction temperature is 58-65°C, and the reaction time is 4.5-6 hours. More preferably, the acylation reaction temperature is 65°C, and the reaction time is 6 hours.

[0014] Preferably, the method for preparing the composite electrode material comprises the following steps: S1: washing 12-20 parts by mass of carbon nanotubes with acid to remove surface impurities, then washing to neutrality, and drying; S2: Place the carbon nanotubes obtained in step S1 into a reaction vessel, add 100-150 parts by mass of Mn(NO 3 ) 2 aqueous solution, stirring and mixing; then adding 100-120 parts by mass of KMnO with a concentration of 0.06-0.1 M 4 The aqueous solution is added dropwise while stirring to obtain the product by reaction; S3: The product obtained in step S2 is washed to neutrality, and then heated at 130-160° C. for 6-10 hours. After the product is cooled to room temperature, it is washed to remove surface residues and dried to obtain the composite electrode material.

[0015] Further preferably, in step S2, KMnO 4 When the aqueous solution is added dropwise, the dropping speed is controlled at 1-2 mL / min, the reaction temperature is 65-80°C, the reaction time is 2.5-4 hours, and after the reaction, the product is allowed to stand for 8-12 hours.

[0016] Further preferably, in step S3, during washing, deionized water is first used for washing 3-5 times, and then washed with ethanol.

[0017] Preferably, the antimony compound is at least one of antimony trioxide, antimony pentoxide and sodium antimonate; the metal sulfate is at least one of stannous sulfate, zinc sulfate and magnesium sulfate; and the lead oxide is at least one of lead tetroxide and lead oxide.

[0018] The present invention also provides a positive electrode lead paste for a high specific capacitance lead-acid battery prepared by the preparation method.

[0019] The present invention also provides a high specific capacitance lead-acid battery positive electrode plate, comprising a positive electrode grid and a positive electrode lead paste coated on the positive electrode grid, wherein the positive electrode lead paste is the high specific capacitance lead-acid battery positive electrode lead paste.

[0020] Compared with the prior art, the present invention has the following beneficial effects: (1) Improvement of specific capacitance: Improve the microstructure and conductivity of the positive electrode lead paste, form a conductive network, increase the electrode-electrolyte contact area, and improve the specific capacitance.

[0021] (2) Improved charge and discharge performance: The positive lead paste of the present invention makes the battery charge and discharge efficiency higher and the voltage output more stable.

[0022] (3) Enhanced electrode stability: Polyester fiber is resistant to oxidation and has good durability. It maintains the integrity of the positive electrode lead paste structure, reduces electrode expansion and shedding, and extends battery life. DETAILED DESCRIPTION

[0023] Example 1

[0024] 1. Positive lead paste formula composition: 980 g lead powder, 85 g dilute sulfuric acid (density of dilute sulfuric acid is 1.3 g / mL), 105 g deionized water, 1.5 g composite electrode material, 0.8 g antimony pentoxide, 1.2 g zinc sulfate, 38 g lead tetroxide, and 0.7 g quinoline-modified polyester fiber (length 1.0 mm, diameter 15 μm).

[0025] 2. Preparation of composite electrode materials: S1: 12 g of carbon nanotubes were placed in 55 g of mixed acid, and ultrasonicated at 50 °C for 3 h to remove surface impurities, and then fully washed to neutrality, and then vacuum dried for 10 h; the mixed acid was concentrated nitric acid / sulfuric acid (1:3, v / v) solution, wherein the concentration of concentrated nitric acid was 65wt%, and the concentration of concentrated sulfuric acid was 98wt%, the same below; S2: 100 g 0.15 M Mn(NO 3 ) 2 The aqueous solution was added to the reaction vessel containing the treated carbon nanotubes, stirred and dispersed, and 100 g of 0.08 M KMnO was added dropwise. 4 , the dropping speed was controlled at 1.5 mL / min, the stirring speed was maintained at 350 rpm, the reaction temperature was 70 °C, the reaction time was 3 h, and after the reaction, the product was allowed to stand for 8 hours; S3: The product was washed with deionized water until the pH of the washing solution was 7, and then transferred to a hydrothermal reactor with a reaction temperature of 140°C and a reaction time of 9 h. After the reaction product was cooled to room temperature, it was first washed with deionized water for 3 times, then washed with ethanol, and dried to obtain the composite electrode material.

[0026] 3. Preparation of quinoline modified polyester fiber: K1: 110 g PET fiber was placed in 1500 g ethylene dichloride, stirred evenly and then 0.3 g ZnCl 2 , heat to 60 °C, slowly add 4 g of 2,3-quinolinedicarboxylic anhydride, react for 5 h, and stir continuously during the process; K2: After the reaction is completed, the fiber is filtered, washed thoroughly with deionized water to remove unreacted substances, and dried to obtain quinoline-modified polyethylene terephthalate fiber.

[0027] 4. Positive electrode lead paste preparation process: Step 1: Accurately weigh the ingredients in each mass portion, add the weighed lead powder, composite electrode material, antimony pentoxide, zinc sulfate and quinoline-modified polyester fiber into the paste mixer, then add the formula amount of lead tetroxide, close the sealing cover of the paste mixer, and then accurately weigh the formula amount of lead powder through the lead powder delivery pipeline of the paste mixer and add it into the paste mixer, start mixing and stirring, dry mix and stir for 7 minutes to make it evenly stirred; Step 2: Add deionized water three times, the mass of deionized water added three times is 40%, 30% and 30% of the formula amount respectively, each time interval is 1.5 min; Step 3: Slowly add dilute sulfuric acid three times, the mass of dilute sulfuric acid added three times is 40%, 20% and 40% of the formula amount respectively, and the total acid addition time is 15 minutes; Step 4: Measure the apparent specific gravity of the lead paste to be 4.38 g / cm³, otherwise adjust it to the specified apparent specific gravity requirement with deionized water; the peak temperature of the entire lead paste preparation process is controlled below 72 ℃, and the paste outlet temperature is lower than 48 ℃.

[0028] Example 2

[0029] 1. Positive lead paste formula composition: 1020 g lead powder, 95 g dilute sulfuric acid (density of dilute sulfuric acid is 1.4 g / mL), 115 g deionized water, 2.5 g composite electrode material, 1.2 g sodium antimonate, 0.6 g magnesium sulfate, 42 g lead oxide, 0.9 g quinoline-modified polyester fiber (length 0.8 mm, diameter 18 μm).

[0030] 2. Preparation of composite electrode materials: S1: 18 g of carbon nanotubes were placed in 58 g of mixed acid, ultrasonicated at 55 °C for 2.5 h to remove surface impurities, washed thoroughly to neutrality, and then vacuum dried for 9 h; S2: 120 g 0.18 M Mn(NO 3 ) 2The aqueous solution was added to the reaction vessel containing the treated carbon nanotubes, stirred and dispersed, and 110 g 0.07 M KMnO was added dropwise. 4 , the dropping speed was controlled at 1.8 mL / min, the stirring speed was maintained at 400 rpm, the reaction temperature was 65 °C, the reaction time was 3.5 h, and after the reaction, the product was allowed to stand for 9 hours; S3: The product was washed with deionized water until the pH of the washing solution was 7, and then transferred to a hydrothermal reactor with a reaction temperature of 150°C and a reaction time of 8 h. After the reaction product was cooled to room temperature, it was first washed with deionized water for 5 times, then washed with ethanol, and dried to obtain the composite electrode material.

[0031] 3. Preparation of quinoline modified polyester fiber: K1: 125 g PET fiber was placed in 1800 g ethylene dichloride, stirred evenly and then 0.5 g ZnCl 2 , raise the temperature to 58 °C, slowly add 5 g of 2,3-quinolinedicarboxylic anhydride, and react for 4.5 h with continuous stirring; K2: After the reaction is completed, the fiber is filtered, washed thoroughly with deionized water to remove unreacted substances, and dried to obtain quinoline-modified polyethylene terephthalate fiber.

[0032] 4. Positive electrode lead paste preparation process: Step 1: Accurately weigh the ingredients in each mass portion, add the weighed lead powder, composite electrode material, sodium antimonate, magnesium sulfate and quinoline-modified polyester fiber into a paste mixer, then add the formulated amount of lead oxide, close the sealing cover of the paste mixer, and then accurately weigh the formulated amount of lead powder through the lead powder delivery pipeline of the paste mixer and add it into the paste mixer, start mixing and stirring, dry mix and stir for 6 minutes to make it evenly stirred; Step 2: Add deionized water three times, the mass of deionized water added three times is 45%, 25% and 30% of the formula amount respectively, each time interval is 2 minutes; Step 3: Slowly add dilute sulfuric acid three times, the mass of dilute sulfuric acid added three times is 38%, 22% and 40% of the formula amount respectively, and the total acid addition time is 17 minutes; Step 4: Measure the apparent specific gravity of the lead paste to be 4.42 g / cm³, otherwise adjust it to the specified apparent specific gravity requirement with deionized water; the peak temperature of the entire lead paste preparation process is controlled below 73°C, and the paste outlet temperature is lower than 49°C.

[0033] Example 3

[0034] 1. Positive lead paste formula composition: 1000 g lead powder, 90 g dilute sulfuric acid (density of dilute sulfuric acid is 1.5 g / mL), 110 g deionized water, 2.0 g composite electrode material, 1.0 g antimony trioxide, 1.0 g stannous sulfate, 40 g lead tetroxide, and 0.8 g quinoline-modified polyester fiber (length 1.2 mm, diameter 12 μm).

[0035] 2. Preparation of composite electrode materials: S1: 15 g of carbon nanotubes were placed in 53 g of mixed acid, ultrasonicated at 58 °C for 3.5 h to remove surface impurities, washed thoroughly to neutrality, and then vacuum dried for 11 h; S2: 140 g 0.12 M Mn(NO 3 ) 2 The aqueous solution was added to the reaction vessel containing the treated carbon nanotubes, stirred and dispersed, and 110 g 0.06 M KMnO was added dropwise. 4 , the dropping speed was controlled at 1.2 mL / min, the stirring speed was maintained at 380 rpm, the reaction temperature was 75 °C, the reaction time was 2.5 h, and after the reaction, the product was allowed to stand for 10 hours; S3: The product was washed with deionized water until the pH of the washing solution was 7, and then transferred to a hydrothermal reactor with a reaction temperature of 130°C and a reaction time of 10 h. After the reaction product was cooled to room temperature, it was first washed with deionized water for 5 times, then washed with ethanol, and dried to obtain the composite electrode material.

[0036] 3. Preparation of quinoline modified polyester fiber: K1: 105 g PET fiber was placed in 1200 g ethylene dichloride, stirred evenly and then 0.2 g ZnCl 2 , raise the temperature to 62 °C, slowly add 3.5 g of 2,3-quinolinedicarboxylic anhydride, and react for 5.5 h with continuous stirring; K2: After the reaction is completed, the fiber is filtered, washed thoroughly with deionized water to remove unreacted substances, and dried to obtain quinoline-modified polyethylene terephthalate fiber.

[0037] 4. Positive electrode lead paste preparation process: Step 1: Accurately weigh the ingredients in each mass portion, add the weighed lead powder, composite electrode material, antimony trioxide, stannous sulfate and quinoline modified polyester fiber into the paste mixer, then add the formula amount of lead tetroxide, close the sealing cover of the paste mixer, and then accurately weigh the formula amount of lead powder through the lead powder delivery pipeline of the paste mixer and add it into the paste mixer, start mixing and stirring, dry mix and stir for 5.5 minutes to make it evenly stirred; Step 2: Add deionized water three times, the mass of deionized water added three times is 35%, 30% and 35% of the formula amount respectively, each time interval is 1.8 minutes; Step 3: Slowly add dilute sulfuric acid three times, the mass of dilute sulfuric acid added three times is 42%, 18% and 40% of the formula amount respectively, and the total acid addition time is 14 minutes; Step 4: Measure the apparent specific gravity of the lead paste to be 4.40 g / cm³, otherwise adjust it to the specified apparent specific gravity requirement with deionized water; the peak temperature of the entire lead paste preparation process is controlled below 71°C, and the paste outlet temperature is lower than 47°C.

[0038] Example 4

[0039] 1. Positive lead paste formula composition: 1040 g lead powder, 100 g dilute sulfuric acid (density of dilute sulfuric acid is 1.6 g / mL), 120 g deionized water, 3.0 g composite electrode material, 1.4 g (0.8 g + 0.6 g) of antimony trioxide / sodium antimonate combination, 0.8 g (0.5 g + 0.3 g) of stannous sulfate / magnesium sulfate combination, 44 g (25 g + 19 g) of lead tetroxide / lead oxide combination, and 1.0 g (length 0.6 mm, diameter 20 μm) of quinoline-modified polyester fiber.

[0040] 2. Preparation of composite electrode materials: S1: 20 g of carbon nanotubes were placed in 60 g of mixed acid, ultrasonicated at 60 °C for 4 h to remove surface impurities, washed thoroughly to neutrality, and then vacuum dried for 8 h; S2: 150 g 0.2 M Mn(NO 3 ) 2 The aqueous solution was added to the reaction vessel containing the treated carbon nanotubes, stirred and dispersed, and 120 g of 0.1 M KMnO was added dropwise. 4 , the dropping speed was controlled at 2 mL / min, the stirring speed was maintained at 450 rpm, the reaction temperature was 80 °C, the reaction time was 4 h, and after the reaction, the product was allowed to stand for 12 hours; S3: The product was washed with deionized water until the pH of the washing solution was 7, and then transferred to a hydrothermal reactor with a reaction temperature of 160°C and a reaction time of 6 h. After the reaction product was cooled to room temperature, it was first washed with deionized water for 5 times, then washed with ethanol, and dried to obtain the composite electrode material.

[0041] 3. Preparation of quinoline modified polyester fiber: K1: 130 g PET fiber was placed in 2000 g ethylene dichloride, stirred evenly, and then 0.66 g ZnCl was added. 2, raise the temperature to 65 °C, slowly add 6 g of 2,3-quinolinedicarboxylic anhydride, and react for 6 h with continuous stirring; K2: After the reaction is completed, the fiber is filtered, washed thoroughly with deionized water to remove unreacted substances, and dried to obtain quinoline-modified polyethylene terephthalate fiber.

[0042] 4. Positive electrode lead paste preparation process: Step 1: Accurately weigh the ingredients in each mass portion, add the weighed lead powder, composite electrode material, antimony trioxide / sodium antimonate combination, stannous sulfate / magnesium sulfate combination and quinoline modified polyester fiber into a paste mixer, then add the formula amount of lead tetroxide / lead oxide combination, close the sealing cover of the paste mixer, and then accurately weigh the formula amount of lead powder through the lead powder delivery pipeline of the paste mixer and add it to the paste mixer, start mixing and stirring, dry mix and stir for 8 minutes to make it evenly stirred; Step 2: Add deionized water three times, the mass of deionized water added three times is 50%, 30% and 20% of the formula amount respectively, each time interval is 1 min; Step 3: Slowly add dilute sulfuric acid three times, the mass of dilute sulfuric acid added three times is 45%, 25% and 30% of the formula amount respectively, and the total acid addition time is 18 minutes; Step 4: Measure the apparent specific gravity of the lead paste to be 4.45 g / cm³, otherwise adjust it to the specified apparent specific gravity requirement with deionized water; the peak temperature of the entire lead paste preparation process is controlled below 74 ℃, and the paste outlet temperature is lower than 50 ℃.

[0043] Comparative Example 1 The difference between this example and Example 1 is that the composite electrode material in the lead paste preparation process is replaced by an equal amount of carbon nanotubes.

[0044] Comparative Example 2 The difference between this example and Example 1 is that the quinoline-modified polyester fiber in the lead paste preparation process is replaced by an equal amount of polyester fiber.

[0045] Test Example 1

[0046] The test method is as follows: 1. Electrode specific capacitance test 1.1 Preparation of working electrode: The positive lead pastes of different embodiments and comparative examples were coated on a lead mesh (area 1 cm2), dried at 60 °C for 24 h and then used. The prepared working electrode and commercial negative electrode plate were combined into a battery system and immersed in 1.08 g / cm 3 The formation was carried out in a sulfuric acid solution. The formation time was 24 h and the formation charge current density was 3~5 mA / cm 2 After the formation is completed, the working electrode is thoroughly washed and dried.

[0047] 1.2 Assembled using a three-electrode system Reference electrode: mercury-mercurous sulfate electrode (SCE), counter electrode: platinum sheet. Test electrolyte: 1.28 g / cm³ H 2 SO 4 Solution.

[0048] 1.3 The specific capacitance was determined by the constant current charge-discharge method (GCD), with a test current density of 1.0 A / g and a voltage range of 0-1.2 V. The specific capacitance C (F / g) was calculated as: C=I·Δt / m·ΔV. Where I is the discharge current, Δt is the discharge time, m is the mass of the active material, and ΔV is the discharge potential window.

[0049] 2. Charge and discharge cycle life test Using a two-electrode system, the negative electrode was prepared with the same mass and ratio of negative electrode lead paste. It was assembled into a 2 V lead-acid battery cell, and the test electrolyte was 1.28 g / cm³ H 2 SO 4 The cycle life test was carried out by constant current charge and discharge (0.2C, end voltage 1.8 V), and the number of cycles when 80% capacity was retained was recorded.

[0050] 3. Charge and discharge efficiency test Calculate the Coulomb efficiency of battery charge and discharge: η=Q discharge / Q charge ×100%. Among them, Q discharge is the discharge capacity, Q charge is the charging capacity.

[0051] Table 1 Test results

[0052] The test results are shown in Table 1. The high specific capacitance lead-acid battery positive electrode lead paste provided by Examples 1-4 of the present invention, based on manganese dioxide / three-dimensional carbon-based composite materials and quinoline-modified polyester fibers, significantly improves the energy storage performance and cycle life of lead-acid batteries and has good application prospects.

Claims

1. A method for preparing a positive lead paste for a high specific capacitance lead-acid battery, characterized in that: The high specific capacitance lead-acid battery positive electrode lead paste is prepared from the following components in parts by mass: 980-1040 parts of lead powder, 85-100 parts of dilute sulfuric acid, 105-120 parts of deionized water, 1.5-3 parts of composite electrode material, 0.8-1.4 parts of antimony compound, 0.6-1.2 parts of metal sulfate, 38-44 parts of lead oxide, and 0.7-1.0 parts of polyester fiber.

2. The method for preparing the positive lead paste of a high specific capacitance lead-acid battery according to claim 1, wherein: The density of the dilute sulfuric acid is 1.3-1.6 g / L.

3. The method for preparing the positive lead paste of high specific capacitance lead-acid battery according to claim 1, characterized in that: The polyester fiber is quinoline-modified polyethylene terephthalate fiber, and the preparation method of the polyester fiber is as follows: 105-130 parts by weight of polyethylene terephthalate fiber is placed in 1200-2000 parts by weight of ethylene dichloride, stirred evenly, and then 0.2-0.66 parts by weight of zinc chloride catalyst is added; 3.5-6 parts by weight of 2,3-quinoline dicarboxylic anhydride is added to carry out acylation reaction to obtain quinoline-modified polyethylene terephthalate fiber.

4. The method for preparing the positive lead paste of high specific capacitance lead-acid battery according to claim 3, characterized in that: The acylation reaction temperature is 58-65°C and the reaction time is 4.5-6 hours.

5. The method for preparing the positive lead paste of high specific capacitance lead-acid battery according to claim 1, characterized in that: The preparation method of the composite electrode material comprises the following steps: S1: washing 12-20 parts by mass of carbon nanotubes with acid to remove surface impurities, then washing to neutrality, and drying; S2: Place the carbon nanotubes obtained in step S1 into a reaction container, add 100-150 parts by mass of a 0.1-0.2 M Mn(NO3)2 aqueous solution, and stir to mix; then dropwise add 100-120 parts by mass of a 0.06-0.1 M KMnO4 aqueous solution, while stirring, and react to obtain a product; S3: The product obtained in step S2 is washed to neutrality, and then heated at 130-160° C. for 6-10 hours. After the obtained product is cooled to room temperature, it is washed to remove surface residues, and dried to obtain the composite electrode material.

6. The method for preparing the positive lead paste of a high specific capacitance lead-acid battery according to claim 5, characterized in that: In step S2, when the KMnO4 aqueous solution is added dropwise, the dropping speed is controlled at 1-2 mL / min, the reaction temperature is 65-80°C, the reaction time is 2.5-4 hours, and after the reaction, the product is allowed to stand for 8-12 hours.

7. The method for preparing the positive lead paste of a high specific capacitance lead-acid battery according to claim 5, characterized in that: In step S3, during washing, first use deionized water to wash for 3-5 times, and then use ethanol to wash.

8. The method for preparing the positive lead paste of high specific capacitance lead-acid battery according to claim 1, characterized in that: The antimony compound is at least one of antimony trioxide, antimony pentoxide and sodium antimonate; The metal sulfate is at least one of stannous sulfate, zinc sulfate and magnesium sulfate; The lead oxide is at least one of trilead tetroxide and lead oxide.

9. A high specific capacitance lead-acid battery positive electrode lead paste prepared by the preparation method according to any one of claims 1 to 8.

10. A positive electrode plate for a high specific capacitance lead-acid battery, comprising a positive electrode grid and a positive electrode lead paste coated on the positive electrode grid, characterized in that: The positive electrode paste is the high specific capacitance lead-acid battery positive electrode paste according to claim 9.

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