CN114267835A - Lead paste of lead-acid storage battery, preparation method of lead paste, pole plate and curing process of pole plate - Google Patents
Lead paste of lead-acid storage battery, preparation method of lead paste, pole plate and curing process of pole plate Download PDFInfo
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- CN114267835A CN114267835A CN202111618790.6A CN202111618790A CN114267835A CN 114267835 A CN114267835 A CN 114267835A CN 202111618790 A CN202111618790 A CN 202111618790A CN 114267835 A CN114267835 A CN 114267835A
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- 239000002253 acid Substances 0.000 title claims abstract description 46
- 238000003860 storage Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000011505 plaster Substances 0.000 claims abstract description 45
- 239000000835 fiber Substances 0.000 claims abstract description 32
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims abstract description 23
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 16
- 230000007797 corrosion Effects 0.000 claims abstract description 14
- 238000005260 corrosion Methods 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
- 239000010439 graphite Substances 0.000 claims abstract description 11
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000009423 ventilation Methods 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000007580 dry-mixing Methods 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 230000003020 moisturizing effect Effects 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229960001922 sodium perborate Drugs 0.000 claims description 4
- 239000012418 sodium perborate tetrahydrate Substances 0.000 claims description 4
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 claims description 4
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 claims description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 229920001197 polyacetylene Polymers 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 2
- -1 polyparaphenylene Polymers 0.000 claims description 2
- 238000004080 punching Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005266 casting Methods 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910001439 antimony ion Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000001999 grid alloy Substances 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
Classifications
-
- 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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- Battery Electrode And Active Subsutance (AREA)
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 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 and 0.03-0.30% of accelerator. 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; in the solidified anode plate, the anode lead plaster and the corrosion layer of the screen punching plate grid are very uniform.
Description
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 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 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 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 concentration of the sulfuric acid solution is 50% by mass.
Preferably, the fumed silica has a specific surface area of 170 m2/g ~200m2/g。
The invention also provides 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 and fumed silica powder, dry-mixing for 30-480 s, and obtaining mixed dry powder with a paste mixer rotating speed of 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 provides a curing process of the lead-acid storage battery plate, wherein the positive plate of the lead-acid storage battery is dried on the surface, neatly stacked and then placed in a curing chamber for curing; the curing comprises the following stages:
in the plate-entering and moisturizing stage, the temperature of the curing chamber is controlled to be 45 ℃, the relative humidity is controlled to be 99%, and the curing time is less than or equal to 6 h; the fan frequency of ventilation is 40% of the rated frequency of the fan;
in the stage 1 of curing, the temperature of a curing chamber is controlled to be 60 ℃, the relative humidity is controlled to be 99 percent, and the curing time is not less than 1 h; the fan frequency of ventilation is 40% of the rated frequency of the fan;
in the stage 2 of curing, the temperature of a curing chamber is controlled to be 75 ℃, the relative humidity is controlled to be 99 percent, and the curing time is not less than 10 hours; the fan frequency of ventilation is 50% of the rated frequency of the fan;
in the 3 rd stage of curing, the temperature of a curing chamber is controlled to be 65 ℃, the relative humidity is controlled to be 99 percent, and the curing time is not less than 3 hours; the fan frequency of ventilation is 50% of the rated frequency of the fan;
in the 4 th stage of curing, the temperature of a curing chamber is controlled to be 60 ℃, the relative humidity is controlled to be 95 percent, and the curing time is not less than 10 hours; the fan frequency of ventilation is 60% of the rated frequency of the fan;
in the 5 th stage of curing, the temperature of a curing chamber is controlled to be 60 ℃, the relative humidity is controlled to be 90 percent, and the curing time is not less than 10 hours; the fan frequency of ventilation is 70% of the rated frequency of the fan;
in the 6 th stage of curing, the temperature of a curing chamber is controlled to be 60 ℃, the relative humidity is controlled to be 80 percent, and the curing time is not less than 10 hours; the frequency of the ventilated fan is 80% of the rated frequency of the fan;
in the 7 th stage of curing, the temperature of a curing chamber is controlled to be 75 ℃, the relative humidity is controlled to be 45 percent, and the curing time is not less than 3 hours; the fan frequency of ventilation is 90% of the rated frequency of the fan;
in the drying stage, the temperature of a curing chamber is controlled to be 75 ℃, the relative humidity is 0 percent, and the curing time is more than or equal to 16 hours; the fan frequency of ventilation is 100% of the rated fan frequency.
Preferably, in each curing stage, the maximum curing temperature is 75 ℃, and the curing time is more than or equal to 10 hours under the condition that the relative humidity is 99 percent.
Preferably, the curing comprises the following stages:
in the plate-entering and moisturizing stage, the temperature of a curing chamber is controlled to be 45 ℃, the relative humidity is controlled to be 99%, and the curing time is 6 hours; the fan frequency of ventilation is 40% of the rated frequency of the fan;
in the stage 1 of curing, the temperature of a curing chamber is controlled to be 60 ℃, the relative humidity is controlled to be 99 percent, and the curing time is 1 h; the fan frequency of ventilation is 40% of the rated frequency of the fan;
in the stage 2 of curing, the temperature of a curing chamber is controlled to be 75 ℃, the relative humidity is controlled to be 99 percent, and the curing time is 10 hours; the fan frequency of ventilation is 50% of the rated frequency of the fan;
in the 3 rd stage of curing, the temperature of a curing chamber is controlled to be 65 ℃, the relative humidity is controlled to be 99 percent, and the curing time is 11 hours; the fan frequency of ventilation is 50% of the rated frequency of the fan;
in the 4 th stage of curing, the temperature of a curing chamber is controlled to be 60 ℃, the relative humidity is controlled to be 95%, and the curing time is 10 hours; the fan frequency of ventilation is 60% of the rated frequency of the fan;
in the 5 th stage of curing, the temperature of a curing chamber is controlled to be 60 ℃, the relative humidity is controlled to be 90 percent, and the curing time is controlled to be 10 hours; the fan frequency of ventilation is 70% of the rated frequency of the fan;
in the 6 th stage of curing, the temperature of a curing chamber is controlled to be 60 ℃, the relative humidity is controlled to be 80 percent, and the curing time is controlled to be 10 hours; the frequency of the ventilated fan is 80% of the rated frequency of the fan;
in the 7 th stage of curing, the temperature of a curing chamber is controlled to be 75 ℃, the relative humidity is controlled to be 45 percent, and the curing time is controlled to be 3 hours; the fan frequency of ventilation is 90% of the rated frequency of the fan;
in the drying stage, the temperature of a curing chamber is controlled to be 75 ℃, the relative humidity is 0%, and the curing time is 16 h; the fan frequency of ventilation is 100% of the rated fan frequency.
The fan is adopted for ventilation of the curing chamber, and the air quantity entering the curing chamber is controlled by controlling the operating frequency of the fans for ventilation at different stages based on the rated frequency of the fan in the ventilation process.
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 curing process is assembled into a lead-acid storage battery, and in the service period of the lead-acid storage battery in the use process, the tin ions and the antimony ions in the positive pole lead plaster can promote PbO on the positive pole plate 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.
Through the curing process, in the cured positive electrode plate, the positive lead paste and the corrosion layer of the screen punching grid are very uniform, and a lead-acid storage battery (more than or equal to 4 batteries/group) assembled by the positive electrode plate produced by the formula and the process has small load pressure difference and good consistency in the use process, and the 100 percent DOD cycle life of the lead-acid storage battery is more than or equal to 250 times.
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; in the solidified anode plate, the anode lead plaster and the corrosion layer of the screen punching plate grid are very uniform.
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:
82.17% 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 and 0.28% 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 accelerator is sodium perborate tetrahydrate. The length of the conductive short fiber is 3 mm; the conductive short fiber is polyaniline conductive fiber.
The mass percentage concentration of the sulfuric acid solution is 50%. The fumed silica has a specific surface area of 180m2/g。
The preparation method of the lead paste of the lead-acid storage battery 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 and fumed silica powder, dry-mixing for 200s, and obtaining mixed dry powder with the rotating speed of a paste mixing machine being 160 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 160 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 11 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 5min at the rotating speed of the paste mixer of 210 r/min;
s5, measuring the apparent density of the lead paste to be 4.36g/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 curing process of the lead-acid storage battery polar plate comprises the steps of drying the surface of the positive polar plate of the lead-acid storage battery, neatly stacking the positive polar plate, and then putting the positive polar plate into a curing chamber for curing, wherein the rated frequency of a fan of the curing chamber is 50 Hz; the curing comprises the following stages:
in the plate-entering and moisturizing stage, the temperature of a curing chamber is controlled to be 45 ℃, the relative humidity is controlled to be 99%, and the curing time is 6 hours; the frequency of a ventilating fan is 20 Hz;
in the stage 1 of curing, the temperature of a curing chamber is controlled to be 60 ℃, the relative humidity is controlled to be 99 percent, and the curing time is 1 h; the frequency of a ventilating fan is 20 Hz;
in the stage 2 of curing, the temperature of a curing chamber is controlled to be 75 ℃, the relative humidity is controlled to be 99 percent, and the curing time is 10 hours; the frequency of a ventilating fan is 25 Hz;
in the 3 rd stage of curing, the temperature of a curing chamber is controlled to be 65 ℃, the relative humidity is controlled to be 99 percent, and the curing time is 11 hours; the frequency of a ventilating fan is 25 Hz;
in the 4 th stage of curing, the temperature of a curing chamber is controlled to be 60 ℃, the relative humidity is controlled to be 95%, and the curing time is 10 hours; the frequency of a ventilating fan is 30 Hz;
in the 5 th stage of curing, the temperature of a curing chamber is controlled to be 60 ℃, the relative humidity is controlled to be 90 percent, and the curing time is controlled to be 10 hours; the frequency of a ventilating fan is 35 Hz;
in the 6 th stage of curing, the temperature of a curing chamber is controlled to be 60 ℃, the relative humidity is controlled to be 80 percent, and the curing time is controlled to be 10 hours; the frequency of a ventilating fan is 40 Hz;
in the 7 th stage of curing, the temperature of a curing chamber is controlled to be 75 ℃, the relative humidity is controlled to be 45 percent, and the curing time is controlled to be 3 hours; the frequency of a ventilating fan is 45 Hz;
in the drying stage, the temperature of a curing chamber is controlled to be 75 ℃, the relative humidity is 0%, and the curing time is 16 h; the fan frequency of the ventilation is 50 Hz.
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:
80.25% of lead powder, 7.7% of sulfuric acid solution, 9.5% of water, 0.12% of conductive short fiber, 0.2% of colloidal graphite, 0.13% of stannous sulfate, 0.15% of antimony trioxide, 1.7% of fumed silica powder and 0.25% 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 accelerator is potassium perborate. The length of the conductive short fiber is 2.5 mm; the conductive short fiber is polypyrrole conductive fiber. The mass percentage concentration of the sulfuric acid solution is 50%. The fumed silica has a specific surface area of 170 m2/g。
The preparation method of the lead paste of the lead-acid storage battery 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 and fumed silica powder, dry-mixing for 60s, and mixing with a paste machine at a rotating speed of 200r/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 200r/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 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 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:
85% 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 and 0.03% 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 is sodium perborate. The length of the conductive short fiber is 3.5 mm; the conductive short fiber is polyacetylene conductive fiber.
The mass percentage concentration of the sulfuric acid solution is 50%. The fumed silica has a specific surface area of 200m2/g。
The preparation method of the lead paste of the lead-acid storage battery 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 and fumed silica powder, dry-mixing for 480s, and mixing with a paste machine at a rotating speed of 120r/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 120r/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 45 ℃ 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 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 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 mass percentage concentration of the sulfuric acid solution is 50%.
5. The lead-acid battery lead paste of claim 1, wherein: the fumed silica has a specific surface area of 170 m2/g ~200m2/g。
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 and fumed silica powder, dry-mixing for 30-480 s, and obtaining mixed dry powder with a paste mixer rotating speed of 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 process for curing a lead-acid battery plate of claim 8, wherein: drying the surface of the positive electrode plate of the lead-acid storage battery, neatly stacking, and then placing the positive electrode plate into a curing chamber for curing; the curing comprises the following stages:
in the plate-entering and moisturizing stage, the temperature of the curing chamber is controlled to be 45 ℃, the relative humidity is controlled to be 99%, and the curing time is less than or equal to 6 h; the fan frequency of ventilation is 40% of the rated frequency of the fan;
in the stage 1 of curing, the temperature of a curing chamber is controlled to be 60 ℃, the relative humidity is controlled to be 99 percent, and the curing time is not less than 1 h; the fan frequency of ventilation is 40% of the rated frequency of the fan;
in the stage 2 of curing, the temperature of a curing chamber is controlled to be 75 ℃, the relative humidity is controlled to be 99 percent, and the curing time is not less than 10 hours; the fan frequency of ventilation is 50% of the rated frequency of the fan;
in the 3 rd stage of curing, the temperature of a curing chamber is controlled to be 65 ℃, the relative humidity is controlled to be 99 percent, and the curing time is not less than 3 hours; the fan frequency of ventilation is 50% of the rated frequency of the fan;
in the 4 th stage of curing, the temperature of a curing chamber is controlled to be 60 ℃, the relative humidity is controlled to be 95 percent, and the curing time is not less than 10 hours; the fan frequency of ventilation is 60% of the rated frequency of the fan;
in the 5 th stage of curing, the temperature of a curing chamber is controlled to be 60 ℃, the relative humidity is controlled to be 90 percent, and the curing time is not less than 10 hours; the fan frequency of ventilation is 70% of the rated frequency of the fan;
in the 6 th stage of curing, the temperature of a curing chamber is controlled to be 60 ℃, the relative humidity is controlled to be 80 percent, and the curing time is not less than 10 hours; the frequency of the ventilated fan is 80% of the rated frequency of the fan;
in the 7 th stage of curing, the temperature of a curing chamber is controlled to be 75 ℃, the relative humidity is controlled to be 45 percent, and the curing time is not less than 3 hours; the fan frequency of ventilation is 90% of the rated frequency of the fan;
in the drying stage, the temperature of a curing chamber is controlled to be 75 ℃, the relative humidity is 0 percent, and the curing time is more than or equal to 16 hours; the fan frequency of ventilation is 100% of the rated fan frequency.
10. The process of curing a lead-acid battery plate of claim 9, wherein: in each curing stage, the highest curing temperature is 75 ℃, and the curing time is more than or equal to 10 hours under the condition that the relative humidity is 99 percent.
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