Preparation method and application of conductive polymer loaded PbSO4 nanoparticle composite

Abstract

The application relates to a preparation method and application of a conductive polymer loaded PbSO4 nanoparticle composite material and belongs to the technical field of electrochemical energy storage materials. 2‑ A lead nitrate solution is added drop by drop into the conductive polymer dispersion liquid to react for 2-8 hours, Pb 2+ In the solution is captured by SO4 2‑ On the conductive polymer molecular chain, PbSO4 nanoparticles are directly generated to realize synthesis of the conductive polymer loaded PbSO4 nanoparticle composite material. The method realizes in-situ loading of the PbSO4 nanoparticles on the conductive polymer, the PbSO4 nanoparticles are more uniformly distributed, and the combination between the two is stronger. The conductive polymer loaded PbSO4 nanoparticle composite material has the advantages of large specific surface area, good conductivity and the like. As a negative lead paste additive, the conductive polymer loaded PbSO4 nanoparticle composite material can significantly inhibit a hydrogen evolution side reaction in a charging process of a lead-carbon battery, can avoid failure caused by serious battery water loss, and can effectively improve the cycle life of the battery.

Description

TECHNICAL FIELD

[0001] The application relates to a preparation method and application of a conductive polymer loaded PbSO4 nanoparticle composite material and belongs to the technical field of electrochemical energy storage materials. BACKGROUND

[0002] Lead-carbon batteries are widely used in various aspects of life due to high safety, low price, and mature recycling technology. Various carbon materials such as activated carbon, carbon black, nanotubes and graphene are explored to be used as additives of negative plates to improve the conductivity. However, the hydrogen evolution overpotential of carbon materials is much lower than that of lead metal, and the introduction of carbon materials makes the lead-acid battery produce more hydrogen gas during battery charging, thereby intensifying the hydrogen evolution of the lead-acid battery, and further causing the electrolyte to dry up, and finally leading to the failure of the battery. SUMMARY

[0003] In view of the problems of serious hydrogen evolution and sulfation of the negative plate in the prior art lead-carbon battery, the application provides a preparation method and application of a conductive polymer loaded PbSO4 nanoparticle composite material. The conductive polymer powder is prepared in a dilute sulfuric acid solution, the conductive polymer molecular chain contains SO4 2- ; lead nitrate solution is added dropwise into the conductive polymer dispersion liquid and reacts at room temperature for 2-8h, Pb 2+ in the solution is captured by SO4 2- on the conductive polymer molecular chain, and PbSO4 nanoparticles are directly generated, so that the synthesis of the conductive polymer loaded PbSO4 nanoparticle composite material is realized. The method realizes in-situ loading of PbSO4 nanoparticles on the conductive polymer, the material distribution is more uniform, and the combination between the two is stronger. The conductive polymer loaded PbSO4 nanoparticle composite material has the advantages of large specific surface area and good conductivity. As an additive of lead paste of the negative plate of the lead-carbon battery, the conductive polymer loaded PbSO4 nanoparticle composite material can significantly inhibit the hydrogen evolution side reaction in the charging process of the lead-carbon battery, avoid the failure caused by serious battery water loss, and effectively improve the cycle life of the battery.

[0004] A preparation method of a conductive polymer loaded PbSO4 nanoparticle composite material is provided, and the specific steps are as follows:

[0005] (1) an oxidizing agent is dissolved in a dilute sulfuric acid solution to obtain an oxidizing agent / sulfuric acid solution, and the oxidizing agent / sulfuric acid solution is pre-cooled at a temperature of-5℃ to-1℃;

[0006] (2) a conductive polymer monomer is dissolved in a dilute sulfuric acid solution, and the monomer solution is uniformly stirred at low temperature; under the low-temperature stirring condition, a slightly excessive pre-cooled oxidizing agent / sulfuric acid solution is added dropwise into the monomer solution to react for 12-24h, solid-liquid separation is performed, the solid is washed to neutral with deionized water, and vacuum drying is performed to obtain a conductive polymer powder;

[0007] (3) dispersing the conductive polymer powder into deionized water to obtain a conductive polymer dispersion liquid, under stirring, dropwise adding a lead nitrate solution into the conductive polymer dispersion liquid and reacting at room temperature for 2-8 h, solid-liquid separation, washing the solid with deionized water, and freeze-drying to obtain a conductive polymer loaded PbSO4 nanoparticle composite material.

[0008] The oxidant in step (1) is one or more of ammonium persulfate, hydrogen peroxide, potassium dichromate, and manganese dioxide.

[0009] The concentration of the dilute sulfuric acid in step (1) is 1-3 mol / L, and the concentration of the oxidant in the oxidant / sulfuric acid solution is 0.5-2 mol / L.

[0010] The conductive polymer in step (2) is polyaniline or polythiophene.

[0011] The concentration of the dilute sulfuric acid solution in step (2) is 1-3 mol / L, the concentration of the conductive polymer monomer in the monomer solution is 0.1-0.5 mol / L, and the low temperature is -5℃-0℃.

[0012] The concentration of the conductive polymer dispersion liquid in step (3) is 10-20 g / L, the concentration of the lead nitrate solution is 0.05-0.2 mol / L, and the mass ratio of lead nitrate to conductive polymer powder is 1:2-2:1.

[0013] The freeze-drying temperature in step (3) is -40--10℃.

[0014] The conductive polymer loaded PbSO4 nanoparticle composite material is used as an additive of lead paste in the preparation of a negative electrode of a lead-carbon battery.

[0015] The additive amount of the conductive polymer loaded PbSO4 nanoparticle composite material is 0.2-1.6 parts, based on 100 parts of the mass of lead in the lead paste.

[0016] Preferably, the lead paste contains 100 parts of lead powder, 0.5-1.5 parts of the conductive polymer@PbSO4 composite material, 0.5-1.6 parts of barium sulfate, 0.1-0.5 parts of short fibers, 0.1-0.4 parts of humic acid, and 0.1-0.4 parts of lignin.

[0017] Preferably, the preparation method of the negative electrode of the lead-carbon battery comprises the following specific steps:

[0018] (1) 100 parts of lead powder, 0.5-1.5 parts of conductive polymer@PbSO4 composite material, 0.5-1.6 parts of barium sulfate, 0.1-0.5 parts of short fiber, 0.1-0.4 parts of humic acid, 0.1-0.4 parts of premixing, under stirring conditions, 11.7 parts of deionized water is added to the premixed powder, continuous stirring and dropwise addition of dilute sulfuric acid to obtain lead paste;

[0019] (2) The lead paste is scraped and coated on the lead calcium tin alloy grid with a size of 6.8*3.8*0.2 cm 3 , and a lead carbon battery negative electrode is obtained after drying and curing.

[0020] The electrochemical activity of the conductive polymer (polyaniline, polythiophene) is derived from the P electron conjugated structure in the molecular chain. With the expansion of the P electron system in the molecular chain, the P bonding state and the P* antibonding state form the valence band and the conduction band, respectively. This non-local P electron conjugated structure can form P-type and N-type conductive states through doping. The conductive polymer (polyaniline, polythiophene) can construct a conductive network in the negative plate, and its own amino and other functional groups can inhibit the hydrogen evolution problem caused by the introduction of carbon materials. The conductive polymer loaded PbSO4 nanoparticle composite material as an additive of lead paste can provide crystal seeds for PbSO4, form smaller PbSO4 particles on the entire negative plate, and the smaller PbSO4 particles are more electrochemically active and are more easily converted into Pb during the charging process to inhibit negative sulfate. The conductive polymer loaded PbSO4 nanoparticles can also inhibit the negative hydrogen evolution side reaction caused by the addition of pure carbon materials. Therefore, the conductive polymer (polyaniline, polythiophene) has its own rich functional groups, conductive network and loaded PbSO4 nanoparticles, which are used as negative additives of lead-carbon batteries to solve the problems of electrolyte hydrogen evolution and reduction of battery service life caused by the introduction of carbon materials with low hydrogen evolution overpotential.

[0021] The beneficial effects of the present application are:

[0022] (1) In the method of the present application, lead nitrate solution is added dropwise into the conductive polymer dispersion. Pb 2+ in the solution is adsorbed onto the conductive polymer material, captured by SO4 2- on the molecular chain of the conductive polymer, and PbSO4 nanoparticles are directly generated in situ, realizing the in-situ loading of PbSO4 nanoparticles by the conductive polymer, making the distribution of PbSO4 nanoparticles more uniform and the combination between them stronger, with larger specific surface area and better conductivity.

[0023] (2) The present application uses the amino functional groups of the high molecular polymer and the way of loading high hydrogen evolution overpotential PbSO4 nanoparticles to realize the high dispersion of high hydrogen evolution overpotential elements and nanoparticles in different forms.

[0024] (3) The conductive polymer@PbSO4 composite material as an additive of lead paste is used for preparing a lead-carbon battery negative electrode. The conductive polymer can construct a conductive network in the lead-acid battery, accelerate the electron transmission between active substances, inhibit sulfation, and improve the conversion efficiency of the negative active material. The loaded PbSO4 nanoparticles can provide crystal nuclei for the deposition of lead sulfate and inhibit the generation of large particles of irreversible lead sulfate.

[0025] (4) The conductive polymer@PbSO4 composite material as an additive of lead paste is used for preparing a lead-carbon battery negative electrode. The conductive polymer can construct a conductive network in the lead-acid battery, accelerate the electron transmission between active substances, inhibit sulfation, and improve the conversion efficiency of the negative active material. The loaded PbSO4 nanoparticles can provide crystal nuclei for the deposition of lead sulfate and inhibit the generation of large particles of irreversible lead sulfate. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 Preparation principle diagram of the polyaniline loaded PbSO4 composite material;

[0027] Figure 2 XRD diagram of the polyaniline loaded PbSO4 composite material of Example 1;

[0028] Figure 3 SEM diagram of the polyaniline loaded PbSO4 composite material of Example 1 at a low magnification;

[0029] Figure 4 SEM diagram of the polyaniline loaded PbSO4 composite material of Example 1 at a high magnification;

[0030] Figure 5 BET diagram of the polyaniline loaded PbSO4 composite material of Example 1;

[0031] Figure 6 TG diagram of the polyaniline loaded PbSO4 composite material of Example 1;

[0032] Figure 7 0.1C discharge capacity diagram of the lead-carbon batteries of the comparative example and the examples;

[0033] Figure 8 HRPSoC cycle diagram of the lead-carbon batteries of the comparative example and the examples at 2C. DETAILED DESCRIPTION

[0034] The application will be further described in conjunction with specific embodiments, but the scope of protection of the application is not limited to the content described.

[0035] Example 1: A preparation method of a conductive polymer loaded PbSO4 nanoparticle composite material (see Figure 1 ), and the specific steps are as follows:

[0036] (1) Oxidant ((NH4)2S2O8) was added to dilute sulfuric acid solution (1 mol / L) to obtain an oxidant / sulfuric acid solution, and the oxidant / sulfuric acid solution was pre-cooled in a refrigeration chamber (temperature -5℃) for 35 min; the concentration of the oxidant in the oxidant / sulfuric acid solution was 0.5 mol / L;

[0037] (2) The conductive polymer monomer (aniline) was dissolved in dilute sulfuric acid solution (1 mol / L) to obtain a monomer solution (0.1 mol / L) by stirring (500 rpm) at low temperature (-1℃); under the condition of stirring (500 rpm) at low temperature (-1℃), a micro-excess of pre-cooled oxidant / sulfuric acid solution was added dropwise to the monomer solution to react for 18 h, and then solid-liquid separation was performed; the solid was washed to neutral with deionized water, and vacuum drying was performed to obtain conductive polymer powder (polyaniline powder); the molecular chain of the conductive polymer (polyaniline powder) contained SO4 2- ;

[0038] (3) The conductive polymer powder (polyaniline powder) was dispersed in deionized water to obtain a conductive polymer dispersion liquid; under the condition of stirring (400 rpm), lead nitrate solution (0.05 mol / L) was added dropwise to the conductive polymer dispersion liquid and reacted at room temperature for 4 h; solid-liquid separation was performed, the solid was washed with deionized water, and freeze-drying was performed at a temperature of -10℃ for 36 h to obtain a polyaniline loaded PbSO4 nanoparticle composite material; the mass ratio of the lead nitrate to the conductive polymer powder (polyaniline powder) was 1:1;

[0039] The conductive polymer loaded PbSO4 nanoparticle composite material was used as an additive of lead paste to prepare a lead-carbon battery negative electrode, and the specific steps were as follows:

[0040] 1) 100 g of lead powder, 0.8 g of polyaniline loaded PbSO4 nanoparticle composite material, 1.2 g of activated carbon, 0.8 g of barium sulfate, 0.13 g of short fibers, 0.2 g of humic acid, and 0.2 g of lignin were uniformly premixed, and under the condition of stirring, 11.7 parts of deionized water was added to the premixed powder, continuous stirring was performed, and 8.3 g of dilute sulfuric acid (concentration 50 wt.%) was added dropwise to obtain lead paste;

[0041] 2) The lead paste was scraped and coated onto a lead-calcium-tin alloy grid with a size of 6.8×3.8×0.2 cm 3 , and drying and curing were performed to obtain a lead-carbon battery negative electrode;

[0042] Three commercial positive plates and two negative plates were placed alternately and at intervals, and an AGM separator was placed between the positive plates and the negative plates; the positive and negative electrodes were placed in a tightly assembled battery box, 40 mL of 38% sulfuric acid electrolyte was injected into the battery box, the assembled battery was subjected to formation, 0.1C capacity test, and HRPSoC cycle test under a current density of 2C.

[0043] Example 2: A method for preparing a conductive polymer loaded PbSO4 nanoparticle composite (see Figure 1 ), the specific steps are as follows:

[0044] (1) Oxidant ((NH4)2S2O8) was added to dilute sulfuric acid solution (2 mol / L) to obtain an oxidant / sulfuric acid solution, and the oxidant / sulfuric acid solution was pre-cooled in a refrigeration chamber (temperature -2℃) for 40 min; the concentration of the oxidant in the oxidant / sulfuric acid solution was 1.0 mol / L;

[0045] (2) The conductive polymer monomer (thiophene) was dissolved in dilute sulfuric acid solution (2 mol / L), and the mixture was stirred (500 rpm) at low temperature (-1℃) to obtain a monomer solution (0.1 mol / L). Under the condition of stirring (500 rpm) at low temperature (-2℃), a small excess of pre-cooled oxidant / sulfuric acid solution was added dropwise to the monomer solution and reacted for 24 h. The solid was washed with deionized water until neutral, and vacuum dried to obtain conductive polymer powder (polythiophene powder). The molecular chain of the conductive polymer (polythiophene powder) contained SO4 2- ;

[0046] (3) The conductive polymer powder (polythiophene powder) was dispersed in deionized water to obtain a conductive polymer dispersion. Under stirring (400 rpm), lead nitrate solution (0.05 mol / L) was added dropwise to the conductive polymer dispersion and reacted at room temperature for 8 h. The solid was washed with deionized water, and freeze-dried at a temperature of -10℃ for 36 h to obtain a polythiophene loaded PbSO4 nanoparticle composite; the mass ratio of lead nitrate to conductive polymer powder (polythiophene powder) was 1:2;

[0047] A lead-carbon battery negative electrode was prepared using the conductive polymer loaded PbSO4 nanoparticle composite as an additive for lead paste, and the specific steps were as follows:

[0048] 1) 100 g of lead powder, 0.8 g of polythiophene loaded PbSO4 nanoparticle composite, 1.2 g of activated carbon, 0.8 g of barium sulfate, 0.13 g of short fibers, 0.2 g of humic acid, and 0.2 g of lignin were uniformly premixed. Under stirring, 11.7 parts of deionized water was added to the premixed powder, and 8.3 g of dilute sulfuric acid (concentration 50 wt.%) was continuously added dropwise to obtain lead paste;

[0049] 2) The lead paste was coated onto a lead-calcium-tin alloy grid with dimensions of 6.8 x 3.8 x 0.2 cm 3 , and dried and cured to obtain a lead-carbon battery negative electrode;

[0050] Three pieces of commercial positive plates and two pieces of negative plates are placed alternately and spaced, and an AGM separator is placed between the positive and negative plates; the positive and negative electrodes are placed in a tightly assembled battery box, 40 mL of 38% sulfuric acid electrolyte is injected into the battery box; the assembled battery is formed, 0.1C capacity test is carried out, and HRPSoC cycle test is carried out under 2C current density.

[0051] Example 3: A preparation method of a conductive polymer loaded PbSO4 nanoparticle composite (see Figure 1 ), and the specific steps are as follows:

[0052] (1) Oxidant ((NH4)2S2O8) is added to a dilute sulfuric acid solution (3 mol / L) to obtain an oxidant / sulfuric acid solution, and the oxidant / sulfuric acid solution is pre-cooled in a refrigeration chamber (temperature -3°C) for 30 min; the concentration of the oxidant in the oxidant / sulfuric acid solution is 2.0 mol / L;

[0053] (2) The conductive polymer monomer (aniline) is dissolved in a dilute sulfuric acid solution (3 mol / L) to obtain a monomer solution (0.4 mol / L) under low temperature (-5°C) and stirring (700 rpm); under the condition of low temperature (-5°C) and stirring (700 rpm), a micro-excess of the pre-cooled oxidant / sulfuric acid solution is added dropwise to the monomer solution for reaction for 12 h, solid-liquid separation is performed, the solid is washed to neutral with deionized water, and vacuum drying is performed to obtain a conductive polymer powder (polyaniline powder), and the molecular chain of the conductive polymer (polyaniline powder) contains SO4 2- ;

[0054] (3) The conductive polymer powder (polyaniline powder) is dispersed into deionized water to obtain a conductive polymer dispersion liquid, lead nitrate solution (0.15 mol / L) is added dropwise to the conductive polymer dispersion liquid under stirring (500 rpm), and reaction is performed at room temperature for 2 h, solid-liquid separation is performed, the solid is washed with deionized water, and freeze-drying is performed at a temperature of -20°C for 24 h to obtain a polyaniline loaded PbSO4 nanoparticle composite; the mass ratio of the lead nitrate to the conductive polymer powder (polyaniline powder) is 1:2;

[0055] The conductive polymer loaded PbSO4 nanoparticle composite is used as an additive of lead paste to prepare a negative electrode of a lead-carbon battery, and the specific steps are as follows:

[0056] 1) 100 g of lead powder, 0.8 g of the polyaniline loaded PbSO4 nanoparticle composite, 1.2 g of activated carbon, 0.8 g of barium sulfate, 0.13 g of short fibers, 0.2 g of humic acid, and 0.2 g of lignin are uniformly premixed, deionized water is added to the premixed powder under stirring, and 8.3 g of dilute sulfuric acid (concentration 50 wt.%) is added dropwise under continuous stirring to obtain lead paste;

[0057] 2) Paste is applied to the dimension of 6.8 x 3.8 x 0.2 cm 3 of lead calcium tin alloy grid, and lead carbon battery negative electrode is obtained after drying and curing;

[0058] Three commercial positive plates and two negative plates are placed alternately and spaced, and an AGM separator is placed between the positive plate and the negative plate; the positive and negative electrodes are placed in a tightly assembled battery box, 40 mL of 38% sulfuric acid electrolyte is injected into the battery box; the assembled battery is formed, 0.1C capacity test is performed, and HRPSoC cycle test is performed under 2C current density.

[0059] Example 4: A preparation method of a conductive polymer loaded PbSO4 nanoparticle composite (see Figure 1 ), and the specific steps are as follows:

[0060] (1) An oxidizing agent (commercial hydrogen peroxide) is added to a dilute sulfuric acid solution (2 mol / L) to obtain an oxidizing agent / sulfuric acid solution, and the oxidizing agent / sulfuric acid solution is pre-cooled in a refrigeration room (temperature 5°C) for 30 min; the concentration of the oxidizing agent in the oxidizing agent / sulfuric acid solution is 1.0 mol / L;

[0061] (2) The conductive polymer monomer (aniline) is dissolved in a dilute sulfuric acid solution (2 mol / L) and stirred (800 rpm) at low temperature (-5°C) to obtain a monomer solution (0.5 mol / L); under the condition of low temperature (-5°C) and stirring (800 rpm), a slightly excessive amount of pre-cooled oxidizing agent / sulfuric acid solution is added dropwise to the monomer solution and reacts for 12 h; solid-liquid separation is performed, the solid is washed to neutral with deionized water, and vacuum drying is performed to obtain a conductive polymer powder (polyaniline powder), and the molecular chain of the conductive polymer (polyaniline powder) contains SO4 2- ;

[0062] (3) The conductive polymer powder (polyaniline powder) is dispersed in deionized water to obtain a conductive polymer dispersion liquid, and under the condition of stirring (500 rpm), a lead nitrate solution (0.2 mol / L) is added dropwise to the conductive polymer dispersion liquid and reacts at room temperature for 8 h; solid-liquid separation is performed, the solid is washed with deionized water, and freeze-drying is performed at a temperature of -40°C for 12 h to obtain a polyaniline loaded PbSO4 nanoparticle composite; the mass ratio of the lead nitrate to the conductive polymer powder (polyaniline powder) is 2:1;

[0063] The conductive polymer loaded PbSO4 nanoparticle composite is used as an additive of lead paste to prepare a lead carbon battery negative electrode, and the specific steps are as follows:

[0064] 1) 100 g of lead powder, 0.8 g of polyaniline loaded PbSO4 nanoparticle composite material, 1.2 g of activated carbon, 0.8 g of barium sulfate, 0.13 g of short fibers, 0.2 g of humic acid, 0.2 g of lignin were premixed uniformly, and 11.7 parts of deionized water was added to the premixed powder under stirring, and 8.3 g of dilute sulfuric acid (concentration 50 wt.%) was added dropwise to obtain a lead paste;

[0065] 2) The lead paste was coated on a lead calcium tin alloy grid with a size of 6.8 x 3.8 x 0.2 cm 3 to obtain a lead-carbon battery negative electrode after drying and curing;

[0066] Three commercial positive plates and two negative plates were placed alternately and spaced, and an AGM separator was placed between the positive and negative plates; the positive and negative electrodes were placed in a tightly assembled battery box, 40 mL of 38% sulfuric acid electrolyte was injected into the battery box; the assembled battery was formed, and 0.1C capacity test and 2C HRPSoC cycle test were performed;

[0067] The 0.1C discharge capacity and 2C HRPSoC cycle stability of the standard 2V lead-acid battery assembled in Comparative Example (without adding conductive polymer loaded PbSO4 nanoparticle composite material in the lead paste) and Examples 1-4 are shown in Table 1;

[0068] Table 1 Comparison of capacity and cycle test of lead-carbon battery

[0069]

[0070]

[0071] As can be seen from Table 1, the 0.1C discharge capacity of the lead-carbon battery of the comparative example without adding conductive polymer loaded PbSO4 nanoparticle composite material in the lead paste is only 3.59 Ah, and the HRPSoC cycle life under 2C condition is 4854 cycles; the 0.1C discharge capacity of the lead-carbon batteries assembled in Examples 1, 2, 3, and 4 is 3.67 Ah, 3.66 Ah, 3.75 Ah, and 3.65 Ah, respectively, and the HRPSoC cycle life under 2C condition is 8584, 10571, 10893, and 7073 cycles, respectively;

[0072] The conductive polymer loaded PbSO4 nanoparticle composite material of Example 3 was used as an additive for the preparation of a lead paste for a lead-carbon battery negative electrode, and the addition amount was 0.2 parts, 0.4 parts, 0.8 parts, 1.2 parts, and 1.6 parts, respectively, and the lead-carbon battery negative electrodes were denoted as A, B, C, D, and E, respectively.

[0073] The 0.1C discharge capacity and HRPSoC cycle stability at 2C of the standard 2V lead-acid battery assembled with the comparative example (PbSO4 nanoparticle composite without adding conductive polymer in the lead paste) and the lead-carbon battery negative electrode (A, B, C, D, E) are compared in Table 2.

[0074] Table 2 Comparison of capacity and cycle test of lead-carbon battery

[0075] 0.1 C discharge capacity HRPSoC cycles Comparative Example 3.59 Ah 4854 cycles A 3.61 Ah 6478 cycles B 3.68 Ah 9213 cycles C 3.75 Ah 10893 cycles D 3.72 Ah 9017 cycles E 3.67 Ah 7435 cycles

[0076] From Table 2, it can be seen that the addition of the composite material can make the active material of the lead-carbon battery negative electrode more evenly distributed, inhibit the unlimited growth of PbSO4 crystal, and inhibit the severe hydrogen evolution of the negative electrode, thereby prolonging the cycle life of the battery. However, the addition of excessive composite material can also exacerbate the hydrogen evolution phenomenon during the charging process of the battery, leading to serious water loss of the battery, reducing the cycle performance of the battery. After exploration, the performance of the lead-carbon battery with 0.8% composite material as the negative electrode additive is better.

[0077] The specific embodiments of the present application are described in detail above, but the present application is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present application.

Claims

1. A method for preparing a conductive polymer supported PbS04 nanoparticle composite, characterized in that, The specific steps are as follows: (1) Dissolve the oxidant in dilute sulfuric acid solution to obtain oxidant / sulfuric acid solution, and pre-cool the oxidant / sulfuric acid solution at a temperature of -5℃ to 5℃; (2) Dissolve the conductive polymer monomer in dilute sulfuric acid solution, stir and mix at low temperature to obtain monomer solution. Under low temperature stirring conditions, add a slightly excess of pre-cooled oxidant / sulfuric acid solution dropwise to monomer solution and react for 12-24 hours. Separate solid and liquid, wash the solid with deionized water until neutral, and vacuum dry to obtain conductive polymer powder. (3) The conductive polymer powder was dispersed in deionized water to obtain a conductive polymer dispersion. Under stirring conditions, lead nitrate solution was added dropwise to the conductive polymer dispersion and reacted at room temperature for 2-8 hours. The solid and liquid were separated, and the solid was washed with deionized water and freeze-dried to obtain a conductive polymer-supported PbSO4 nanoparticle composite material.

2. The method for preparing the conductive polymer-supported PbSO4 nanoparticle composite material according to claim 1, characterized in that: Step (1) The oxidant is one or more of ammonium persulfate, hydrogen peroxide, potassium dichromate, and manganese dioxide.

3. The method for preparing the conductive polymer-supported PbSO4 nanoparticle composite material according to claim 1, characterized in that: Step (1) The concentration of dilute sulfuric acid is 1-3 mol / L, and the concentration of oxidant in the sulfuric acid solution is 0.5-2 mol / L.

4. The method for preparing the conductive polymer-supported PbSO4 nanoparticle composite material according to claim 1, characterized in that: Step (2) The conductive polymer is polyaniline or polythiophene.

5. The method for preparing the conductive polymer-supported PbSO4 nanoparticle composite material according to claim 1, characterized in that: Step (2) The concentration of the dilute sulfuric acid solution is 1-3 mol / L, the concentration of the conductive polymer monomer in the monomer solution is 0.1-0.5 mol / L, and the low temperature is -5℃ to 0℃.

6. The method for preparing the conductive polymer-supported PbSO4 nanoparticle composite material according to claim 1, characterized in that: In step (3), the concentration of the conductive polymer dispersion is 10-20 g / L, the concentration of the lead nitrate solution is 0.05-0.2 mol / L, and the mass ratio of lead nitrate to conductive polymer powder is 1:2-2:

1.

7. The method for preparing the conductive polymer-supported PbSO4 nanoparticle composite material according to claim 1, characterized in that: Step (3) Freeze-drying temperature is -40 to -10℃.

8. The application of the conductive polymer-supported PbSO4 nanoparticle composite material prepared by the preparation method according to any one of claims 1 to 7 as an additive in lead paste for the preparation of lead-carbon battery anodes.

9. The application according to claim 8, characterized in that: Based on 100 parts by mass of lead in lead paste, the amount of conductive polymer-supported PbSO4 nanoparticle composite material added is 0.2 to 1.6 parts.

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