CN114204033A - Lead paste of lead-acid storage battery, preparation method of lead paste, pole plate and high-temperature curing process of pole plate - Google Patents

Lead paste of lead-acid storage battery, preparation method of lead paste, pole plate and high-temperature curing process of pole plate Download PDF

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Publication number
CN114204033A
CN114204033A CN202111618541.7A CN202111618541A CN114204033A CN 114204033 A CN114204033 A CN 114204033A CN 202111618541 A CN202111618541 A CN 202111618541A CN 114204033 A CN114204033 A CN 114204033A
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lead
controlled
equal
temperature
curing
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CN202111618541.7A
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Chinese (zh)
Inventor
祝皎皎
梁天宝
孙茂汉
梁艳丽
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Henan Chilwee Genshore Power Co ltd
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Henan Chilwee Genshore Power Co ltd
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Priority to CN202111618541.7A priority Critical patent/CN114204033A/en
Publication of CN114204033A publication Critical patent/CN114204033A/en
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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
    • 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
    • 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
    • H01M4/14—Electrodes for lead-acid accumulators
    • H01M4/16—Processes of manufacture
    • H01M4/20—Processes of manufacture of pasted electrodes
    • H01M4/21—Drying 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
    • H01M4/36—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
    • 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
    • H01M4/624—Electric conductive fillers
    • 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
    • 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
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/73—Grids for lead-acid accumulators, e.g. frame plates
    • 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
    • H01M2004/028—Positive electrodes

Abstract

The invention relates to the technical field of storage batteries, and discloses lead paste of a lead-acid storage battery, a preparation method of the lead paste, a polar plate and a high-temperature curing process of the polar plate, wherein the lead paste of the lead-acid storage battery is positive lead paste; the positive lead plaster comprises the following components in percentage by mass: 70-90% of lead powder, 3-15% of sulfuric acid solution, 5-20% of water, 0.05-2% of conductive short fibers, 0.1-0.4% of colloidal graphite, 0.05-0.5% of stannous sulfate, 0.05-2.5% of antimony trioxide, 0.0-2.5% of fumed silica powder, 0.1-2.0% of tetrabasic lead sulfate and 0.03-0.30% of accelerator. The positive lead plaster can form a good corrosion layer with a positive grid; by adopting high-temperature curing, the corrosion layers of the positive grid and the positive lead plaster can be formed more quickly, the whole curing period can be shortened, and the utilization rate of curing equipment is improved.

Description

Lead paste of lead-acid storage battery, preparation method of lead paste, pole plate and high-temperature curing process of pole plate
Technical Field
The invention relates to the technical field of storage batteries, in particular to lead paste of a lead-acid storage battery, a preparation method of the lead paste, a polar plate and a high-temperature curing process of the polar plate.
Background
The traditional grid manufacturing process of the lead-acid storage battery is casting, the grid casting mold adopts cork powder as a mold release agent, the surface of the cast grid is rough, the contact surface with lead plaster is large, and a good interface can be formed after a polar plate is solidified. In the prior art, the screen punching plate grid obtained by adopting a continuous casting, rolling and continuous punching process has a relatively small specific surface area due to smooth section, and the contact area between the screen punching plate grid and lead paste is relatively small when the screen punching plate grid is used; in addition, the punched plate grid crystal grain obtained by adopting the continuous casting, rolling and punching process is more compact and has better corrosion resistance, and if the corrosion layer of the lead plaster and the grid corrosion interface does not reach the expectation or is not ideal enough after the polar plate is solidified, the battery can fail in advance.
Disclosure of Invention
The invention aims to overcome the defects and provides lead paste for a lead-acid storage battery, a preparation method of the lead paste, a polar plate and a high-temperature curing process of the polar plate.
In order to achieve the purpose, the invention is implemented according to the following technical scheme:
the lead-acid storage battery lead plaster is a positive electrode lead plaster; the positive lead plaster comprises the following components in percentage by mass:
70-90% of lead powder, 3-15% of sulfuric acid solution, 5-20% of water, 0.05-2% of conductive short fibers, 0.1-0.4% of colloidal graphite, 0.05-0.5% of stannous sulfate, 0.05-2.5% of antimony trioxide, 0.0-2.5% of fumed silica powder, 0.1-2.0% of tetrabasic lead sulfate (4 BS), and 0.03-0.30% of accelerator.
Preferably, the lead powder is an Shimadzu lead powder or a Barton lead powder.
Preferably, the length of the conductive short fiber is 2-4 mm; the conductive short fiber is at least one of polyaniline conductive fiber, polypyrrole conductive fiber, polyparaphenylene conductive fiber and polyacetylene conductive fiber.
Preferably, the accelerant promotes formation of a corrosive interface between the lead paste and the grid; the accelerator is at least one of potassium perborate, sodium perborate and sodium perborate tetrahydrate.
Preferably, the tetrabasic lead sulfate accounts for 0.5-1.0% of the total mass of the positive lead plaster.
Preferably, the fumed silica has a specific surface area of 170 m2/g ~200m2(ii)/g; the mass percentage concentration of the sulfuric acid solution is 50%.
The invention also discloses a preparation method of the lead paste of the lead-acid storage battery, which comprises the following steps:
s1, putting lead powder into a paste combining machine; then, sequentially adding conductive short fibers, colloidal graphite, stannous sulfate, antimony trioxide, fumed silica powder and tetrabasic lead sulfate, dry-mixing for 30-480 s, and obtaining mixed dry powder when the rotating speed of a paste mixing machine is 120-200 r/min;
s2, adding water into the mixed dry powder for mixing, wherein the mixing time is less than or equal to 1min, and the rotating speed of a paste mixing machine is 120-200 r/min, so as to obtain a mixed wet material; s3, adding a sulfuric acid solution into the wet mixed material, stirring and mixing, wherein the feeding speed of the sulfuric acid solution is 9-13 kg/min;
s4, adding an accelerant when the temperature of the materials in the paste mixer is 45-49 ℃ in the stirring process after the sulfuric acid solution is completely added, and then mixing for 4-6 min at the rotating speed of 180-240 r/min;
s5, measuring the apparent density of the lead paste to be 4.25-4.50 g/cm3And when the temperature of the lead paste is lower than 45 ℃, discharging the paste to obtain the anode lead paste.
Preferably, the temperature in the lead plaster machine is controlled to be less than or equal to 60 ℃ in the preparation process of the positive lead plaster.
The lead-acid storage battery positive plate is prepared by coating the positive lead plaster prepared by the preparation method on a positive grid; the positive grid is a punched grid; in the punched grid, the Sn content is more than 1.2 wt%.
The invention also discloses a high-temperature curing process of the lead-acid storage battery plate, which is characterized in that the positive plate of the lead-acid storage battery is dried on the surface, stacked in order and placed in a curing chamber for high-temperature curing; the high temperature curing includes the following stages:
in the 1 st stage, the temperature of a curing chamber is controlled to be 45 ℃, the relative humidity is more than or equal to 99 percent, and the curing time is less than or equal to 3 hours; the air volume is 40%;
in the 2 nd stage, the temperature of the curing chamber is controlled to be more than or equal to 96 ℃, the relative humidity is controlled to be more than or equal to 99 percent, and the curing time is controlled to be more than or equal to 3 hours; the air volume is 40%;
in the 3 rd stage, the temperature of the curing chamber is controlled to be more than or equal to 50 ℃, the relative humidity is controlled to be more than or equal to 97 percent, and the curing time is controlled to be more than or equal to 10 hours; the air volume is 50%;
in the 4 th stage, the temperature of the curing chamber is controlled to be more than or equal to 55 ℃, the relative humidity is controlled to be more than or equal to 97%, and the curing time is controlled to be more than or equal to 1 h; the air volume is 50%;
in the 5 th stage, the temperature of the curing chamber is controlled to be more than or equal to 55 ℃, the relative humidity is controlled to be more than or equal to 95%, and the curing time is controlled to be more than or equal to 8 h; the air volume is 50%;
in the 6 th stage, the temperature of the curing chamber is controlled to be more than or equal to 55 ℃, the relative humidity is controlled to be more than or equal to 90 percent, and the curing time is controlled to be more than or equal to 1 h; the air volume is 50%;
in the 7 th stage, the temperature of the curing chamber is controlled to be more than or equal to 55 ℃, the relative humidity is controlled to be more than or equal to 90 percent, and the curing time is controlled to be more than or equal to 8 hours; the air volume is 50%;
in the 8 th stage, the temperature of the curing chamber is controlled to be more than or equal to 55 ℃, the relative humidity is controlled to be more than or equal to 80 percent, and the curing time is controlled to be more than or equal to 1 h; the air volume is 50%;
in the 9 th stage, the temperature of the curing chamber is controlled to be more than or equal to 55 ℃, the relative humidity is controlled to be more than or equal to 80 percent, and the curing time is controlled to be more than or equal to 8 hours; the air volume is 50%;
in the 10 th stage, the temperature of the curing chamber is controlled to be more than or equal to 60 ℃, the relative humidity is controlled to be more than or equal to 45%, and the curing time is controlled to be more than or equal to 1 h; the air volume is 60%;
in the 11 th stage, the temperature of the curing chamber is controlled to be more than or equal to 60 ℃, the relative humidity is controlled to be more than or equal to 45 percent, and the curing time is controlled to be more than or equal to 7 hours; the air volume is 60%;
in the 12 th stage, the temperature of the curing chamber is controlled to be more than or equal to 65 ℃, the relative humidity is controlled to be more than or equal to 20%, and the curing time is controlled to be more than or equal to 5 h; the air volume is 80%;
in the 13 th stage, the temperature of the curing chamber is controlled to be less than or equal to 75 ℃, the relative humidity is 0 percent, and the curing time is controlled to be more than or equal to 13 hours; the air volume is 100%.
Preferably, in each high-temperature curing stage, the maximum curing temperature is 96 ℃, and the curing time is more than or equal to 3 hours under the condition that the relative humidity is 99%.
Preferably, the method comprises the following stages:
in the 1 st stage, the temperature of a curing chamber is controlled to be 45 ℃, the relative humidity is controlled to be 99 percent, and the curing time is less than or equal to 3 hours; the air volume is 40%;
in the 2 nd stage, the temperature of the curing chamber is controlled to be 96 ℃, the relative humidity is controlled to be 99 percent, and the curing time is controlled to be 3 hours; the air volume is 40%;
in the 3 rd stage, the temperature of the curing chamber is controlled to be 50 ℃, the relative humidity is controlled to be 97%, and the curing time is controlled to be 10 h; the air volume is 50%;
in the 4 th stage, the temperature of the curing chamber is controlled to be 55 ℃, the relative humidity is controlled to be 97 percent, and the curing time is controlled to be 1 h; the air volume is 50%;
in the 5 th stage, the temperature of the curing chamber is controlled to be 55 ℃, the relative humidity is controlled to be 95%, and the curing time is controlled to be 8 h; the air volume is 50%;
in the 6 th stage, the temperature of the curing chamber is controlled to be 55 ℃, the relative humidity is controlled to be 90 percent, and the curing time is controlled to be 1 h; the air volume is 50%;
in the 7 th stage, the temperature of the curing chamber is controlled to be 55 ℃, the relative humidity is controlled to be 90 percent, and the curing time is controlled to be 8 hours; the air volume is 50%;
in the 8 th stage, the temperature of the curing chamber is controlled to be 55 ℃, the relative humidity is controlled to be 80 percent, and the curing time is controlled to be 1 h; the air volume is 50%;
in the 9 th stage, the temperature of the curing chamber is controlled to be 55 ℃, the relative humidity is controlled to be 80 percent, and the curing time is controlled to be 8 hours; the air volume is 50%;
in the 10 th stage, the temperature of a curing chamber is controlled to be 60 ℃, the relative humidity is controlled to be 45%, and the curing time is controlled to be 1 h; the air volume is 60%;
in the 11 th stage, the temperature of the curing chamber is controlled to be 60 ℃, the relative humidity is controlled to be 45%, and the curing time is controlled to be 7 h; the air volume is 60%;
in the 12 th stage, the temperature of a curing chamber is controlled to be 65 ℃, the relative humidity is controlled to be 20%, and the curing time is controlled to be 5 h; the air volume is 80%;
in the 13 th stage, the temperature of a curing chamber is controlled to be 75 ℃, the relative humidity is 0 percent, and the curing time is 13 h; the air volume is 100%.
The invention has the following function principle:
the positive lead plaster comprises the formula components of an accelerant, and the accelerant can promote the formation of a corrosion interface between the positive lead plaster and a positive grid. The promoter is at least one of potassium perborate, sodium perborate, and sodium perborate tetrahydrate. In the preparation process of the positive lead plaster, the accelerant is uniformly dispersed in the positive lead plaster, so that free lead is oxidized when a positive plate passes through a surface drying kiln and is solidified, the internal temperature of the positive plate is increased, and the free lead is decomposed to release oxygen to promote the oxidation of the contact surface of the positive lead plaster and a positive plate grid, thereby forming a good corrosion layer.
The positive pole plate prepared by the positive pole lead plaster and the high-temperature curing process is assembled into the lead-acid plateIn the service period of the storage battery in the use process, the tin ions and the antimony ions in the positive lead paste can promote PbO of the positive grid interfacen(n is less than or equal to 1.4, high resistance) oxidation to form PbOn(n is more than 1.6 and less than 2.0, and the resistance is low), so that the internal resistance of the interface of the positive lead paste and the positive grid is reduced, the charge acceptance is improved, and the PCL-1 effect in the use process of the lead-acid storage battery can be effectively inhibited. The Sn content in the screen punching plate grid alloy is more than 1.2 percent, and the Sn in the alloy strengthens PbO2The connection among the particles can effectively inhibit the PCL-2 effect in the use process of the lead-acid storage battery; thereby prolonging the cycle life of the lead-acid storage battery.
Tetrabasic lead sulfate (4 BS) is added into the positive lead plaster formula, the positive pole plate is solidified at the temperature of 96 ℃, regular 4BS small particles are generated in the lead plaster, and the lead plaster is charged and converted into regular alpha-PbO2The active material structure, thereby the cycle life of the lead-acid storage battery is prolonged. The lead-acid storage battery assembled by the positive pole plate prepared by the method and the process has 100 percent DOD cycle life of more than or equal to 350 times; in addition, due to the adoption of high-temperature curing, the corrosion layers of the positive grid and the positive lead plaster can be formed more quickly, the whole curing period can be shortened, and the utilization rate of curing equipment is improved.
Compared with the prior art, the invention has the beneficial effects that:
the positive lead plaster can form a good corrosion layer with a positive grid; the internal resistance of the interface of the positive lead paste and the positive grid is reduced, the charge receiving capacity is improved, and the PCL-1 effect of the lead-acid storage battery in the use process can be effectively inhibited; by adopting high-temperature curing, the corrosion layers of the positive grid and the positive lead plaster can be formed more quickly, the whole curing period can be shortened, and the utilization rate of curing equipment is improved.
Detailed Description
The present invention will be further described with reference to specific examples, which are illustrative of the invention and are not to be construed as limiting the invention.
Example 1
The lead-acid storage battery lead plaster is a positive electrode lead plaster; the positive lead plaster comprises the following components in percentage by mass:
81.42% of lead powder, 7% of sulfuric acid solution, 8% of water, 0.1% of conductive short fibers, 0.25% of colloidal graphite, 0.1% of stannous sulfate, 0.1% of antimony trioxide, 2.0% of fumed silica powder, 0.75% of tetrabasic lead sulfate (4 BS) and 0.28% of accelerant.
The lead powder is Shimadzu lead powder; the accelerant promotes the formation of a corrosion interface between the lead paste and the grid; the accelerator is potassium perborate. The length of the conductive short fiber is 3 mm; the conductive short fiber is polyaniline conductive fiber. The fumed silica has a specific surface area of 185m2(ii)/g; the mass percentage concentration of the sulfuric acid solution is 50%.
The invention also discloses a preparation method of the lead paste of the lead-acid storage battery, which comprises the following steps:
s1, putting lead powder into a paste combining machine; then, sequentially adding conductive short fibers, colloidal graphite, stannous sulfate, antimony trioxide, fumed silica powder and tetrabasic lead sulfate, dry mixing for 260s, and mixing with a paste machine at a rotating speed of 160r/min to obtain mixed dry powder;
s2, adding water into the mixed dry powder for mixing for less than or equal to 1min, and mixing with a paste machine at a rotating speed of 160r/min to obtain a mixed wet material;
s3, adding a sulfuric acid solution into the wet mixed material, stirring and mixing, wherein the feeding speed of the sulfuric acid solution is 11 kg/min;
s4, adding an accelerant when the temperature of the materials in the paste mixer is 46 ℃ in the stirring process after the sulfuric acid solution is completely added, and then mixing for 5min at the rotating speed of the paste mixer of 210 r/min;
s5, measuring the apparent density of the lead paste to be 4.30-4.40 g/cm3And when the temperature of the lead paste is lower than 45 ℃, discharging the paste to obtain the anode lead paste.
In the preparation process of the positive lead plaster, the temperature in the lead plaster machine is controlled to be less than or equal to 60 ℃.
The lead-acid storage battery positive plate is prepared by coating the positive lead plaster prepared by the preparation method on a positive grid; the positive grid is a punched grid; in the punched grid, the Sn content is more than 1.2 wt%.
The high-temperature curing process of the lead-acid storage battery plate comprises the steps of drying the surface of the positive plate of the lead-acid storage battery, neatly stacking the positive plate, and placing the positive plate into a curing chamber for high-temperature curing; the high temperature curing includes the following stages:
in the 1 st stage, the temperature of a curing chamber is controlled to be 45 ℃, the relative humidity is controlled to be 99 percent, and the curing time is less than or equal to 3 hours; the air volume is 40%;
in the 2 nd stage, the temperature of the curing chamber is controlled to be 96 ℃, the relative humidity is controlled to be 99 percent, and the curing time is controlled to be 3 hours; the air volume is 40%;
in the 3 rd stage, the temperature of the curing chamber is controlled to be 50 ℃, the relative humidity is controlled to be 97%, and the curing time is controlled to be 10 h; the air volume is 50%;
in the 4 th stage, the temperature of the curing chamber is controlled to be 55 ℃, the relative humidity is controlled to be 97 percent, and the curing time is controlled to be 1 h; the air volume is 50%;
in the 5 th stage, the temperature of the curing chamber is controlled to be 55 ℃, the relative humidity is controlled to be 95%, and the curing time is controlled to be 8 h; the air volume is 50%;
in the 6 th stage, the temperature of the curing chamber is controlled to be 55 ℃, the relative humidity is controlled to be 90 percent, and the curing time is controlled to be 1 h; the air volume is 50%;
in the 7 th stage, the temperature of the curing chamber is controlled to be 55 ℃, the relative humidity is controlled to be 90 percent, and the curing time is controlled to be 8 hours; the air volume is 50%;
in the 8 th stage, the temperature of the curing chamber is controlled to be 55 ℃, the relative humidity is controlled to be 80 percent, and the curing time is controlled to be 1 h; the air volume is 50%;
in the 9 th stage, the temperature of the curing chamber is controlled to be 55 ℃, the relative humidity is controlled to be 80 percent, and the curing time is controlled to be 8 hours; the air volume is 50%;
in the 10 th stage, the temperature of a curing chamber is controlled to be 60 ℃, the relative humidity is controlled to be 45%, and the curing time is controlled to be 1 h; the air volume is 60%;
in the 11 th stage, the temperature of the curing chamber is controlled to be 60 ℃, the relative humidity is controlled to be 45%, and the curing time is controlled to be 7 h; the air volume is 60%;
in the 12 th stage, the temperature of a curing chamber is controlled to be 65 ℃, the relative humidity is controlled to be 20%, and the curing time is controlled to be 5 h; the air volume is 80%;
in the 13 th stage, the temperature of a curing chamber is controlled to be 75 ℃, the relative humidity is 0 percent, and the curing time is 13 h; the air volume is 100%.
Example 2
The lead-acid storage battery lead plaster is a positive electrode lead plaster; the positive lead plaster comprises the following components in percentage by mass:
79.75% of lead powder, 7.7% of sulfuric acid solution, 9.5% of water, 0.12% of conductive short fibers, 0.2% of colloidal graphite, 0.13% of stannous sulfate, 0.15% of antimony trioxide, 1.7% of fumed silica powder, 0.5% of tetrabasic lead sulfate (4 BS) and 0.25% of accelerator.
The lead powder is a Barton type lead powder. The accelerant promotes the formation of a corrosion interface between the lead paste and the grid; the accelerator sodium perborate. The length of the conductive short fiber is 2.5 mm; the conductive short fiber is polypyrrole conductive fiber. The fumed silica has a specific surface area of 170 m2(ii)/g; the mass percentage concentration of the sulfuric acid solution is 50%.
The invention also discloses a preparation method of the lead paste of the lead-acid storage battery, which comprises the following steps:
s1, putting lead powder into a paste combining machine; then, sequentially adding conductive short fibers, colloidal graphite, stannous sulfate, antimony trioxide, fumed silica powder and tetrabasic lead sulfate, dry-mixing for 60s, and obtaining mixed dry powder when the rotating speed of a paste mixing machine is 120 r/min;
s2, adding water into the mixed dry powder for mixing for less than or equal to 1min, and mixing with a paste machine at a rotating speed of 120 r/min to obtain a mixed wet material;
s3, adding a sulfuric acid solution into the wet mixed material, stirring and mixing, wherein the feeding speed of the sulfuric acid solution is 9 kg/min;
s4, adding an accelerant when the temperature of the materials in the paste mixer is 49 ℃ in the stirring process after the sulfuric acid solution is completely added, and then mixing for 4min at the paste mixer rotation speed of 180 r/min;
s5, measuring the apparent density of the lead paste to be 4.25g/cm3And when the temperature of the lead paste is lower than 45 ℃, discharging the paste to obtain the anode lead paste.
In the preparation process of the positive lead plaster, the temperature in the lead plaster machine is controlled to be less than or equal to 60 ℃.
The lead-acid storage battery positive plate is prepared by coating the positive lead plaster prepared by the preparation method on a positive grid; the positive grid is a punched grid; in the punched grid, the Sn content is more than 1.2 wt%.
The high temperature curing process for the lead acid battery plate was the same as in example 1.
Example 3
The lead-acid storage battery lead plaster is a positive electrode lead plaster; the positive lead plaster comprises the following components in percentage by mass:
84% of lead powder, 6.34% of sulfuric acid solution, 5.3% of water, 0.1% of conductive short fibers, 0.4% of colloidal graphite, 0.13% of stannous sulfate, 0.2% of antimony trioxide, 2.5% of fumed silica powder, 1.0% of tetrabasic lead sulfate (4 BS) and 0.03% of accelerator.
The lead powder is Shimadzu lead powder; the accelerant promotes the formation of a corrosion interface between the lead paste and the grid; the accelerant is; sodium perborate tetrahydrate. The length of the conductive short fiber is 3.5 mm; the conductive short fiber is polyacetylene conductive fiber. The fumed silica has a specific surface area of 200m2(ii)/g; the mass percentage concentration of the sulfuric acid solution is 50%.
The invention also discloses a preparation method of the lead paste of the lead-acid storage battery, which comprises the following steps:
s1, putting lead powder into a paste combining machine; then, sequentially adding conductive short fibers, colloidal graphite, stannous sulfate, antimony trioxide, fumed silica powder and tetrabasic lead sulfate, dry-mixing for 480s, and mixing with a paste machine at a rotating speed of 200 r/min to obtain mixed dry powder;
s2, adding water into the mixed dry powder for mixing for less than or equal to 1min, and mixing with a paste machine at a rotating speed of 200 r/min to obtain a mixed wet material;
s3, adding a sulfuric acid solution into the wet mixed material, stirring and mixing, wherein the feeding speed of the sulfuric acid solution is 13 kg/min;
s4, adding an accelerant when the temperature of the materials in the paste mixer is 47 ℃ in the stirring process after the sulfuric acid solution is completely added, and then mixing for 6min at the rotating speed of the paste mixer of 240 r/min;
s5, measuring the apparent density of the lead paste to be 4.50g/cm3And when the temperature of the lead paste is lower than 45 ℃, discharging the paste to obtain the anode lead paste.
In the preparation process of the positive lead plaster, the temperature in the lead plaster machine is controlled to be less than or equal to 60 ℃.
The lead-acid storage battery positive plate is prepared by coating the positive lead plaster prepared by the preparation method on a positive grid; the positive grid is a punched grid; in the punched grid, the Sn content is more than 1.2 wt%.
The high temperature curing process for the lead acid battery plate was the same as in example 1.
The technical solution of the present invention is not limited to the limitations of the above specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention.

Claims (10)

1. Lead plaster of lead-acid storage battery, which is characterized in that: the lead plaster of the lead-acid storage battery is positive lead plaster; the positive lead plaster comprises the following components in percentage by mass:
70-90% of lead powder, 3-15% of sulfuric acid solution, 5-20% of water, 0.05-2% of conductive short fibers, 0.1-0.4% of colloidal graphite, 0.05-0.5% of stannous sulfate, 0.05-2.5% of antimony trioxide, 0.0-2.5% of fumed silica powder, 0.1-2.0% of tetrabasic lead sulfate and 0.03-0.30% of accelerator.
2. The lead-acid battery lead paste of claim 1, wherein: the lead powder is Shimadzu lead powder or Baton lead powder; the length of the conductive short fiber is 2-4 mm; the conductive short fiber is at least one of polyaniline conductive fiber, polypyrrole conductive fiber, polyparaphenylene conductive fiber and polyacetylene conductive fiber.
3. The lead-acid battery lead paste of claim 1, wherein: the accelerant promotes the formation of a corrosion interface between the lead paste and the grid; the accelerator is at least one of potassium perborate, sodium perborate and sodium perborate tetrahydrate.
4. The lead-acid battery lead paste of claim 1, wherein: the tetrabasic lead sulfate accounts for 0.5-1.0% of the total mass of the positive lead plaster.
5. The lead-acid battery lead paste of claim 1, wherein: the fumed silica has a specific surface area of 170 m2/g ~200m2(ii)/g; the mass percentage concentration of the sulfuric acid solution is 50%.
6. The method for preparing lead paste for lead-acid batteries according to any of claims 1 to 5, characterized in that it comprises the following steps: s1, putting lead powder into a paste combining machine; then, sequentially adding conductive short fibers, colloidal graphite, stannous sulfate, antimony trioxide, fumed silica powder and tetrabasic lead sulfate, dry-mixing for 30-480 s, and obtaining mixed dry powder when the rotating speed of a paste mixing machine is 120-200 r/min;
s2, adding water into the mixed dry powder for mixing, wherein the mixing time is less than or equal to 1min, and the rotating speed of a paste mixing machine is 120-200 r/min, so as to obtain a mixed wet material; s3, adding a sulfuric acid solution into the wet mixed material, stirring and mixing, wherein the feeding speed of the sulfuric acid solution is 9-13 kg/min;
s4, adding an accelerant when the temperature of the materials in the paste mixer is 45-49 ℃ in the stirring process after the sulfuric acid solution is completely added, and then mixing for 4-6 min at the rotating speed of 180-240 r/min;
s5, measuring the apparent density of the lead paste to be 4.25-4.50 g/cm3And when the temperature of the lead paste is lower than 45 ℃, discharging the paste to obtain the anode lead paste.
7. The method for preparing lead paste for lead-acid storage batteries according to claim 6, characterized in that: in the preparation process of the positive lead plaster, the temperature in the lead plaster machine is controlled to be less than or equal to 60 ℃.
8. Lead-acid storage battery polar plate, its characterized in that: coating the positive lead plaster prepared by the preparation method of any one of claims 6 to 7 on a positive grid to prepare a positive plate of the lead-acid storage battery; the positive grid is a punched grid; in the punched grid, the Sn content is more than 1.2 wt%.
9. The high temperature curing process for lead acid battery plates of claim 8, wherein: drying the surface of the positive electrode plate of the lead-acid storage battery, neatly stacking, and placing the positive electrode plate into a curing chamber for high-temperature curing; the high temperature curing includes the following stages:
in the 1 st stage, the temperature of a curing chamber is controlled to be 45 ℃, the relative humidity is more than or equal to 99 percent, and the curing time is less than or equal to 3 hours; the air volume is 40%;
in the 2 nd stage, the temperature of the curing chamber is controlled to be more than or equal to 96 ℃, the relative humidity is controlled to be more than or equal to 99 percent, and the curing time is controlled to be more than or equal to 3 hours; the air volume is 40%;
in the 3 rd stage, the temperature of the curing chamber is controlled to be more than or equal to 50 ℃, the relative humidity is controlled to be more than or equal to 97 percent, and the curing time is controlled to be more than or equal to 10 hours; the air volume is 50%;
in the 4 th stage, the temperature of the curing chamber is controlled to be more than or equal to 55 ℃, the relative humidity is controlled to be more than or equal to 97%, and the curing time is controlled to be more than or equal to 1 h; the air volume is 50%;
in the 5 th stage, the temperature of the curing chamber is controlled to be more than or equal to 55 ℃, the relative humidity is controlled to be more than or equal to 95%, and the curing time is controlled to be more than or equal to 8 h; the air volume is 50%;
in the 6 th stage, the temperature of the curing chamber is controlled to be more than or equal to 55 ℃, the relative humidity is controlled to be more than or equal to 90 percent, and the curing time is controlled to be more than or equal to 1 h; the air volume is 50%;
in the 7 th stage, the temperature of the curing chamber is controlled to be more than or equal to 55 ℃, the relative humidity is controlled to be more than or equal to 90 percent, and the curing time is controlled to be more than or equal to 8 hours; the air volume is 50%;
in the 8 th stage, the temperature of the curing chamber is controlled to be more than or equal to 55 ℃, the relative humidity is controlled to be more than or equal to 80 percent, and the curing time is controlled to be more than or equal to 1 h; the air volume is 50%;
in the 9 th stage, the temperature of the curing chamber is controlled to be more than or equal to 55 ℃, the relative humidity is controlled to be more than or equal to 80 percent, and the curing time is controlled to be more than or equal to 8 hours; the air volume is 50%;
in the 10 th stage, the temperature of the curing chamber is controlled to be more than or equal to 60 ℃, the relative humidity is controlled to be more than or equal to 45%, and the curing time is controlled to be more than or equal to 1 h; the air volume is 60%;
in the 11 th stage, the temperature of the curing chamber is controlled to be more than or equal to 60 ℃, the relative humidity is controlled to be more than or equal to 45 percent, and the curing time is controlled to be more than or equal to 7 hours; the air volume is 60%;
in the 12 th stage, the temperature of the curing chamber is controlled to be more than or equal to 65 ℃, the relative humidity is controlled to be more than or equal to 20%, and the curing time is controlled to be more than or equal to 5 h; the air volume is 80%;
in the 13 th stage, the temperature of the curing chamber is controlled to be less than or equal to 75 ℃, the relative humidity is 0 percent, and the curing time is controlled to be more than or equal to 13 hours; the air volume is 100%.
10. The high temperature curing process of lead acid battery plates of claim 9, wherein: in each high-temperature curing stage, the highest curing temperature is 96 ℃, and the curing time is more than or equal to 3 hours under the condition that the relative humidity is 99 percent.
CN202111618541.7A 2021-12-28 2021-12-28 Lead paste of lead-acid storage battery, preparation method of lead paste, pole plate and high-temperature curing process of pole plate Pending CN114204033A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115842106A (en) * 2023-02-20 2023-03-24 淄博火炬能源有限责任公司 Plate type positive electrode of lead-acid battery and manufacturing process thereof

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10125329A (en) * 1996-10-24 1998-05-15 Tokuyama Corp Positive electrode plate and lead-acid battery
CN1894810A (en) * 2003-10-21 2007-01-10 约翰逊控制技术公司 Battery paste material and method
CN102664256A (en) * 2012-04-27 2012-09-12 天能电池集团有限公司 Anode lead plaster of power lead-acid storage battery polar plate
CN103943831A (en) * 2014-03-25 2014-07-23 超威电源有限公司 Electrode plate solidification technology for lead-acid battery
CN107887591A (en) * 2017-11-13 2018-04-06 河南超威电源有限公司 Improve lead plaster and cream of process for positive slab lattice of lead-acid accumulator and lead plaster adhesion and preparation method thereof
CN109509883A (en) * 2018-10-24 2019-03-22 山东久力工贸集团有限公司 A kind of lead-acid accumulator anode diachylon and preparation method
CN111129612A (en) * 2019-12-12 2020-05-08 双登集团股份有限公司 Method for prolonging cycle service life of positive electrode of lead-carbon battery
CN111600028A (en) * 2020-05-08 2020-08-28 浙江埃登达新能源材料有限公司 Storage battery polar plate lead plaster containing modified silicon powder, storage battery polar plate and storage battery
CN113506859A (en) * 2021-07-08 2021-10-15 江苏理士电池有限公司 Curing and drying method for long-life valve-regulated lead-acid storage battery wet lead plaster polar plate

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10125329A (en) * 1996-10-24 1998-05-15 Tokuyama Corp Positive electrode plate and lead-acid battery
CN1894810A (en) * 2003-10-21 2007-01-10 约翰逊控制技术公司 Battery paste material and method
CN102664256A (en) * 2012-04-27 2012-09-12 天能电池集团有限公司 Anode lead plaster of power lead-acid storage battery polar plate
CN103943831A (en) * 2014-03-25 2014-07-23 超威电源有限公司 Electrode plate solidification technology for lead-acid battery
CN107887591A (en) * 2017-11-13 2018-04-06 河南超威电源有限公司 Improve lead plaster and cream of process for positive slab lattice of lead-acid accumulator and lead plaster adhesion and preparation method thereof
CN109509883A (en) * 2018-10-24 2019-03-22 山东久力工贸集团有限公司 A kind of lead-acid accumulator anode diachylon and preparation method
CN111129612A (en) * 2019-12-12 2020-05-08 双登集团股份有限公司 Method for prolonging cycle service life of positive electrode of lead-carbon battery
CN111600028A (en) * 2020-05-08 2020-08-28 浙江埃登达新能源材料有限公司 Storage battery polar plate lead plaster containing modified silicon powder, storage battery polar plate and storage battery
CN113506859A (en) * 2021-07-08 2021-10-15 江苏理士电池有限公司 Curing and drying method for long-life valve-regulated lead-acid storage battery wet lead plaster polar plate

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115842106A (en) * 2023-02-20 2023-03-24 淄博火炬能源有限责任公司 Plate type positive electrode of lead-acid battery and manufacturing process thereof

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