CN107732251B - controllable preparation method of anticorrosive modified coating of lead-carbon battery positive grid - Google Patents

controllable preparation method of anticorrosive modified coating of lead-carbon battery positive grid Download PDF

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CN107732251B
CN107732251B CN201710933355.XA CN201710933355A CN107732251B CN 107732251 B CN107732251 B CN 107732251B CN 201710933355 A CN201710933355 A CN 201710933355A CN 107732251 B CN107732251 B CN 107732251B
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CN107732251A (en
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林海波
包金鹏
李洪坤
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Jilin Province Kai Yu Electrochemical Energy Storage Technology Development Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/68—Selection of materials for use in lead-acid accumulators
    • H01M4/685—Lead alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H01M4/16—Processes of manufacture
    • H01M4/20—Processes of manufacture of pasted electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention discloses a highly controllable lead-carbon battery positive grid anticorrosion coating and a preparation method of a related polar plate thereof, wherein the anticorrosion coating is Pb-PbO prepared by anodic electrochemical oxidationx(x<2) the composite, the polar plate is composed of lead powder, colloidal graphite and short fibers. Pb-PbOx(x<2) the composite coating is composed of multiple phases, Pb phase is connected with lead-calcium slab lattice, PbOxThe phase is connected with an active substance which is mainly lead dioxide, Pb and PbOxAre tightly connected with each other by means of electrochemical deposition. The coating provided by the invention can effectively improve the corrosion resistance of the grid and the connectivity between the grid and the lead plaster, effectively relieve the phenomena of positive grid fracture and lead plaster falling under the high-rate partial charge state, and prolong the overall cycle life of the battery. The advantages of low cost, simple operation, high controllability and easy large-scale production of the electrochemical oxidation are fully exerted.

Description

Controllable preparation method of anticorrosive modified coating of lead-carbon battery positive grid
The technical field is as follows:
The invention relates to a lead-carbon battery, in particular to a positive grid of the lead-carbon battery
Background art:
With the increasing popularity of electrical devices, there is an increasing demand for energy storage devices. As an energy storage device with the history of nearly two hundred years, the lead-acid battery has the advantages of low cost, good low-temperature stability, safety, reliability and the like. But the application range is limited due to the defects of low energy density and short cycle life.
the lead-carbon battery is known as the next generation of lead-acid battery, and the lead-acid battery is formed by adding a carbon material into the negative electrode of the lead-acid battery. Because the carbon material has good conductivity, chemical stability in a strong acid environment and a specific surface area far higher than that of pure lead, compared with the traditional lead-acid battery, the sulfation of the negative electrode of the lead-carbon battery is obviously inhibited, the effective utilization rate of the negative electrode active substance is obviously improved, and the overall cycle life and the energy density are obviously enhanced. The lead-carbon battery is the most advanced technology in the field of lead-acid batteries, is the key direction of the international new energy storage industry, and has a wide development space.
As a new lead-acid battery, the lead-carbon battery has several advantages and some problems. Along with the improvement of the performance of the negative electrode, the matching problem of the positive electrode and the negative electrode becomes increasingly prominent. Compared with the traditional lead-acid battery positive electrode, the lead-carbon battery positive electrode faces higher working potential and more extreme cycle environment, which provides further challenges for the corrosion resistance of the grid and the connectivity of the grid and lead paste.
The artificial manufacture of the anti-corrosion layer on the grid is an effective solution. The anti-corrosion layers including the tin-antimony intermediate layer, the platinum intermediate layer, the titanium-thallium intermediate layer and the like can obviously enhance the corrosion resistance of the grid in an extreme environment and the connectivity with lead paste. Patent CN104485445A discloses a lead-acid battery positive electrode anti-corrosion layer, the lead-acid battery using the positive plate has good stability of heavy current discharge, strong low-temperature starting capability, excellent corrosion resistance, long cycle charge and discharge life and excellent comprehensive performance. In addition, the direct modification of the plate grid alloy is also the main idea at present. Patent CN105177354A discloses a grid alloy containing rare earth elements for positive electrode of lead storage battery, which improves the strength of grid and enhances the corrosion resistance of polar plate, thus improving the high temperature float charge life and deep cycle life of battery. However, these patents have the defects of complex preparation method, high price and the like, and are difficult to popularize on a large scale on the premise of large market quotas of the existing lead-carbon batteries.
In the charge-discharge cycle process of the traditional lead-acid battery, a natural electrochemical anti-corrosion layer is formed between a positive electrode plate and lead plaster, and the intermediate layer is in a structure of transition from lead to lead dioxide, namely Pb and PbOx(x<2) in the formula. Natural corrosion protection due to etching of grids in an electrochemical processThe layer conforms to the battery reaction requirement of electrochemical reaction, has the advantages of good conductivity, compact distribution, excellent connection with lead paste and the like, and is an ideal intermediate layer material.
The electrochemical anodic oxidation has the advantages of highly controllable product, low energy consumption, simple method and the like, and is a direction of attention for artificially preparing the natural ideal interlayer material. The alpha-PbO on the surface of the positive plate grid can be effectively regulated by an electrochemical anodic oxidation method2、β-PbO2And PbOxThe proportion and the distribution of the etching solution can be used for etching the plate grid in a highly controllable way, and the industrial production with simple operation, low cost and obvious effect can be realized.
The invention content is as follows:
The invention aims to provide a positive grid anti-corrosion layer with high controllability, stable structure and uniform distribution by utilizing an electrochemical anodic oxidation method with the best controllability. When the positive plate grid is applied to a lead-carbon battery, the corrosion resistance of the positive plate grid and the connectivity of the plate grid and lead paste are obviously enhanced, and the cycle service life of the high-rate partial charge state is obviously prolonged.
Therefore, the invention adopts the following technical scheme:
A preparation method of a positive electrode plate of a lead-carbon battery at least comprises the following steps:
1)Pb-PbOx(x<2) preparation of the coating
The method adopts the electrochemical anode oxidation method of a lead alloy grid, the lead-calcium anode alloy grid is placed in a mixed solution of 0.5-1M lead salt, 0.1-0.2M strong acid and 0.01-0.05M surface dispersant, and the counter electrode is a platinum electrode. The initial oxidation current density is 10-80mA/cm2Preferably 60-80mA/cm2(ii) a The deposition time is 1-16h, and the deposition temperature is 20-40 deg.C, preferably 25-40 deg.C. Reducing after oxidation with current density of 10-80mA/cm2preferably 50-80mA/cm2(ii) a Depositing for 1-16h at 20-40 deg.C, preferably 25-40 deg.C to obtain Pb-PbOx(x<2) coating.
(2) preparation of lead plaster
80-90 wt% of lead powder and 5-10 wt% of alpha/beta-PbO2-SiO2Uniformly mixing the compound, 1-5 wt% of colloidal graphite and 1-5 wt% of short fibers to prepare an active substance, and slowly adding water accounting for 10-15 wt% of the total weight of the active substance and sulfuric acid accounting for 4-8 wt% of the total weight of the active substance after mixing to uniformly stir to form lead plaster; the lead powder is preferably 85-90 wt%, alpha/beta-PbO2-SiO2The composite is preferably 8 to 10 wt%, the colloidal graphite is preferably 1 to 3 wt%, and the short fiber is preferably 1 to 3 wt%.
(3) Preparation of positive electrode plate of lead-carbon battery
Coating the lead plaster prepared in the step (2) on the lead-containing material with Pb-PbOx(x<And (2) drying and curing the lead alloy grid coated with the coating to prepare the positive plate of the lead-carbon battery.
The lead salt in the step (1) is one or more of lead nitrate, lead sulfate, lead chloride and lead perchlorate.
In the step (1), the strong acid is one or more of nitric acid, sulfuric acid, hydrochloric acid and perchloric acid.
The surface dispersant in the step (1) is one or more of sodium tripolyphosphate, triethylhexylphosphoric acid and sodium dodecyl sulfate.
The short fibers in the step (2) comprise one or more of terylene and acrylon, and the length of the fibers is 1-40 mm.
The concentration of the sulfuric acid added in the step (2) is 4-5mol/L, and the adding speed is 1-5 mL/s.
The drying and curing step in the step (3) is as follows:
1) Keeping constant temperature at 55 deg.C and air humidity of 96-98%, preferably 98%, for 1-5 hr, preferably 2 hr
2) Keeping constant temperature at 60 deg.C and air humidity of 96-98%, preferably 98%, for 5-20 hr, preferably 10 hr
3) At 65 deg.C, air humidity of 96-98%, preferably 98%, and constant temperature for 25-35 hr, preferably 32 hr
4) Keeping constant temperature at 60 deg.C and air humidity of 60-80%, preferably 70%, for 1-5 hr, preferably 3 hr
5) Keeping the temperature at 70 deg.C and air humidity of 20-50%, preferably 30%, for 1-5h, preferably 3 h.
artificially constructing natural ideal Pb-PbO by electrochemical anodic oxidation methodx(x<2) intermediate layer, radicalthe combination mode and the strength of the lead paste composition with a lead alloy grid and the performance of a polar plate product are different, the corrosion resistance of the positive grid and the connectivity of the positive grid and the lead paste are enhanced through the analysis of raw materials and structures, the combination of a large number of tests, the preparation method of the specific coating, the corresponding steps of drying, curing and the like, and the cycle life of the battery is further prolonged. The advantages of low cost, simple operation and high controllability of the electrochemical oxidation are fully exerted. The lead-carbon storage battery with the anode plate has a wide application prospect in the fields of starting and stopping automobiles, solar energy and wind energy storage.
Drawings
FIG. 1: cyclic voltammetry test chart of untreated plate grid
FIG. 2: cyclic voltammetry test chart of example 1
FIG. 3: example 2 cyclic voltammetry test chart
the specific implementation mode is as follows:
The invention is further illustrated by the following examples:
Example 1
the lead-calcium positive alloy grid is placed in a mixed solution of 1M lead sulfate, 0.2M sulfuric acid and 0.01M sodium dodecyl sulfate by adopting a lead alloy grid electrochemical anodic oxidation method, and the counter electrode is a platinum electrode. The initial oxidation current density was 80mA/cm2The deposition time was 4h and the deposition temperature was 25 ℃. After oxidation, reduction was carried out at a current density of 70mA/cm2The deposition time is 6h, the deposition temperature is 25 ℃, and Pb-PbO is preparedx(x<2) coating.
85 wt% of lead powder and 10 wt% of alpha/beta-PbO2-SiO2Uniformly mixing the compound, 2.5 wt% of colloidal graphite and 2.5 wt% of 40mm polyester staple fiber to prepare an active substance, and slowly adding water accounting for 12 wt% of the total weight of the active substance and 8 wt% of 2mL/s 4.7mol/L sulfuric acid into the active substance after mixing and uniformly stirring to obtain lead plaster; coating the prepared lead plaster on the lead-bearing material with Pb-PbOx(x<And (2) drying and curing the lead alloy grid coated with the coating to prepare the positive plate of the lead-carbon battery. The curing steps are as follows:
1) Keeping the temperature at 55 ℃ and the air humidity at 98 percent for 2h
2) keeping the temperature at 60 ℃ and the air humidity at 98 percent for 10 hours
3) The temperature is 65 ℃, the air humidity is 98 percent, and the temperature is kept for 32 hours
4) keeping the temperature at 60 ℃ and the air humidity at 70 percent for 3 hours
5) keeping the temperature at 70 ℃ and the air humidity at 30% for 3 h.
Example 2
The method adopts the electrochemical anode oxidation method of a lead alloy grid, the lead-calcium anode alloy grid is placed in a mixed solution of 0.5M lead chloride, 0.1M sulfuric acid and 0.01-0.05M sodium tripolyphosphate, and the counter electrode is a platinum electrode. The initial oxidation current density was 60mA/cm2The deposition time is 12h, and the deposition temperature is 30 ℃. After oxidation, reduction is carried out with a current density of 50mA/cm2the deposition time is 8h, the deposition temperature is 40 ℃, and Pb-PbO is preparedx(x<2) coating.
85 wt% of lead powder and 10 wt% of alpha/beta-PbO2-SiO2Uniformly mixing the compound, 2.5 wt% of colloidal graphite and 2.5 wt% of 40mm polyester staple fiber to prepare an active substance, and slowly adding water accounting for 12 wt% of the total weight of the active substance and 8 wt% of 2mL/s 4.7mol/L sulfuric acid into the active substance after mixing and uniformly stirring to obtain lead plaster; coating the prepared lead plaster on the lead-bearing material with Pb-PbOx(x<And (2) drying and curing the lead alloy grid coated with the coating to prepare the positive plate of the lead-carbon battery. The curing steps are as follows:
1) Keeping the temperature at 55 ℃ and the air humidity at 98 percent for 2h
2) Keeping the temperature at 60 ℃ and the air humidity at 98 percent for 10 hours
3) The temperature is 65 ℃, the air humidity is 98 percent, and the temperature is kept for 32 hours
4) Keeping the temperature at 60 ℃ and the air humidity at 70 percent for 3 hours
5) Keeping the temperature at 70 ℃ and the air humidity at 30% for 3h
example 3
The method adopts the electrochemical anode oxidation method of a lead alloy grid, the lead-calcium anode alloy grid is placed in a mixed solution of 0.5M lead nitrate, 0.2M sulfuric acid and 0.05M sodium tripolyphosphate, and the counter electrode is a platinum electrode. The initial oxidation current density was 80mA/cm2The deposition time is 10h, and the deposition temperature isat 40 ℃. After oxidation, reduction is carried out with a current density of 60mA/cm2The deposition time is 16h, the deposition temperature is 30 ℃, and Pb-PbO is preparedx(x<2) coating.
85 wt% of lead powder and 10 wt% of alpha/beta-PbO2-SiO2Uniformly mixing the compound, 2.5 wt% of colloidal graphite and 2.5 wt% of 40mm terylene to prepare an active substance, and slowly adding water accounting for 12 wt% of the total weight of the active substance and 8 wt% of 2mL/s 4.7mol/L sulfuric acid into the mixed active substance in sequence and uniformly stirring to obtain lead plaster; coating the prepared lead plaster on the lead-bearing material with Pb-PbOx(x<and (2) drying and curing the lead alloy grid coated with the coating to prepare the positive plate of the lead-carbon battery. The curing steps are as follows:
1) Keeping the temperature at 55 ℃ and the air humidity at 98 percent for 2h
2) keeping the temperature at 60 ℃ and the air humidity at 98 percent for 10 hours
3) The temperature is 65 ℃, the air humidity is 98 percent, and the temperature is kept for 32 hours
4) Keeping the temperature at 60 ℃ and the air humidity at 70 percent for 3 hours
5) Keeping the temperature at 70 ℃ and the air humidity at 30% for 3h
The grid prepared in example 1 was subjected to a standard three-electrode test with a platinum counter electrode, a mercury/mercurous sulfate reference electrode, and 4.7M concentrated sulfuric acid electrolyte. Untreated grids were also tested under the same conditions, and all results are shown in fig. 1 and 2. The oxidation reduction peak observed in the potential window of-1.6-0V is the faradaic reaction between lead and lead sulfate, and by comparing the reduction peak height in the sixth turn, it can be found that the grid coated with the anti-corrosion layer has a significantly higher response current than the untreated grid, indicating that the grid shows a more significant faradaic reaction. However, as the circulation is carried out, the reduction peak heights of the sixty th circles of the two grids are basically close, which shows that the etching rate of the grid coated with the anti-corrosion layer is lower than that of the untreated grid, and the grid has great advantages in long-term circulation.
The same three electrode test was performed as in example 2, but the cell window was changed to 0-1.6V, i.e., the test for oxidation reaction between lead dioxide and lead sulfate. As shown in fig. 3, the oxidation-reduction peaks of the first ring indicate the presence of active lead dioxide in the corrosion protection layer indicated by the grid, while the reduction peaks at around 1.15V and 1.55V indicate that the lead oxide obtained has a different degree of oxidation. While the oxidation peaks around 1.15V and 1.05V further indicate the formation of various lead oxides. With the increase of the number of turns, the left shift of the reduction peak and the change of the ratio of the two oxidation peaks can be obviously seen, on one hand, the generated lead oxides are gradually converted with each other along with the Faraday reaction, and on the other hand, the lead is gradually exposed to the strong acid environment in the oxidation process, so that more lead oxides are generated.
Pb-PbO-coated substrates prepared in examples 1 to 3x(x<2) the positive pole plate of the anti-corrosion layer, the negative pole plate of the lead-carbon battery, the AGM diaphragm and 4.7M sulfuric acid electrolyte are assembled into a 6Ah flooded battery, and the lead-carbon battery is manufactured through internal formation. The lead-carbon batteries with the additives of examples 1-3 added were subjected to the HRPSoC test according to the following procedure:
(1) discharging until 30% Soc is 0.5C (3A) constant current, and discharging for 1.4 h;
(2) HRPSoC cycle:
a. Charging: 1C (6A), 2.4V constant-current constant-voltage charging for 60 s;
b. Discharging: 0.45C (2.7A) constant current discharge 59s, then 3C (18A) constant current discharge 1 s;
c. The HRPSoC cycle was repeated until the voltage was less than 1.75V. Recording the cycle life;
HRPSoC cycle data are shown in the following Table, coated with Pb-PbOx(x<2) the positive electrode plate of the anti-corrosion layer has excellent current adaptability, and the service life is obviously prolonged in high-rate charge and discharge. In the disassembly analysis of the failed battery, the failure of the positive plate is mainly concentrated between the plate grid and the lug, and the phenomenon that the active substance falls off is basically avoided, so that the construction effect among multiple phases is remarkable. Different cycle lives indicate that the synthesis conditions can affect the corrosion layer performance and there is room for optimization of the grids prepared in examples 1-3.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.

Claims (7)

1. A preparation method of a positive electrode plate of a lead-carbon battery is characterized by comprising the following steps: at least comprises the following steps:
(1)Pb-PbOx，x<preparation of ═ 2 coatings
Putting a lead-calcium positive electrode alloy grid into a mixed solution of 0.5-1M lead salt, 0.1-0.2M strong acid and 0.01-0.05M surface dispersant by adopting a lead alloy grid electrochemical anodic oxidation method, wherein a counter electrode is a platinum electrode; the initial oxidation current density is 10-80mA/cm2the deposition time is 1-16h, and the deposition temperature is 20-40 ℃; reducing after oxidation with current density of 10-80mA/cm2The deposition time is 1-16h, the deposition temperature is 20-40 ℃, and Pb-PbO is preparedx，x<2 coating; the surface dispersing agent is one or more of sodium tripolyphosphate, triethylhexylphosphoric acid and sodium dodecyl sulfate;
(2) Preparation of lead plaster
80-90 wt% of lead powder and 5-10 wt% of alpha/beta-PbO2-SiO2Uniformly mixing the compound, 1-5 wt% of colloidal graphite and 1-5 wt% of short fibers to prepare an active substance, and slowly adding water accounting for 10-15 wt% of the total weight of the active substance and sulfuric acid accounting for 4-8 wt% of the total weight of the active substance after mixing to uniformly stir to form lead plaster; the concentration of the sulfuric acid added in the step (2) is 4-5mol/L, and the adding speed is 1-5 mL/s;
(3) Preparation of positive electrode plate of lead-carbon battery
Coating the lead plaster prepared in the step (2) on the lead-containing material with Pb-PbOx，x<and (3) drying and curing the lead alloy grid with the 2 coating to prepare the positive plate of the lead-carbon battery.
2. the method for preparing the positive plate of the lead-carbon battery according to claim 1, wherein the method comprises the following steps: the lead salt in the step (1) is one or more of lead nitrate, lead sulfate, lead chloride and lead perchlorate.
3. The method for preparing the positive plate of the lead-carbon battery according to claim 1, wherein the method comprises the following steps: in the step (1), the strong acid is one or more of nitric acid, sulfuric acid, hydrochloric acid and perchloric acid.
4. The method for preparing the positive plate of the lead-carbon battery according to claim 1, wherein the method comprises the following steps: the short fibers in the step (2) comprise one or more of terylene and acrylon, and the length of the fibers is 1-40 mm.
5. The method for preparing the positive plate of the lead-carbon battery according to claim 1, wherein the method comprises the following steps: the initial oxidation current density is 60-80mA/cm2The deposition time is 1-16h, and the deposition temperature is 25-40 ℃; reducing after oxidation with a current density of 50-80mA/cm2(ii) a The deposition time is 1-16h, and the deposition temperature is 25-40 ℃.
6. The method for preparing the positive plate of the lead-carbon battery according to claim 1, wherein the method comprises the following steps: the drying and curing step in the step (3) is as follows:
1) Keeping the temperature at 55 ℃ and the air humidity at 96-98% for 1-5h,
2) Keeping the temperature at 60 ℃ and the air humidity at 96-98% for 5-20h,
3) Keeping the temperature at 65 ℃ and the air humidity at 96-98% for 25-35h,
4) Keeping the temperature at 60 ℃ and the air humidity at 60-80% for 1-5h,
5) Keeping the temperature at 70 ℃ and the air humidity at 20-50% for 1-5 h.
7. The method for preparing the positive plate of the lead-carbon battery according to claim 6, wherein the method comprises the following steps: the drying and curing step in the step (3) is as follows:
1) Keeping the temperature at 55 ℃ and the air humidity at 98 percent for 2h
2) Keeping the temperature at 60 ℃ and the air humidity at 98 percent for 10 hours
3) the temperature is 65 ℃, the air humidity is 98 percent, and the temperature is kept for 32 hours
4) Keeping the temperature at 60 ℃ and the air humidity at 70 percent for 3 hours
5) Keeping the temperature at 70 ℃ and the air humidity at 30% for 3 h.
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