A high-rate lead-acid battery negative electrode material and a preparation method thereof

Abstract

The application discloses a high-multiplying lead-acid battery negative electrode material and a preparation method thereof, and belongs to the technical field of electrochemistry. A lead-containing compound, modified acetylene black, deionized water and ethanol are added into a flask, ultrasonic treatment is conducted, filtration is conducted, and drying is conducted to obtain a composite material; polyvinyl alcohol, sodium polystyrene sulfonate and deionized water are mixed to obtain a premix 2, the premix 2 is poured into a premix 1 obtained by mixing and grinding lead sulfate, conductive graphite, the composite material and barium sulfate, stirring, grinding, coating, compaction and drying are conducted to obtain the negative electrode material. The zinc oxide and indium oxide are firmly present in the modified acetylene black, and in addition to the high dispersity of the modified acetylene black and the lead-containing compound in the negative electrode material, the negative electrode material can improve the distribution of the conductive graphite, is more conducive to ion and electron transmission, can inhibit hydrogen evolution, improve the hydrogen evolution overpotential, improve the charge and discharge acceptance capacity and efficiency of the electrode, can also reduce the electrode internal resistance and polarization, relieve the sulfation of the negative electrode, improve the cycle performance of the electrode and prolong the service life of the electrode.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of electrochemistry, and particularly relates to a high-rate lead-acid battery negative electrode material and a preparation method thereof. BACKGROUND

[0002] The lead-acid battery is a high-safety, low-cost and high-quality industrial product. The lead-acid battery is widely used as a car starting power source, an electric two-wheeled vehicle power source, an uninterrupted backup power source, a diesel submarine underwater navigation power source, a communication industry backup power source and the like, and has a wide application. In recent years, with the development of renewable energy, the lead-acid battery is also applied to large-scale energy storage power sources.

[0003] However, the current lead-acid battery generally has a low discharge rate, or a short service life under a high-rate discharge working condition, and also has problems of hydrogen evolution and irreversible sulfation, which limit the use of the lead-acid battery. SUMMARY

[0004] The application aims to overcome the defects of the prior art and provide a high-rate lead-acid battery negative electrode material and a preparation method thereof.

[0005] The object of the application can be achieved by the following technical scheme.

[0006] A high-rate lead-acid battery negative electrode material and a preparation method thereof, comprising the following steps:

[0007] (1) a lead-containing compound, modified acetylene black, deionized water and ethanol are added to a dry single-neck flask, ultrasonic dispersion is performed for 1 h, then filtration is performed, and 80 DEG C drying is performed for 12 h to obtain a composite material;

[0008] (2) lead sulfate, conductive graphite, the composite material and barium sulfate are mixed and uniformly ground to obtain a premix 1; polyvinyl alcohol, sodium polystyrene sulfonate and deionized water are added to a beaker and uniformly mixed to obtain a premix 2; the premix 2 is poured into the premix 1, and stirring and grinding are continuously performed to be paste-shaped, and then the paste-shaped material is coated on a lead-calcium alloy grid, and then an oil press is used for compaction, and finally 70 DEG C drying is performed for 24 h to obtain the high-rate lead-acid battery negative electrode material.

[0009] Further, the lead-containing compound in the step (1) is one of lead, lead oxide and triplumbous oxide.

[0010] Further, the modified acetylene black in the step (1) is prepared by the following steps.

[0011] S1, under nitrogen protection, benzimidazole-5-carboxylic acid, EDC (1-(3- dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride), NHS (N-hydroxysuccinimide) and DMF (N,N-dimethylformamide) were added into a dry three-neck flask, after stirring and dissolving, the temperature was raised to 50°C, then D-glucamine was slowly added, and the reaction was kept at this temperature for 6h. After the reaction was completed, the temperature was cooled to room temperature, and distilled under reduced pressure. After column chromatography purification (eluent: mixed solvent of chloroform and acetone, volume ratio of chloroform to acetone was 7:3), it was distilled under reduced pressure to obtain intermediate 1; the amount ratio of D-glucamine, benzimidazole-5-carboxylic acid, EDC, NHS and DMF was 19.6g:16.2g:3.8g:2.3g:200mL;

[0012] The molar ratio of D-glucamine to benzimidazole-5-carboxylic acid was controlled to be 1.05-1.1:1, and the -COOH of benzimidazole-5-carboxylic acid and the -NH2 of D-glucamine were subjected to amidation reaction under the action of EDC and NHS, and the reaction equation was as shown below:

[0013]

[0014] S2, acetylene black and concentrated sulfuric acid were added into a dry three-neck flask, stirred and heated to 80°C, then refluxed for 12h. After stopping stirring, the temperature was cooled to room temperature, filtered, washed with deionized water, and dried at 110°C under vacuum for 6h to obtain pretreated acetylene black. The pretreated acetylene black, 10% sodium hydroxide solution and chloroform were mixed uniformly, stirred and heated to 60°C, then epichlorohydrin was slowly added, and the reaction was continued at 60°C for 6h. After the reaction was completed, rotary evaporation was performed, deionized water was washed for 3 times, and then dried at 110°C for 6h to obtain intermediate 2; the amount ratio of acetylene black to concentrated sulfuric acid was 10g:330mL; the amount ratio of pretreated acetylene black to epichlorohydrin was 7.7g:10mL;

[0015]

[0016] S3, under nitrogen protection, intermediate 2, triethylamine and DMF were added into a dry three-neck flask, stirred and heated to 80°C, then intermediate 1 was slowly added, and after the addition was completed, the reaction was kept at this temperature for 6h. After the reaction was completed, it was distilled under reduced pressure, washed with deionized water for 3 times, and then dried at 110°C for 6h to obtain intermediate 3; the amount ratio of intermediate 1, intermediate 2, triethylamine and DMF was 43.7g:14g:20.5mL:220mL;

[0017]

[0018] S4, adding intermediate 3 and deionized water into a beaker, ultrasonic treatment for 30 min to make intermediate 3 fully dispersed; then adding the mixed powder of zinc oxide and indium oxide, continuing ultrasonic treatment for 1 h, then filtering, vacuum drying at 110℃ for 12 h to obtain modified acetylene black; the dosage ratio of intermediate 3, zinc oxide, indium oxide and deionized water is 30 g:0.015 g:0.015 g:250 mL.

[0019] The role of indium oxide added in the negative material of lead-acid battery is to improve the performance of the battery, including increasing the discharge capacity, prolonging the cycle life, inhibiting the negative sulfate and hydrogen evolution problems; the role of zinc oxide in the lead-acid battery mainly reflects in improving the cycle life, safety performance of the battery and enhancing the stability and durability of the battery by improving the sulfation phenomenon of the negative plate.

[0020] Since the surfaces of zinc oxide and indium oxide both contain rich hydroxyl groups, zinc oxide and indium oxide can produce hydrogen bond interaction with the hydroxyl groups on the surface of intermediate 3. In addition, the nitrogen atom in the benzimidazole structure on intermediate 3 contains lone pair electrons, which has strong coordination ability and is easy to form a complex with zinc oxide and indium oxide, and the formed complex has a good rigid planar structure and rich π electrons, as well as excellent electron delocalization environment. Moreover, the π-π stacking effect of the aromatic ring in the benzimidazole structure on intermediate 3 makes the complex more stable, and then zinc oxide and indium oxide can exist firmly in the modified acetylene black to play a synergistic role, so as to improve the discharge capacity, prolong the cycle life, inhibit the negative sulfate and hydrogen evolution problems, and enhance the stability and durability of the battery.

[0021] In addition, the surface of the modified acetylene black contains rich hydroxyl groups, which can produce hydrogen bond interaction with the hydroxyl groups in deionized water and ethanol, and then the modified acetylene black can be more fully dispersed in the system, and the lead-containing compounds can be more uniformly loaded on the surface of the acetylene black. Further, the composite material prepared in step (1) of the present application can effectively improve the electrochemical performance of the electrode, reduce the hydrogen evolution problem in the charging process at low rate, improve the charge-discharge efficiency, bear part of the discharge current at high rate, alleviate the accumulation of lead sulfate, reduce polarization, and at the same time, improve the cycle life, safety performance of the battery and enhance the stability and durability of the battery by improving the sulfation phenomenon of the negative plate.

[0022] Further, the dosage ratio of the lead-containing compound, modified acetylene black, deionized water and ethanol in step (1) is (0.02-0.06) g:0.12 g:50 mL:50 mL.

[0023] Further, the mass ratio of the lead sulfate, the conductive graphite, the composite material, the barium sulfate, the polyvinyl alcohol and the sodium polystyrene sulfonate in the step (2) is 1:(0.015-0.03):(0.005-0.015):0.02:0.005:0.002.

[0024] A high-rate lead-acid battery negative electrode material is prepared according to the preparation method of the high-rate lead-acid battery negative electrode material.

[0025] The zinc oxide and the indium oxide are firmly present in the modified acetylene black by chemical action, and play a synergistic role, and the modified acetylene black and the lead-containing compound have high dispersity in the negative electrode material, so that the negative electrode material can improve the distribution of the conductive graphite, and is more conducive to ion and electron transmission; meanwhile, the negative electrode material can inhibit hydrogen evolution, improve hydrogen evolution overpotential, improve the charge and discharge acceptance capacity and efficiency of the electrode, reduce the internal resistance and polarization of the electrode, relieve the sulfation of the negative electrode, improve the cycle performance of the electrode, and prolong the service life of the electrode. Therefore, the finished battery prepared by using the negative electrode material has excellent electrochemical performance. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0027] Embodiment 1

[0028] The modified acetylene black is prepared, and the specific steps are as follows:

[0029] S1, 16.2g of benzimidazole-5-carboxylic acid, 3.8g of EDC, 2.3g of NHS and 200mL of DMF are added into a 500mL dry three-necked flask under nitrogen protection, and after stirring and dissolving, the temperature is increased to 50℃, then 19.6g of D-glucose amine is slowly added, and the reaction is kept at 50℃ for 6h, then the reaction is cooled to room temperature, distilled under reduced pressure, and purified by column chromatography (the eluent is a mixed solvent of chloroform and acetone, and the volume ratio of chloroform to acetone is 7:3), and then distilled under reduced pressure to obtain the intermediate 1;

[0030] S2, 10 g of acetylene black, 330 mL of concentrated sulfuric acid were added into a 500 mL dry three-necked flask, stirred to 80℃, and then refluxed for 12 h. After stopping stirring, it was cooled to room temperature, filtered, washed with deionized water, and dried at 110℃ for 6 h in vacuum to obtain the pretreated acetylene black. 7.7 g of the pretreated acetylene black, 50 mL of 10% sodium hydroxide solution and 100 mL of chloroform were mixed uniformly, stirred to 60℃, and then 10 mL of epichlorohydrin was slowly added. The reaction was continued at 60℃ for 6 h. After the reaction was completed, it was rotary evaporated, washed with deionized water for 3 times, and dried at 110℃ for 6 h to obtain the intermediate 2.

[0031] S3, 14 g of the intermediate 2, 20.5 mL of triethylamine and 220 mL of DMF were added into a 500 mL dry three-necked flask under nitrogen protection, stirred to 80℃, and then 43.7 g of the intermediate 1 was slowly added. After the addition was completed, the reaction was continued for 6 h. After the reaction was completed, it was distilled under reduced pressure, washed with deionized water for 3 times, and dried at 110℃ for 6 h to obtain the intermediate 3.

[0032] S4, 30 g of the intermediate 3 and 250 mL of deionized water were added into a beaker, and ultrasonic treatment was carried out for 30 min to make the intermediate 3 fully dispersed. Then, the powder obtained by mixing 0.015 g of zinc oxide and 0.015 g of indium oxide was added, and ultrasonic treatment was continued for 1 h. Subsequently, it was filtered and dried at 110℃ for 12 h in vacuum to obtain the modified acetylene black.

[0033] Example 2

[0034] The specific steps for preparing the high-rate lead-acid battery negative electrode material are as follows:

[0035] (1) 0.06 g of triplumbous oxide, 0.12 g of the modified acetylene black prepared in Example 1, 50 mL of deionized water and 50 mL of ethanol were added into a 250 mL dry single-necked flask, ultrasonic dispersed for 1 h, and then filtered and dried at 80℃ for 12 h to obtain the composite material.

[0036] (2) Lead sulfate, conductive graphite, the composite material and barium sulfate were mixed and ground uniformly to obtain a premix 1. Polyvinyl alcohol, sodium polystyrene sulfonate and deionized water were added into a beaker and mixed uniformly to obtain a premix 2. The mass ratio of the lead sulfate, the conductive graphite, the composite material, the barium sulfate, the polyvinyl alcohol and the sodium polystyrene sulfonate was 1:0.03:0.015:0.02:0.005:0.002. The premix 2 was poured into the premix 1, and then stirred and ground to be paste-like. The paste was coated on a lead-calcium alloy grid, and then compacted by an oil press. Finally, it was dried at 70℃ for 24 h to obtain the high-rate lead-acid battery negative electrode material.

[0037] Example 3

[0038] A high rate lead-acid battery negative electrode material is prepared according to the following steps:

[0039] (1) 0.04 g of lead oxide, 0.12 g of the modified acetylene black prepared in Example 1, 50 mL of deionized water and 50 mL of ethanol are added into a 250 mL dry single-necked flask, ultrasonic dispersion is performed for 1 h, then filtration is performed, and drying is performed at 80 DEG C for 12 h to obtain a composite material;

[0040] (2) Lead sulfate, conductive graphite, the composite material and barium sulfate are mixed and ground uniformly to obtain a premix 1; polyvinyl alcohol, sodium polystyrene sulfonate and deionized water are added into a beaker and mixed uniformly to obtain a premix 2, wherein the mass ratio of the lead sulfate, the conductive graphite, the composite material, the barium sulfate, the polyvinyl alcohol and the sodium polystyrene sulfonate is 1:0.025:0.01:0.02:0.005:0.002; the premix 2 is poured into the premix 1, and stirring and grinding are continuously performed to obtain a paste, which is coated on a lead-calcium alloy grid, and then an oil press is used for compacting, and finally drying is performed at 70 DEG C for 24 h to obtain the high rate lead-acid battery negative electrode material.

[0041] Example 4

[0042] A high rate lead-acid battery negative electrode material is prepared according to the following steps:

[0043] (1) 0.02 g of lead, 0.12 g of the modified acetylene black prepared in Example 1, 50 mL of deionized water and 50 mL of ethanol are added into a 250 mL dry single-necked flask, ultrasonic dispersion is performed for 1 h, then filtration is performed, and drying is performed at 80 DEG C for 12 h to obtain a composite material;

[0044] (2) Lead sulfate, conductive graphite, the composite material and barium sulfate are mixed and ground uniformly to obtain a premix 1; polyvinyl alcohol, sodium polystyrene sulfonate and deionized water are added into a beaker and mixed uniformly to obtain a premix 2, wherein the mass ratio of the lead sulfate, the conductive graphite, the composite material, the barium sulfate, the polyvinyl alcohol and the sodium polystyrene sulfonate is 1:0.015:0.005:0.02:0.005:0.002; the premix 2 is poured into the premix 1, and stirring and grinding are continuously performed to obtain a paste, which is coated on a lead-calcium alloy grid, and then an oil press is used for compacting, and finally drying is performed at 70 DEG C for 24 h to obtain the high rate lead-acid battery negative electrode material.

[0045] Comparative Example 1

[0046] A lead-acid battery negative electrode material is prepared according to the following steps:

[0047] The remaining steps are unchanged, and only the modified acetylene black in step (1) of Example 2 is replaced with acetylene black without any treatment to prepare the lead-acid battery negative electrode material.

[0048] Comparative Example 2

[0049] The lead-acid battery negative electrode material is prepared by the following specific steps:

[0050] The remaining steps are unchanged, and the composite material in step (2) of Example 2 is removed, and the lead-acid battery negative electrode material is prepared.

[0051] Performance test

[0052] The lead-acid battery negative electrode materials prepared in Examples 2-4 and Comparative Examples 1-2 are prepared into lead-acid batteries, and the following tests are performed:

[0053] Service life test: the cycle number test is performed on the lead-acid batteries of Examples 2-4 and Comparative Examples 1-2, and the cycle number higher than 700 is recorded as qualified, otherwise it is unqualified; stability test: the discharge time of the lead-acid batteries of Examples 2-4 and Comparative Examples 1-2 at 300 cycles is detected, and if it is higher than 150 min, it is recorded as qualified, otherwise it is unqualified, and the test results are shown in the following table:

[0054]

[0055]

[0056] In the description of the specification, the description of the reference terms "one embodiment", "example", "specific example" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are contained in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0057] The above is only an example and description of the present application, and those skilled in the art can make various modifications or supplements or use similar ways to replace the described specific embodiments, as long as they do not deviate from the invention or exceed the scope defined by the present claims, and should belong to the protection scope of the present application.

Claims

1. A method for preparing a negative electrode material for a high-rate lead-acid battery, characterized in that: The following steps are involved: (1) Add the lead-containing compound, modified acetylene black, deionized water and ethanol into a flask, ultrasonically disperse for 1 h, filter and dry to obtain a composite material; (2) Lead sulfate, conductive graphite, composite material, and barium sulfate are mixed and ground to obtain premix 1; polyvinyl alcohol, sodium polystyrene sulfonate, and deionized water are mixed to obtain premix 2; premix 2 is poured into premix 1, stirred, ground, and coated on a lead-calcium alloy grid, compacted with an oil press, and dried to obtain a high-rate lead-acid battery negative electrode material; Wherein, the modified acetylene black in step (1) is prepared by the following steps: S1. Benzimidazole-5-carboxylic acid, EDC, NHS, and DMF were added to a flask under nitrogen protection, heated to 50°C with stirring, and D-glucosamine was added. The mixture was reacted for 6 h, cooled, and evaporated under reduced pressure. The mixture was purified by column chromatography and evaporated under reduced pressure to obtain intermediate 1. S2. Add acetylene black and concentrated sulfuric acid into a flask, reflux at 80° C. for 12 h, cool, filter, wash, and dry to obtain pretreated acetylene black; Pretreated acetylene black, 10% sodium hydroxide solution and chloroform were stirred and heated to 60°C, epichlorohydrin was added, reacted for 6 hours, rotary evaporated, washed and dried to obtain intermediate 2; S3. Under nitrogen protection, intermediate 2, triethylamine and DMF were added to a flask, the temperature was raised to 80°C with stirring, intermediate 1 was added, the reaction was continued for 6 hours, and the product was evaporated under reduced pressure, washed and dried to obtain intermediate 3. S4. Add intermediate 3 and deionized water into a beaker, sonicate for 30 minutes, add zinc oxide and indium oxide mixed powder, sonicate for 1 hour, filter, and dry to obtain modified acetylene black. 。 2. The method for preparing a negative electrode material for a high-rate lead-acid battery according to claim 1, wherein: The usage ratio of D-glucosamine, benzimidazole-5-carboxylic acid, EDC, NHS and DMF in step S1 is 19.6 g:16.2 g:3.8 g:2.3 g:200 mL.

3. The method for preparing a negative electrode material for a high-rate lead-acid battery according to claim 1, wherein: The usage ratio of acetylene black and concentrated sulfuric acid in step S2 is 10 g:330 mL; the usage ratio of pretreated acetylene black and epichlorohydrin is 7.7 g:10 mL.

4. The method for preparing a negative electrode material for a high-rate lead-acid battery according to claim 1, wherein: The usage ratio of intermediate 1, intermediate 2, triethylamine and DMF in step S3 is 43.7 g:14 g:20.5 mL:220 mL.

5. The method for preparing a negative electrode material for a high-rate lead-acid battery according to claim 1, wherein: The usage ratio of intermediate 3, zinc oxide, indium oxide and deionized water in step S4 is 30 g:0.015 g:0.015 g:250 mL.

6. The method for preparing a negative electrode material for a high-rate lead-acid battery according to claim 1, wherein: The lead-containing compound in step (1) is one of lead, lead oxide, and lead tetroxide.

7. The method for preparing a negative electrode material for a high-rate lead-acid battery according to claim 1, wherein: The lead-containing compound, modified acetylene black, deionized water and ethanol in step (1) are used in a ratio of (0.02-0.06) g:0.12 g:50 mL:50 mL.

8. The method for preparing a negative electrode material for a high-rate lead-acid battery according to claim 1, wherein: The mass ratio of lead sulfate, conductive graphite, composite material, barium sulfate, polyvinyl alcohol and sodium polystyrene sulfonate in step (2) is 1:(0.015-0.03):(0.005-0.015):0.02:0.005:0.

002.

9. A high-rate lead-acid battery negative electrode material, characterized in that: It is prepared according to the method for preparing a high-rate lead-acid battery negative electrode material according to any one of claims 1-8.

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