CN-117613271-B - Preparation method of composite PbO/ZnO three-dimensional porous lead-carbon battery additive

Abstract

The invention relates to a preparation method of a composite PbO/ZnO three-dimensional porous lead-carbon battery additive, and belongs to the technical field of lead-carbon batteries. The preparation method comprises the steps of carrying out degreasing pretreatment on a titanium base, then placing the titanium base in a nitric acid-hydrochloric acid mixed solution for etching and activating to obtain an activated titanium base, uniformly mixing three-dimensional hierarchical porous carbon, carbon black and a binder PVDF to obtain a mixture, adding N-pyrrolidone into the mixture, uniformly mixing to obtain three-dimensional hierarchical porous carbon slurry, uniformly coating the three-dimensional hierarchical porous carbon slurry on the surface of the activated titanium base, drying to obtain a carbon-based anode, taking a lead nitrate-zinc oxide mixed solution as an electroplating solution, taking the carbon-based anode as an anode, taking a copper plate as a cathode, electroplating for 1-2 hours at the temperature of 40-50 ℃ under the stirring condition, taking out the anode after electroplating, cleaning by deionized water, scraping the electroplated layer from the surface of the titanium base, and carrying out vacuum drying to obtain the composite PbO/ZnO three-dimensional porous lead carbon battery additive. The PbO/ZnO in the additive is uniformly modified on the three-dimensional hierarchical porous carbon material, and can be used as the lead-carbon battery additive to effectively inhibit hydrogen evolution reaction.

Inventors

• CHEN ZHEN
• WANG MENG
• YU QIANG
• HUANG HUI
• LI SHUTING
• LI HUIXI
• ZHU WEI
• GUO ZHONGCHENG

Assignees

• 昆明理工恒达科技股份有限公司
• 昆明理工大学

Dates

Publication Date

20260505

Application Date

20231109

Claims (5)

1. 1. The preparation method of the composite PbO/ZnO three-dimensional porous lead-carbon battery additive is characterized by comprising the following specific steps: (1) Pretreating the titanium base by degreasing, and then placing the pretreated titanium base in a nitric acid-hydrochloric acid mixed solution for etching and activating to obtain an activated titanium base; (2) Uniformly mixing three-dimensional hierarchical porous carbon, carbon black and a binder PVDF to obtain a mixture, adding N-pyrrolidone into the mixture, and uniformly mixing to obtain three-dimensional hierarchical porous carbon slurry; (3) Uniformly coating the three-dimensional graded porous carbon slurry on the surface of the activated titanium base, and drying to obtain a carbon base anode; (4) Taking a lead nitrate-zinc oxide mixed solution as an electroplating solution, taking a carbon-based anode as an anode, taking a copper plate as a cathode, electroplating for 1-2 hours at the temperature of 40-50 ℃ under the stirring condition, taking out the electroplated anode, cleaning with deionized water, scraping an electroplated layer from the titanium-based surface, and vacuum drying to obtain the composite PbO/ZnO three-dimensional porous lead-carbon battery additive; the concentration of nitric acid in the nitric acid-hydrochloric acid mixed solution in the step (1) is 0.1-0.3 mol/L, the concentration of hydrochloric acid is 0.3-0.6 mol/L, and the etching activation time is 60-80 s; The mass fraction of the mixture in the step (2) is 100%, the three-dimensional hierarchical porous carbon accounts for 70-80%, the carbon black accounts for 10-15%, the binder PVDF accounts for 10-15%, and the addition amount of the N-pyrrolidone is 10-15% of the mass of the mixture; The preparation method of the three-dimensional hierarchical porous carbon in the step (2) comprises the following specific steps: 1) Placing carbonized biomass charcoal into NaOH solution for etching, washing by hydrochloric acid and deionized water in sequence, and vacuum drying to obtain etched biomass charcoal; 2) Uniformly mixing etched biomass carbon and an activating agent, then placing the mixture in a tube furnace, uniformly heating to 700-800 ℃ under a nitrogen atmosphere, preserving heat for 1-2 hours, cooling to room temperature, washing and vacuum drying to obtain three-dimensional graded porous carbon; In the step 1), the mass concentration of the NaOH solution is 10-15%, the etching temperature is 60-90 ℃, the etching time is 2-2.5 h, and the mass concentration of the hydrochloric acid is 10-15%; The activating agent in the step 2) is KOH, the mass ratio of the etched biomass charcoal to the activating agent is 1:3-5, and the heating rate is 5-10 ℃ per minute.
2. 2. The preparation method of the composite PbO/ZnO three-dimensional porous lead carbon battery additive, which is disclosed in claim 1, is characterized in that the loading amount of three-dimensional graded porous carbon on the surface of the carbon-based anode in the step (3) is 2.5-3.0 mg/cm 2 .
3. 3. The preparation method of the composite PbO/ZnO three-dimensional porous lead-carbon battery additive is characterized in that the concentration of lead nitrate in the electroplating solution in the step (4) is 190-250 g/L, the concentration of zinc oxide is 12-20 g/L, and the pH value of the electroplating solution is 6-8.
4. 4. The preparation method of the composite PbO/ZnO three-dimensional porous lead-carbon battery additive is characterized in that the particle size of zinc oxide is 50-60 nm.
5. 5. The preparation method of the composite PbO/ZnO three-dimensional porous lead-carbon battery additive, which is disclosed in claim 1, is characterized in that the anode current density of electroplating in the step (4) is 2-4A/dm 2 , and the stirring speed is 250-320 r/min.

Description

Preparation method of composite PbO/ZnO three-dimensional porous lead-carbon battery additive Technical Field The invention relates to a preparation method of a composite PbO/ZnO three-dimensional porous lead-carbon battery additive, and belongs to the technical field of lead-carbon batteries. Background The lead-acid battery has the advantages of low price, high safety performance, wide application, high battery recovery rate and the like. In recent years, lead acid batteries are considered as one of the most widely used power sources in transportation at this stage. However, the wide application of lead-acid batteries is largely limited by the disadvantages of low mass specific energy, large occupied space, short cycle life, poor rate capability, etc. of conventional lead-acid batteries. Particularly, under the working condition of high-rate partial charge state (HRPSC) charge and discharge, the negative electrode of the lead-acid battery is extremely easy to generate irreversible sulfation of an active material, so that the service life and capacity of the lead-acid battery are reduced. The lead-carbon battery (LCB) is a novel battery developed by adding a carbon material into a lead-acid battery design, has the advantages of instantaneous high-capacity charging of a super capacitor, high charging capacity, excellent multiplying power performance, long cycle life under high multiplying power and the like, and is widely applied to new fields of hybrid electric vehicles, wind energy, solar energy storage and the like. However, the addition of the carbon material has a plurality of problems that the hydrogen evolution overpotential of the carbon material is lower, the charging and discharging electrode is easy to cause serious hydrogen evolution reaction under the high-rate condition, and the structural stability of the electrode is damaged by the hydrogen evolution, so that the cycle stability of the battery is reduced. Current solutions to the above problems include: (1) The carbon material is functionalized, and hetero atoms with electronegativity larger than that of C atoms are modified to ensure that the carbon end is positively charged, so that the aim of inhibiting hydrogen evolution is fulfilled. However, the source materials of the hetero atoms are organic matters such as pyridine and pyrrole, which can pollute the environment. (2) Directly adding high hydrogen evolution overpotential metal and oxide thereof, and directly adding high hydrogen evolution overpotential metal and metal oxide thereof, which is easy to generate carbon floating phenomenon. Because the bond between the metal and the carbon material is unstable, it is physically bonded. (3) Adding lead-carbon compound. Lead-carbon composites are currently being studied more widely because Pb and its oxides are active species of lead-carbon composites and do not introduce impurity ions. Meanwhile, the lead-carbon compound has a stable structure, and can effectively solve the problem of carbon floating, but the problems of uneven distribution of metallic lead and oxides thereof in carbon materials, easy agglomeration and difficult control of the particle size of the hydrogen evolution inhibitor still exist. Disclosure of Invention Aiming at the problems that the hydrogen evolution overpotential of a carbon material in the existing lead-carbon battery (LCB) is low, serious hydrogen evolution reaction is easy to be caused by charging and discharging an electrode under the condition of high multiplying power, the structural stability of the electrode is damaged by the precipitation of hydrogen, and the cycle stability of the lead-carbon battery is reduced, the invention provides a preparation method of the composite PbO/ZnO three-dimensional porous lead-carbon battery additive. The preparation method of the composite PbO/ZnO three-dimensional porous lead-carbon battery additive comprises the following specific steps: (1) Pretreating the titanium base by degreasing, and then placing the pretreated titanium base in a nitric acid-hydrochloric acid mixed solution for etching and activating to obtain an activated titanium base; (2) Uniformly mixing three-dimensional hierarchical porous carbon, carbon black and a binder PVDF to obtain a mixture, adding N-pyrrolidone into the mixture, and uniformly mixing to obtain three-dimensional hierarchical porous carbon slurry; (3) Uniformly coating the three-dimensional graded porous carbon slurry on the surface of the activated titanium base, and drying to obtain a carbon base anode; (4) The method comprises the steps of taking a lead nitrate-zinc oxide mixed solution as an electroplating solution, taking a carbon-based anode as an anode, taking a copper plate as a cathode, electroplating for 1-2 hours at the temperature of 40-50 ℃ under the stirring condition, taking out the electroplated anode, cleaning by deionized water, scraping the electroplated layer from the titanium-based surface, and vacuum drying to