CN111081986A - Preparation method of high-power external application type lead-carbon battery cathode - Google Patents
Preparation method of high-power external application type lead-carbon battery cathode Download PDFInfo
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- CN111081986A CN111081986A CN201911253673.7A CN201911253673A CN111081986A CN 111081986 A CN111081986 A CN 111081986A CN 201911253673 A CN201911253673 A CN 201911253673A CN 111081986 A CN111081986 A CN 111081986A
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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
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
- H01M4/57—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead of "grey lead", i.e. powders containing lead and lead oxide
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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
Abstract
The invention discloses a preparation method of a high-power external application type lead-carbon battery cathode, which consists of three parts of lead paste, a carbon sheet and gel. The structure that the carbon sheet is pasted on the surface of the lead plaster can improve the potential distribution of the electrode, inhibit the surface sulfation and improve the effective utilization rate of active substances. When lead ions in the electrolyte contact the negative carbon plate, under the electrochemical action, the surface of the carbon plate is subjected to oxidation-reduction circulation of lead and lead sulfate to generate sulfation, so that the power density and the circulation stability of the electrode are reduced. The gel can inhibit lead ions from contacting the surface of the carbon material, avoid lead ion reduction, inhibit sulfation on the surface of the carbon material, ensure normal exertion of the beneficial effect of the carbon material, improve the charging and discharging efficiency of the electrode and prolong the cycle service life of the electrode. The external application lead-carbon battery composed of the cathode has higher heavy current bearing capacity and cycling stability, and is suitable for the fields of starting and stopping automobiles, solar energy, wind energy storage and the like.
Description
The technical field is as follows:
the invention relates to a preparation method of a high-power external application type lead-carbon battery cathode
Background art:
with the acceleration of global electrification process, the development of advanced energy storage systems with good safety, low cost and high performance is imminent. The lead-acid battery has the advantages of strong low-temperature stability, high cost performance and mature technology, but the power density is not high (<200W Kg & lt-1 & gt), and the cycle capacity is low (1C, 80% DOD, 400 circles).
The externally applied lead-carbon battery belongs to power lead-acid battery, and aims at strengthening the large current bearing capacity and the charge state cycle life of high-rate part. The external application type lead-carbon battery pastes the carbon material on the surface of the negative lead plaster, and ensures that the carbon material is fully contacted with the electrolyte, and simultaneously, the carbon material and the lead plaster form a serial-parallel structure, so that on one hand, the double-capacitance characteristic of capacitance carbon is fully exerted, electronic buffer is provided for high-rate charging and discharging of the battery, polarization is slowed down, on the other hand, sulfation mainly occurs on the surface of an electrode during high-rate charging and discharging, and the pasted structure is beneficial to exerting the sulfation inhibition capability of the carbon material.
Generally, the failure mechanism of the external application type lead-carbon battery cathode under high current is the same as that of a lead-acid battery cathode, on one hand, the high current accelerates the sulfation process, lead sulfate is more difficult to convert into elemental lead, the service life of the electrode is reduced, on the other hand, the high current improves the hydrogen evolution rate, and the charging and discharging efficiency of the electrode is reduced. In response to these side reactions, a series of research results have been made on the electrical conductivity, specific surface area, surface modification, and the like of carbon materials. Patent CN102856528B discloses a method for preparing an external application type lead-carbon battery cathode, which is characterized in that a part of lead paste on a polar plate is removed and replaced by carbon paste, so that the operation is convenient and easy, and the adverse effect on the battery performance caused by directly adding a carbon plate in the battery is avoided, and the prepared storage battery has high performance and long service life. The method has strong operability and is suitable for mass production in workshops. The patent CN105355912B discloses another preparation method of an externally-applied lead-carbon battery cathode, and the activated carbon provided by the invention loads organic bismuth for inhibiting hydrogen evolution reaction while improving hydrophilicity, so that the compactness and charging performance of activated lead paste of the lead-carbon battery are improved, the impedance of the lead paste is reduced, the falling off of the activated carbon in the charging and discharging processes is avoided, and the cycle life of the lead-carbon battery is greatly prolonged. However, the external application type lead-carbon battery also has a special phenomenon of lead deposition on the surface of negative electrode carbon, namely: 1) in the discharging process, the positive electrode and the negative electrode can provide free lead ions for the electrolyte; 2) during the charging process, free lead ions can contact with lead paste to be reduced and can also contact with a carbon material; 3) the deposited simple substance lead can be rapidly sulfated in the high-rate circulation process, and is changed into insoluble and unreacted massive lead sulfate which is adsorbed on the surface of the electrode. If the surface of the carbon material is sulfated, the double electric layers and the catalytic property of the carbon material are disturbed, so that the cycle life of the electrode is shortened, and the power density is reduced. The phenomenon of lead deposition on the surface of the negative carbon material of the external application type lead-carbon battery is not well solved.
The invention content is as follows:
the invention aims to provide a preparation method of a high-power externally-applied lead-carbon battery cathode, which can inhibit the occurrence of lead deposition on the surface of carbon, and when the cathode is applied to a lead-carbon battery, the sulfation rate of the surface of a carbon material is reduced, the capacitance and the catalytic capability are normally exerted, the hydrogen evolution and the capacity attenuation of the cathode caused by sulfation are slowed down, and the power density is improved.
Therefore, the invention adopts the following technical scheme:
a preparation method of a high-power external application type lead-carbon battery cathode at least comprises the following steps:
(1) preparation of lead plaster
Uniformly mixing 85-95 wt% of lead powder, 0.5-3 wt% of humic acid, 0.5-3 wt% of short fiber, 0.5-3 wt% of barium sulfate, 0.5-3 wt% of sodium lignosulfonate and 0.5-3 wt% of acetylene black to prepare an active substance, and slowly adding water accounting for 5.0-10.0 wt% of the total weight of the active substance and 10.0-15.0 wt% of sulfuric acid into the active substance and uniformly stirring to prepare lead plaster;
(2) preparation of carbon sheets
Uniformly mixing 80-90 wt% of activated carbon material, 5-10 wt% of conductive carbon material and 5-10 wt% of connecting agent in absolute ethyl alcohol, wherein the mass of the absolute ethyl alcohol is 150-fold and 200-fold of that of the activated carbon material. The anhydrous ethanol was evaporated to dryness by stirring at constant temperature of 90 ℃ to obtain a uniform mixture. Adding 0.1-0.3ml/mg absolute ethanol into the mixture, rolling into tablet, and drying at 90 deg.C for 12 hr to obtain carbonAnd (3) slicing. The loading amount of the mixture in the carbon sheet is 2-3mg/cm2；
(3) Preparation of the gel
Mixing 50-60 wt% of adhesive, 10-20 wt% of conductive carbon material and 20-40 wt% of activated carbon material into sufficient deionized water, and stirring uniformly. Heating at 80 deg.C, stirring to remove 80 wt% water solvent, and naturally cooling to room temperature to obtain black viscous colloid. The total mass of the activated carbon material and the conductive carbon material is the same as the mass of the solvent of the black viscous colloid;
(4) preparation of external application type lead-carbon battery negative electrode plate
And (2) coating the lead plaster prepared in the step (1) on a lead alloy grid, and curing to obtain a green plate. Cutting the carbon sheet in the step (2) into sheets according to the length and width of the lead alloy grid, then respectively pressing the two cut carbon sheets on two sides of a green plate by using the pressure of 2-4Mpa, uniformly coating black viscous colloid in the step (3) with the mass of 50% of the carbon sheets on the surface of the carbon sheet, naturally evaporating 10 wt% of water to dryness, and soaking an electrode in a 5M sulfuric acid solution for storage to obtain an external application type lead-carbon battery negative electrode plate;
the short fibers in the step (1) 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 (1) is 4-5mol/L, and the adding speed is 1-5 mL/s.
The specific surface area of the activated carbon material in the step (2) is 1500-2/g。
The conductive carbon material in the step (2) is one or more of carbon black, acetylene black and colloidal graphite.
And (3) in the step (2), the connecting agent is one or more of polyvinyl alcohol, polyvinylidene fluoride and polytetrafluoroethylene.
The adhesive in the step (3) is one or more of polyvinyl alcohol, polystyrene, polyvinyl chloride and polycarbonate.
The specific surface area of the activated carbon material in the step (3) is 1500-2/g。
And (3) the conductive carbon material is one or more of carbon black, acetylene black and expanded graphite.
The drying and curing step in the step (4) comprises the following steps:
1) keeping the temperature at 40 ℃ and the air humidity at 99% for 12h
2) Keeping the temperature at 45 ℃ and the air humidity at 99 percent for 14h
3) Keeping the temperature at 45 ℃ and the air humidity at 75% for 8h
4) The temperature is 55 ℃, the air humidity is 90 percent, and the constant temperature is kept for 8 hours
5) Keeping the temperature at 65 ℃ and the air humidity at 80 percent for 10 hours
6) Keeping the temperature at 45 ℃ and the air humidity at 75% for 4h
7) Keeping the temperature at 65 ℃ and the air humidity at 30 percent for 4 hours
8) Keeping the temperature at 75 ℃ and the air humidity at 30 percent for 12h
The carbon material has the beneficial effects that the effective utilization rate of active substances can be improved by the pasted carbon material, the surface potential distribution of the electrode is improved, the sulfation of lead paste is slowed down, the gel can inhibit lead ions from contacting the surface of the carbon material, the phenomenon of inhibiting the sulfation on the surface of the carbon material due to the reduction of the lead ions is avoided, the normal exertion of the beneficial effect of the carbon material is ensured, the power density of the electrode is improved, and the cycle service life of the electrode is prolonged. The lead-carbon storage battery with the negative plate has a wide application prospect in the fields of starting and stopping automobiles, solar energy and wind energy storage.
Description of the drawings:
fig. 1 is a life test chart of example 1.
The specific implementation mode is as follows:
the present invention will be further illustrated by the following examples
Example 1:
uniformly mixing 85% of lead powder, 3 wt% of humic acid, 3 wt% of 10mm long polyester, 3 wt% of barium sulfate, 3 wt% of sodium lignosulfonate and 3 wt% of acetylene black to prepare an active substance, and slowly adding 8 wt% of water and 12.5 wt% of 4.6mol/L sulfuric acid into the mixed active substance in sequence and uniformly stirring to prepare lead plaster;
85 wt% 1960m2The active carbon material is mixed evenly in absolute ethyl alcohol by the weight of 10 wt% of carbon black and 5 wt% of polytetrafluoroethylene, and the absolute ethyl alcohol is the active carbon material180 times of the material mass. The anhydrous ethanol was evaporated to dryness by stirring at constant temperature of 90 ℃ to obtain a uniform mixture. 0.3ml/mg of absolute ethanol is added into the mixture to be rolled into a sheet, and then the sheet is dried at 90 ℃ for 12 hours to obtain the carbon sheet. The loading amount of the mixture in the carbon sheet was 3mg/cm2；
50 wt% of polystyrene, 25 wt% of acetylene black, 25 wt% of 1530m2Mixing the activated carbon material per gram into enough deionized water, and uniformly stirring. Heating at 80 deg.C, stirring to remove 80 wt% water solvent, and naturally cooling to room temperature to obtain black viscous colloid. The total mass of the activated carbon material and the conductive carbon material is the same as the mass of the solvent of the black viscous colloid;
and coating the lead paste on a lead alloy grid, and curing to obtain a green plate. Cutting a carbon sheet into pieces according to the length and the width of a lead alloy grid, then respectively pressing and covering two cut carbon sheets on two sides of a green plate by using the pressure of 3Mpa, uniformly coating black viscous colloid accounting for 50% of the mass of the carbon sheet on the surface of the carbon sheet, naturally evaporating 10 wt% of water to dryness, and then soaking an electrode in 5M sulfuric acid solution for storage to obtain an external application type lead-carbon battery negative electrode plate;
the drying and curing steps are as follows:
1) keeping the temperature at 40 ℃ and the air humidity at 99% for 12h
2) Keeping the temperature at 45 ℃ and the air humidity at 99 percent for 14h
3) Keeping the temperature at 45 ℃ and the air humidity at 75% for 8h
4) The temperature is 55 ℃, the air humidity is 90 percent, and the constant temperature is kept for 8 hours
5) Keeping the temperature at 65 ℃ and the air humidity at 80 percent for 10 hours
6) Keeping the temperature at 45 ℃ and the air humidity at 75% for 4h
7) Keeping the temperature at 65 ℃ and the air humidity at 30 percent for 4 hours
8) Keeping the temperature at 75 ℃ and the air humidity at 30 percent for 12h
Example 2:
uniformly mixing 85% of lead powder, 3 wt% of humic acid, 3 wt% of 10mm long polyester, 3 wt% of barium sulfate, 3 wt% of sodium lignosulfonate and 3 wt% of acetylene black to prepare an active substance, and slowly adding 8 wt% of water and 12.5 wt% of 4.6mol/L sulfuric acid into the mixed active substance in sequence and uniformly stirring to prepare lead plaster;
85 wt% 1960m2The active carbon material per gram, the carbon black with the weight percentage of 10 percent and the polytetrafluoroethylene with the weight percentage of 5 percent are evenly mixed in the absolute ethyl alcohol, and the mass of the absolute ethyl alcohol is 180 times of that of the active carbon material. The anhydrous ethanol was evaporated to dryness by stirring at constant temperature of 90 ℃ to obtain a uniform mixture. 0.3ml/mg of absolute ethanol is added into the mixture to be rolled into a sheet, and then the sheet is dried at 90 ℃ for 12 hours to obtain the carbon sheet. The loading amount of the mixture in the carbon sheet was 3mg/cm2；
55 wt% of polystyrene, 25 wt% of acetylene black, and 20 wt% of 1530m2Mixing the activated carbon material per gram into enough deionized water, and uniformly stirring. Heating at 80 deg.C, stirring to remove 80 wt% water solvent, and naturally cooling to room temperature to obtain black viscous colloid. The total mass of the activated carbon material and the conductive carbon material is the same as the mass of the solvent of the black viscous colloid;
and coating the lead paste on a lead alloy grid, and curing to obtain a green plate. Cutting a carbon sheet into pieces according to the length and the width of a lead alloy grid, then respectively pressing and covering two cut carbon sheets on two sides of a green plate by using the pressure of 3Mpa, uniformly coating black viscous colloid accounting for 50% of the mass of the carbon sheet on the surface of the carbon sheet, naturally evaporating 10 wt% of water to dryness, and then soaking an electrode in 5M sulfuric acid solution for storage to obtain an external application type lead-carbon battery negative electrode plate;
the drying and curing steps are as follows:
1) keeping the temperature at 40 ℃ and the air humidity at 99% for 12h
2) Keeping the temperature at 45 ℃ and the air humidity at 99 percent for 14h
3) Keeping the temperature at 45 ℃ and the air humidity at 75% for 8h
4) The temperature is 55 ℃, the air humidity is 90 percent, and the constant temperature is kept for 8 hours
5) Keeping the temperature at 65 ℃ and the air humidity at 80 percent for 10 hours
6) Keeping the temperature at 45 ℃ and the air humidity at 75% for 4h
7) Keeping the temperature at 65 ℃ and the air humidity at 30 percent for 4 hours
8) Keeping the temperature at 75 ℃ and the air humidity at 30 percent for 12h
Example 3:
uniformly mixing 85% of lead powder, 3 wt% of humic acid, 3 wt% of 10mm long polyester, 3 wt% of barium sulfate, 3 wt% of sodium lignosulfonate and 3 wt% of acetylene black to prepare an active substance, and slowly adding 8 wt% of water and 12.5 wt% of 4.6mol/L sulfuric acid into the mixed active substance in sequence and uniformly stirring to prepare lead plaster;
85 wt% 1960m2The active carbon material per gram, the carbon black with the weight percentage of 10 percent and the polytetrafluoroethylene with the weight percentage of 5 percent are evenly mixed in the absolute ethyl alcohol, and the mass of the absolute ethyl alcohol is 180 times of that of the active carbon material. The anhydrous ethanol was evaporated to dryness by stirring at constant temperature of 90 ℃ to obtain a uniform mixture. 0.3ml/mg of absolute ethanol is added into the mixture to be rolled into a sheet, and then the sheet is dried at 90 ℃ for 12 hours to obtain the carbon sheet. The loading amount of the mixture in the carbon sheet was 3mg/cm2；
60 wt% of polystyrene, 20 wt% of acetylene black and 20 wt% of 1530m2Mixing the activated carbon material per gram into enough deionized water, and uniformly stirring. Heating at 80 deg.C, stirring to remove 80 wt% water solvent, and naturally cooling to room temperature to obtain black viscous colloid. The total mass of the activated carbon material and the conductive carbon material is the same as the mass of the solvent of the black viscous colloid;
and coating the lead paste on a lead alloy grid, and curing to obtain a green plate. Cutting a carbon sheet into pieces according to the length and the width of a lead alloy grid, then respectively pressing and covering two cut carbon sheets on two sides of a green plate by using the pressure of 3Mpa, uniformly coating black viscous colloid accounting for 50% of the mass of the carbon sheet on the surface of the carbon sheet, naturally evaporating 10 wt% of water to dryness, and then soaking an electrode in 5M sulfuric acid solution for storage to obtain an external application type lead-carbon battery negative electrode plate;
the drying and curing steps are as follows:
1) keeping the temperature at 40 ℃ and the air humidity at 99% for 12h
2) Keeping the temperature at 45 ℃ and the air humidity at 99 percent for 14h
3) Keeping the temperature at 45 ℃ and the air humidity at 75% for 8h
4) The temperature is 55 ℃, the air humidity is 90 percent, and the constant temperature is kept for 8 hours
5) Keeping the temperature at 65 ℃ and the air humidity at 80 percent for 10 hours
6) Keeping the temperature at 45 ℃ and the air humidity at 75% for 4h
7) Keeping the temperature at 65 ℃ and the air humidity at 30 percent for 4 hours
8) Keeping the temperature at 75 ℃ and the air humidity at 30 percent for 12h
The external negative electrode prepared in the embodiment 1 to 3, a positive electrode plate of a lead-carbon battery, an AGM diaphragm and 4.7M sulfuric acid electrolyte are assembled into a 4Ah flooded battery, and the lead-carbon battery is prepared through internal formation. Performing HRPSoC test on the lead-carbon battery according to the following steps:
(1) discharging for 1.4h until 30% Soc is constant current of 0.5C;
(2) HRPSoC cycle:
a. charging: charging at 1C, 2.4V for 60s at constant current and constant voltage;
b. discharging: 0.45C constant current discharge for 59s, then 3C constant current discharge for 1 s;
c. the HRPSoC cycle was repeated until the voltage was less than 1.75V. Recording the cycle life;
example 1 a 100% DOD cycle test was performed in addition to the HRPSoC test:
(1) charging at constant current of 0.5A/g until the voltage reaches 2.4V;
(2) constant current discharge of 0.5A/g is carried out until the voltage reaches 1.75V
The 100% DOD cycle test result of example 1 is shown in fig. 1, and compared with an external application type lead-carbon battery without the electrode of the present invention, the capacity retention rate is improved from 76.01% to 83.75% after 2000 times, the charge-discharge efficiency is improved from 44.12% to 97.45%, the battery discharge capacity is improved by 250%, and the electrochemical property is improved significantly. The results of the HRPSoC test after assembling the batteries of examples 1-3 are shown in the following table, and it can be found that the composition of the gel has a large influence on the life of the battery, and that example 2 has the best charge and discharge stability and much higher cycle life than the other examples.
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 (10)
1. A preparation method of a high-power external application type lead-carbon battery cathode is characterized by comprising the following steps: at least comprises the following steps:
(1) preparation of lead plaster
Uniformly mixing 85-95 wt% of lead powder, 0.5-3 wt% of humic acid, 0.5-3 wt% of short fiber, 0.5-3 wt% of barium sulfate, 0.5-3 wt% of sodium lignosulfonate and 0.5-3 wt% of acetylene black to prepare an active substance, and slowly adding water accounting for 5.0-10.0 wt% of the total weight of the active substance and 10.0-15.0 wt% of sulfuric acid into the active substance and uniformly stirring to prepare lead plaster;
(2) preparation of carbon sheets
Uniformly mixing 80-90 wt% of activated carbon material, 5-10 wt% of conductive carbon material and 5-10 wt% of connecting agent in absolute ethyl alcohol, wherein the mass of the absolute ethyl alcohol is 150-fold and 200-fold of that of the activated carbon material. The anhydrous ethanol was evaporated to dryness by stirring at constant temperature of 90 ℃ to obtain a uniform mixture. Adding 0.1-0.3ml/mg absolute ethyl alcohol into the mixture, rolling into tablets, and drying at 90 ℃ for 12h to obtain the carbon tablets. The loading amount of the mixture in the carbon sheet is 2-3mg/cm2；
(3) Preparation of the gel
Mixing 50-60 wt% of adhesive, 10-20 wt% of conductive carbon material and 20-40 wt% of activated carbon material into sufficient deionized water, and stirring uniformly. Heating at 80 deg.C, stirring to remove 80 wt% water solvent, and naturally cooling to room temperature to obtain black viscous colloid. The total mass of the activated carbon material and the conductive carbon material is the same as the mass of the solvent of the black viscous colloid;
(4) preparation of external application type lead-carbon battery negative electrode plate
And (2) coating the lead plaster prepared in the step (1) on a lead alloy grid, and curing to obtain a green plate. Cutting the carbon sheet in the step (2) into sheets according to the length and width of the lead alloy grid, then respectively pressing the two cut carbon sheets on two sides of a green plate under the pressure of 2-4Mpa, uniformly coating black viscous colloid in the step (3) with the mass of 50% of the carbon sheets on the surface of the carbon sheet, naturally evaporating 10 wt% of water to dryness, and then soaking the electrode in a 5M sulfuric acid solution for storage to obtain the external application type lead-carbon battery negative electrode plate.
2. The method for preparing the negative electrode plate of the lead-carbon battery according to claim 1, which is characterized in that: the short fibers in the step (1) comprise one or more of terylene and acrylon, and the length of the fibers is 1-40 mm.
3. The method for preparing the negative electrode plate of the lead-carbon battery according to claim 1, which is characterized in that: the concentration of the sulfuric acid added in the step (1) is 4-5mol/L, and the adding speed is 1-5 mL/s.
4. The method for preparing the negative electrode plate of the lead-carbon battery according to claim 1, which is characterized in that: the specific surface area of the activated carbon material in the step (2) is 1500-2/g。
5. The method for preparing the negative electrode plate of the lead-carbon battery according to claim 1, which is characterized in that: the conductive carbon material in the step (2) is one or more of carbon black, acetylene black and colloidal graphite.
6. The method for preparing the negative electrode plate of the lead-carbon battery according to claim 1, which is characterized in that: and (3) in the step (2), the connecting agent is one or more of polyvinyl alcohol, polyvinylidene fluoride and polytetrafluoroethylene.
7. The method for preparing the negative electrode plate of the lead-carbon battery according to claim 1, which is characterized in that: the adhesive in the step (3) is one or more of polyvinyl alcohol, polystyrene, polyvinyl chloride and polycarbonate.
8. The method for preparing the negative electrode plate of the lead-carbon battery according to claim 1, which is characterized in that: activity in the step (3)The specific surface area of the carbon material is 1500-2/g。
9. The method for preparing the negative electrode plate of the lead-carbon battery according to claim 1, which is characterized in that: and (3) the conductive carbon material is one or more of carbon black, acetylene black and expanded graphite.
10. The method for preparing the negative electrode plate of the lead-carbon battery according to claim 1, which is characterized in that: the drying and curing step in the step (4) comprises the following steps:
1) keeping the temperature at 40 ℃ and the air humidity at 99% for 12h
2) Keeping the temperature at 45 ℃ and the air humidity at 99 percent for 14h
3) Keeping the temperature at 45 ℃ and the air humidity at 75% for 8h
4) The temperature is 55 ℃, the air humidity is 90 percent, and the constant temperature is kept for 8 hours
5) Keeping the temperature at 65 ℃ and the air humidity at 80 percent for 10 hours
6) Keeping the temperature at 45 ℃ and the air humidity at 75% for 4h
7) Keeping the temperature at 65 ℃ and the air humidity at 30 percent for 4 hours
8) Keeping the temperature at 75 ℃ and the air humidity at 30% for 12 h.
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Cited By (3)
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| CN111668456A (en) * | 2020-05-12 | 2020-09-15 | 吉林省凯禹电化学储能技术发展有限公司 | External application type lead-carbon start-stop battery negative plate and preparation method thereof and battery |
| CN111710835A (en) * | 2020-06-12 | 2020-09-25 | 吉林省凯禹电化学储能技术发展有限公司 | Preparation method of long-life external-application lead-carbon battery cathode |
| CN113506683A (en) * | 2020-06-12 | 2021-10-15 | 吉林大学 | Lead-carbon supercapacitor cathode and preparation method thereof |
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| US20120263977A1 (en) * | 2009-08-27 | 2012-10-18 | Jun Furukawa | Method for producing hybrid negative plate for lead-acid storage battery and lead-acid storage battery |
| CN110400907A (en) * | 2019-06-10 | 2019-11-01 | 吉林大学 | A kind of preparation method of external application formula lead carbon battery cathode |
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| US20120263977A1 (en) * | 2009-08-27 | 2012-10-18 | Jun Furukawa | Method for producing hybrid negative plate for lead-acid storage battery and lead-acid storage battery |
| CN110400907A (en) * | 2019-06-10 | 2019-11-01 | 吉林大学 | A kind of preparation method of external application formula lead carbon battery cathode |
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| CN111668456A (en) * | 2020-05-12 | 2020-09-15 | 吉林省凯禹电化学储能技术发展有限公司 | External application type lead-carbon start-stop battery negative plate and preparation method thereof and battery |
| CN111668456B (en) * | 2020-05-12 | 2021-05-25 | 吉林省凯禹电化学储能技术发展有限公司 | External application type lead-carbon start-stop battery negative plate and preparation method thereof and battery |
| CN111710835A (en) * | 2020-06-12 | 2020-09-25 | 吉林省凯禹电化学储能技术发展有限公司 | Preparation method of long-life external-application lead-carbon battery cathode |
| CN113506683A (en) * | 2020-06-12 | 2021-10-15 | 吉林大学 | Lead-carbon supercapacitor cathode and preparation method thereof |
| CN111710835B (en) * | 2020-06-12 | 2022-01-14 | 吉林省凯禹电化学储能技术发展有限公司 | Preparation method of long-life external-application lead-carbon battery cathode |
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