CN112490437B - Formula of lead paste for positive plate of start-stop storage battery, positive plate and preparation method of positive plate - Google Patents
Formula of lead paste for positive plate of start-stop storage battery, positive plate and preparation method of positive plate Download PDFInfo
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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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/12—Construction or manufacture
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
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- H01M4/73—Grids for lead-acid accumulators, e.g. frame plates
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Abstract
The invention discloses a lead plaster formula of a start-stop storage battery positive plate, the positive plate and a preparation method thereof, wherein the lead plaster formula comprises the following raw materials in percentage by weight: 0.06-0.1% of tin phosphate, 0.01-0.05% of lithium phosphate, 0.03-0.1% of basic antimony carbonate, 0.1-0.3% of 4BS seed crystal, 0.01-0.03% of sodium perborate, 0.03-0.05% of nano Keqin black, 0.01-0.05% of graphite, 9-10% of dilute sulfuric acid, 10-12% of pure water, 0.1-0.12% of carbon fiber and the balance of lead powder with the oxidation degree of 71-73%. The invention can obviously improve the charge acceptance of the positive plate and the shallow cycle service life.
Description
Technical Field
The invention belongs to the technical field of storage batteries, and particularly relates to a positive plate lead paste formula of a start-stop storage battery, a positive plate and a preparation method of the positive plate.
Background
The starting lead-acid storage battery for the general vehicle has the performance requirements on the battery such as instantaneous starting discharge capacity and low-temperature starting performance, so that the starting and stopping system has higher requirements on the battery service life, charge and discharge and large-current discharge of the storage battery.
In order to improve the charge acceptance and the shallow cycle service life of the start-stop storage battery, a series of technical researches and improvements on slab lattice alloy, lead paste formula and curing process are needed.
Chinese patent publication No. CN105322181A discloses an EFB start-stop battery grid positive alloy, which is made of the following materials by weight percent: calcium: 0.055-0.062%, tin: 1.01% -1.07%, silver: 0.014-0.018%, aluminum: 0.023 to 0.029 percent, less than or equal to 0.001 percent of copper, less than or equal to 0.001 percent of arsenic, less than or equal to 0.004 percent of bismuth, less than or equal to 0.001 percent of iron, less than or equal to 0.0005 percent of antimony, less than or equal to 0.001 percent of nickel, and the balance of lead. The grid alloy can improve the mechanical strength of the grid and the corrosion resistance, but can not obviously improve the charge acceptance of the storage battery.
Chinese patent publication No. CN105047908A discloses an anode lead paste for an AGM start-stop battery and a preparation method thereof, wherein the anode lead paste comprises the following components in parts by weight: 70-90 parts of lead powder, 0.01-0.1 part of polyester fiber, 0.01-0.1 part of glass fiber, 0-0.8 part of 4BS seed crystal, 5-12 parts of red lead, 6-8 parts of sulfuric acid and 7-9 parts of pure water. The anode lead paste can improve the cycle life of the AGM start-stop storage battery, particularly 50% DOD cycle life, but can not obviously improve the charge acceptance of the storage battery.
The start-stop system is characterized in that the storage battery is required to frequently start an engine in a shallow discharge state, and the storage battery is required to have good charge acceptance and good shallow discharge cycle capacity, so that the start-stop lead-acid storage battery has higher requirements on the technology, and the technical difficulties of the start-stop lead-acid storage battery are the charge acceptance and the shallow cycle service life of the positive plate.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the positive plate lead paste formula of the start-stop storage battery positive plate, the positive plate and the preparation method thereof, which can improve the charge acceptance of the positive plate and prolong the service life of the positive plate in a shallow cycle.
The lead plaster formula of the positive plate of the start-stop storage battery comprises the following raw materials in percentage by weight: 0.06-0.1% of tin phosphate, 0.01-0.05% of lithium phosphate, 0.03-0.1% of basic antimony carbonate, 0.1-0.3% of 4BS seed crystal, 0.01-0.03% of sodium perborate, 0.03-0.05% of nano Keqin black, 0.01-0.05% of graphite and 9-10% of dilute sulfuric acid (the density is 1.4 g/cm)3) 10 to 12 percent of pure water, 0.1 to 0.12 percent of carbon fiber and the balance of lead powder with the oxidation degree of 71 to 73 percent.
The invention adds a plurality of conductive substances into the positive lead paste to improve the utilization rate of active substances of the storage battery, such as graphite, the conductivity of the graphite is one hundred times higher than that of common non-metallic ores, the graphite has good chemical stability at normal temperature, can resist acid, alkali and organic solvent corrosion, not only can charge a wire in a conductive network, but also has good heat-conducting property which is beneficial to heat dissipation during charging and discharging of the battery, reduces polarization of the battery, improves high and low temperature performance of the battery and prolongs the service life of the battery.
Nano ketjen black: compared with conductive carbon black, the conductive carbon black has a unique branched-chain form, and has the advantages that the conductive carbon black has more conductive contacts, and the branched chains form more conductive paths, so that the extremely high conductivity can be achieved only by a small amount of addition (other carbon blacks are mostly spherical or flaky, so that the required electrical property can be achieved only by a high amount of addition).
Carbon fiber: the chopped carbon fiber material is a high-conductivity chopped carbon fiber material, has the characteristics of outstanding conductivity and permanent conductivity, and has the advantages of low density, high strength, light weight, corrosion resistance and the like.
4BS seed crystal: the method is beneficial to the generation of tetrabasic lead sulfate, and improves the cycle life and deep discharge recovery capability of the storage battery.
Sodium perborate: the corrosion oxidation capacity of the lead paste of the positive plate and the grid is improved, the contact resistance of the lead paste and the grid is reduced, the charge and discharge performance of the active substance is improved, and the deep charge and discharge capacity of the storage battery is improved.
Basic antimony carbonate: the antimony is added in a compound form and slowly converted in the electrochemical reaction of the storage battery, so that the segregation is avoided, the early-stage capacity loss is avoided, and the cycle life performance of the storage battery is improved.
Tin phosphate: the method has the advantages of improving the crystal boundary reaction capability of the lead paste and the grid, promoting the good combination of the lead paste and the grid, improving the combination capability between lead paste crystals, and having a good effect on reducing the crystal boundary resistance of the lead paste and the grid, thereby improving the charge acceptance capability and the cycle life of the polar plate.
Lithium phosphate: the porosity of the lead paste can be improved, the charge acceptance of the polar plate is improved, and the hydrogen evolution voltage of the polar plate is reduced, so that the water consumption of the polar plate is reduced.
The invention also provides a start-stop storage battery positive plate which comprises a positive plate grid alloy and positive lead plaster coated on two sides of the positive plate grid alloy, wherein the positive lead plaster is prepared by adopting the lead plaster formula.
Preferably, the positive grid alloy comprises the following raw materials in percentage by weight: 1.2 to 1.5 percent of tin, 0.05 to 0.07 percent of calcium, 0.01 to 0.02 percent of aluminum, 0.3 to 0.5 percent of neodymium, 0.07 to 0.15 percent of rhenium, and the balance of lead.
In the raw materials of the positive plate grid alloy, the rare earth element neodymium is one of rare earth metals, so that the crystal of the lead alloy can be greatly refined, the plate grid crystal is compact, the corrosion resistance of a polar plate is improved, and the cycle service life of the storage battery is prolonged; the rare earth element rhenium can also refine lead alloy grains, improve the corrosion resistance of the grid and improve the charge acceptance of the storage battery.
The two rare earth elements are supplemented together, so that the lead alloy plate has remarkable significance for refining lead alloy grains, is not easy to burn at high temperature compared with other rare earth elements, and can ensure the stability of the alloy elements during the manufacture of a plate grid.
The invention also provides a preparation method of the positive plate of the start-stop storage battery, wherein the preparation method of the positive lead paste comprises the following steps:
(1) mixing the tin phosphate, the nanometer Ketjen black and the sodium perborate according to the formula ratio, stirring, keeping the temperature, shearing at a high speed, stirring, and cooling to normal temperature for later use;
(2) mixing lithium phosphate, basic antimony carbonate and graphite according to the formula amount, adding 20-40% of dilute sulfuric acid according to the formula amount, mixing and stirring, adding the substance prepared in the step (1), heating to 55-70 ℃, and then recovering to a normal temperature and normal pressure state;
(3) mixing and stirring the 4BS crystal seeds and the substance prepared in the step (2), adding the lead powder according to the formula amount, mixing, adding the pure water according to the formula amount and the dilute sulfuric acid according to the rest formula amount, and performing paste mixing according to a paste mixing process, wherein the temperature of the lead paste in the paste mixing process is not more than 70 ℃.
Further, in the step (1), during high-speed shearing and stirring, the high-speed shearing and stirring is carried out at a speed of 2000-3000 r/min for 40-80 min.
Go toStep one, after adding 20 to 40 percent of dilute sulfuric acid according to the formula amount in the step (2), the mixture is mixed by a high-speed jet mixer at the speed of 10 to 11r/m.s-1The speed of the mixing device is 110-140 Kpa of the maximum pressure of the whole flow field, and the mixing and stirring are carried out for 15-25 min.
Further, in the step (3), when the lead powder with the formula amount is added and mixed, stirring is carried out for 8-12 min at the speed of 25-35 r/min.
Compared with the prior art, the invention has the following beneficial effects:
1. the lead plaster formula of the positive plate improves the utilization rate of active substances of the storage battery by reasonably adding conductive substances, has a new breakthrough in improving the charge acceptance of the storage battery, improves the charge acceptance of the manufactured storage battery by 20-30 percent, and prolongs the cycle life.
2. The slab lattice alloy of the positive plate is added with two substances of neodymium and rhenium, the two rare earth elements are supplemented and used together, the slab lattice alloy has remarkable significance for refining lead alloy grains, is difficult to burn at high temperature compared with other rare earth elements, and can ensure the stability of alloy elements during slab lattice manufacturing.
Detailed Description
The present invention is described in further detail below with reference to examples, which are intended to facilitate the understanding of the present invention without limiting it in any way.
The grid alloy of the negative plate adopts a conventional grid and a formula plate; the positive plate adopts the positive grid alloy provided by the invention, the grid production mode is a grid punching polar plate, and the paste mixing formula adopts the formula parameters provided by the invention; the polar plate is produced by adopting a conventional curing process.
During assembly, the battery pole group assembly production is carried out by adopting the matching mode specified by the invention, and an internal formation process is adopted; after the formation is finished, acid pouring and secondary acid adding are carried out by adopting a production mode of a rich-solution battery, and the liquid level of the electrolyte is 10-20 mm higher than the busbar; the density of the electrolyte is 1.27-1.29 g/cm3, sodium sulfate is added into the electrolyte, and 10-15 g of sodium sulfate is added into each liter of electrolyte.
Comparative example 1
1. The formula of the storage battery grid is as follows: tin Sn 1.2 wt.%; calcium Ca 0.06 wt.%, aluminum 0.02.0 wt.%; the balance being lead.
2. Lead plaster formula
The positive lead plaster comprises the following components: 100kg of lead powder, 0.05kg of short fibers, 10.5kg of water and 9.8kg of dilute sulfuric acid with the density of 1.4g/cm 3.
The negative pole lead plaster comprises the following components: 100kg of lead powder, 0.6kg of barium sulfate, 0.4kg of humic acid, 0.125kg of sodium lignosulfonate, 0.05kg of short fiber, 10.5kg of water and 1.4g/cm of density38.4kg of pure dilute sulfuric acid.
3. And (3) paste mixing process: adding lead powder with a formula amount into a paste mixer, adding an additive, starting the mixer to stir for 1min, then opening a purified water valve to add formula water at a uniform flow rate for about 3min, opening an acid inlet valve, simultaneously opening a cooling device to cool, uniformly spraying formula acid into the paste mixer within 5-8 min, continuously stirring for 15-18 min, and making the paste mixing process temperature not more than 65 ℃ to obtain the required positive/negative lead paste.
4. Curing process
(1) The green plate with the dried surface needs to enter a curing chamber for curing within 10 minutes, the temperature of the curing chamber is not higher than 45 ℃, and the relative humidity is 100%;
(2) the curing temperature is 45 ℃, the relative humidity is 90-100%, the curing time is 48h, and the circulating air speed is less than 30%;
(3) after curing, drying, wherein the heating rate is less than or equal to 1 ℃/20min, the temperature is increased to 65 ℃, the humidity reduction rate is less than or equal to 1%/10 min, the relative humidity is reduced to 0%, the wind speed increase rate is less than or equal to 1%/10 min, the normal drying process requirement is met within 6-9 hours, and the humidity is stable and unchanged until the drying cycle is continued for 2 hours;
(4) and naturally cooling to normal temperature after the solidification and drying are finished.
5. Packaging kit
And placing the positive plate to be packaged on the plate frame, and automatically packaging the plate by a PE partition plate packaging and assembling machine to obtain the PE single-layer packaging plate. The packaging matching group should pay attention to whether the strength of the edge covering meets the requirement or not, the edge covering cannot be inclined, and the partition plate needs to be cut to be level.
6. And matching the encapsulated positive plate with the negative plate, welding the plate group, and assembling the storage battery.
Example 1
1. The positive grid formula of the storage battery is as follows: tin 1.2 wt.%; calcium 0.05 wt.%; 0.01 wt.% aluminum; neodymium 0.3 wt.%; rhenium 0.07 wt.%; the balance being lead.
The formula of the negative plate grid of the storage battery is as follows: 1.2% of tin Sn; 0.03 percent of calcium Ca and the balance of lead.
2. Lead plaster formula
0.06 wt.% tin phosphate; lithium phosphate 0.01 wt.%; 0.03 wt.% antimony hydroxycarbonate; 4BS seed 0.1 wt.%; sodium perborate 0.01 wt.%; ketjen black 0.05 wt.%; 0.01-wt.% of graphite; dilute sulfuric acid 9 wt.% (density 1.4 g/cm)3) (ii) a Pure water 10 wt.%; 0.12 wt.% of carbon fiber, and the balance of lead powder with the oxidation degree of 71-73%.
The components and the paste mixing manner of the negative electrode lead paste are as described in comparative example 1.
3. Preparation method of positive lead paste
(1) Mixing tin phosphate, ketjen black and sodium perborate according to the formula ratio, stirring, keeping the temperature, shearing and stirring at a high speed of 2500r/min for 60min, and then cooling to the normal temperature for later use;
(2) mixing the lithium phosphate, the basic antimony carbonate and the graphite according to the formula ratio, adding the mixture into 2.8kg of cream acid, and mixing the mixture by a high-speed jet mixer at the speed of 10.3r/m.s-1Mixing and stirring at the speed of 125.8Kpa of the maximum pressure of the whole flow field for 20min, adding the substance prepared in the step 1, heating to the temperature of 60 ℃, and recovering to the normal temperature and normal pressure state;
(3) mixing 4BS crystal seeds with the substance prepared in the step 2, stirring at the speed of 30r/min for 10min, mixing with 100kg of lead powder, adding 6.2kg of diacidic acid and 10kg of water, and carrying out the diacidic process according to the diacidic temperature not higher than 70 ℃.
4. Curing process
And (3) curing by adopting the same curing process as in the comparative example 1, encapsulating and matching, and then carrying out electrode group welding to assemble the storage battery.
Example 2
1. The positive grid formula of the storage battery is as follows: tin 1.2 wt.%; calcium 0.05 wt.%; 0.01 wt.% aluminum; neodymium 0.5 wt.%; rhenium 0.07 wt.%; the balance being lead.
The formula of the negative plate grid of the storage battery is as follows: 1.2% of tin Sn; 0.03 percent of calcium Ca and the balance of lead.
2. Lead plaster formula
0.06 wt.% tin phosphate; lithium phosphate 0.01 wt.%; 0.1 wt.% antimony hydroxycarbonate; 4BS seed 0.3 wt.%; sodium perborate 0.03 wt.%; ketjen black 0.03 wt.%; 0.01 wt.% graphite; dilute sulfuric acid 9 wt.% (density 1.4 g/cm)3) (ii) a Pure water 11 wt.%; 0.1 wt.% of carbon fiber, and the balance of lead powder with the oxidation degree of 71-73%.
The components and the paste mixing manner of the negative electrode lead paste are as described in comparative example 1.
3. Preparation method of positive lead paste
(1) Mixing tin phosphate, ketjen black and sodium perborate according to the formula ratio, stirring, keeping the temperature, shearing and stirring at a high speed of 2500r/min for 60min, and then cooling to the normal temperature for later use;
(2) mixing the lithium phosphate, the basic antimony carbonate and the graphite according to the formula ratio, adding the mixture into 2.8kg of cream acid, and mixing the mixture by a high-speed jet mixer at the speed of 10.3r/m.s-1Mixing and stirring at the speed of 125.8Kpa of the maximum pressure of the whole flow field for 20min, adding the substance prepared in the step 1, heating to the temperature of 60 ℃, and recovering to the normal temperature and normal pressure state;
(3) mixing 4BS crystal seeds with the substance prepared in the step 2, stirring at the speed of 30r/min for 10min, mixing with 100kg of lead powder, adding 6.2kg of diacidic acid and 10kg of water, and carrying out the diacidic process according to the diacidic temperature not higher than 70 ℃.
4. Curing process
And (3) curing by adopting the same curing process as in the comparative example 1, encapsulating and matching, and then carrying out electrode group welding to assemble the storage battery.
Example 3
1. The positive grid formula of the storage battery is as follows: 1.5 wt.% tin; calcium 0.07 wt.%; aluminum 0.02.0 wt.%; neodymium 0.5 wt.%; rhenium 0.15 wt.%; the balance being lead.
The formula of the negative plate grid of the storage battery is as follows: 1.2% of tin Sn; 0.03 percent of calcium Ca and the balance of lead.
2. Lead plaster formula
0.1 wt.% tin phosphate; lithium phosphate 0.05 wt.%; 0.1 wt.% antimony hydroxycarbonate; 4BS seed 0.1 wt.%; sodium perborate 0.01 wt.%; ketjen black 0.03 wt.%; graphite 0.05 wt.%; dilute sulfuric acid 10 wt.% (density 1.4 g/cm)3) (ii) a Pure water 10 wt.%; 0.12 wt.% of carbon fiber, and the balance of lead powder with the oxidation degree of 71-73%.
The components and the paste mixing manner of the negative electrode lead paste are as described in comparative example 1.
3. Preparation method of positive lead paste
(1) Mixing tin phosphate, ketjen black and sodium perborate according to the formula ratio, stirring, keeping the temperature, shearing and stirring at a high speed of 2500r/min for 60min, and then cooling to the normal temperature for later use;
(2) mixing the lithium phosphate, the basic antimony carbonate and the graphite according to the formula ratio, adding the mixture into 2.8kg of cream acid, and mixing the mixture by a high-speed jet mixer at the speed of 10.3r/m.s-1Mixing and stirring at the speed of 125.8Kpa of the maximum pressure of the whole flow field for 20min, adding the substance prepared in the step 1, heating to the temperature of 60 ℃, and recovering to the normal temperature and normal pressure state;
(3) mixing 4BS crystal seeds with the substance prepared in the step 2, stirring at the speed of 30r/min for 10min, mixing with 100kg of lead powder, adding 6.2kg of diacidic acid and 10kg of water, and carrying out the diacidic process according to the diacidic temperature not higher than 70 ℃.
4. Curing process
And (3) curing by adopting the same curing process as in the comparative example 1, encapsulating and matching, and then carrying out electrode group welding to assemble the storage battery.
Example 4
1. The positive grid formula of the storage battery is as follows: 1.5 wt.% tin; calcium 0.07 wt.%; 0.01 wt.% aluminum; neodymium 0.5 wt.%; rhenium 0.15 wt.%; the balance being lead.
The formula of the negative plate grid of the storage battery is as follows: 1.2% of tin Sn; 0.03 percent of calcium Ca and the balance of lead.
2. Lead plaster formula
0.08 wt.% tin phosphate; lithium phosphate 0.03 wt.%; 0.08 wt.% antimony hydroxycarbonate; 4BS seed 0.2 wt.%; sodium perborate 0.02 wt.%; ketjen black 0.04 wt.%; 0.03 wt.% graphite; dilute sulfurAcid 10 wt.% (density 1.4 g/cm)3) (ii) a Pure water 11 wt.%; 0.11 wt.% of carbon fiber, and the balance of lead powder with the oxidation degree of 71-73%.
The components and the paste mixing manner of the negative electrode lead paste are as described in comparative example 1.
3. Preparation method of positive lead paste
(1) Mixing tin phosphate, ketjen black and sodium perborate according to the formula ratio, stirring, keeping the temperature, shearing and stirring at a high speed of 2500r/min for 60min, and then cooling to the normal temperature for later use;
(2) mixing the lithium phosphate, the basic antimony carbonate and the graphite according to the formula ratio, adding the mixture into 2.8kg of cream acid, and mixing the mixture by a high-speed jet mixer at the speed of 10.3r/m.s-1Mixing and stirring at the speed of 125.8Kpa of the maximum pressure of the whole flow field for 20min, adding the substance prepared in the step 1, heating to the temperature of 60 ℃, and recovering to the normal temperature and normal pressure state;
(3) mixing 4BS crystal seeds with the substance prepared in the step 2, stirring at the speed of 30r/min for 10min, mixing with 100kg of lead powder, adding 6.2kg of diacidic acid and 10kg of water, and carrying out the diacidic process according to the diacidic temperature not higher than 70 ℃.
4. Curing process
And (3) curing by adopting the same curing process as in the comparative example 1, encapsulating and matching, and then carrying out electrode group welding to assemble the storage battery.
Application example
The pole groups prepared in the comparative example and the embodiment are manufactured into a maintenance-free storage battery (capacity: 80 Ah; low-temperature large-current discharge Icc 800A) with the model number of 6-QTF-80 according to the conventional process, and the battery performance test is carried out according to GB/T5008.1-2013 and JB/T2666-.
1. Rated capacity of 20h
The detection method comprises the following steps: discharging at 25 + -2 deg.C with 4A, terminating voltage at 10.5 + -0.05 v, and recording time.
2. Low temperature detection at-18 deg.C
The detection method comprises the following steps: keeping the temperature at minus 18 +/-1 ℃ for not less than 24 h. The battery was discharged at 800A for 10s, the voltage was recorded for 10s, at rest for 10s, at 480A to 6.0V terminal voltage of the battery, and the terminal voltage at 20s and the time to 6.0V terminal voltage were recorded, respectively.
3. Rated capacity of 20h
The detection method comprises the following steps: discharging at 25 + -2 deg.C with 4A, terminating voltage at 10.5 + -0.05 v, and recording time.
4. Low temperature detection at-29 deg.C
The detection method comprises the following steps: keeping the temperature at minus 29 +/-1 ℃ for not less than 24 h. The discharge was carried out for 30s at 600A, and the voltage was recorded for 10s and 30 s.
5. Charge acceptance capability
The detection method comprises the following steps: after the storage battery is fully charged, the storage battery is kept at the ambient temperature of 25 +/-2 ℃ as I0(8.22A) discharging for 5h, standing at 0 + -1 deg.C for 20h, taking out for 1min, charging at 14.4 + -0.10 v, and recording charging current I after 10minca。
6. 50% DOD cycle life (JB/T2666-2016 Start-stop Battery technical Condition 5.3.11)
The detection method comprises the following steps:
the following cycle is repeated for a fully charged battery in a thermostatted water bath at 40 ℃ ± 2 ℃: discharging at 40A for 2h, and terminating the test when the terminal voltage of the storage battery is lower than 10.0V; after the discharge is finished, charging for 5 hours by using a constant voltage of 15.6V +/-0.05V (current limiting 40A), and charging for 1 hour by using a constant current of 8A; after the storage battery is opened and kept stand in the water bath for 72 hours, the storage battery is placed in a low-temperature box with the temperature of minus 18 +/-1 ℃ for 24 hours, and then the storage battery is taken out and discharged within 2 minutes. Discharging at 480A for 30s, wherein the change of the current value in the discharging time is not more than +/-0.5%, and recording the terminal voltage of the storage battery at the time of discharging for 30 s.
Specific results are shown in table 1 below.
TABLE 1
The above table shows that the conventional formula is adopted in the comparative example 1, the formula and the process disclosed by the invention are adopted in the embodiment, and through experimental comparison, the capacity and the low temperature of the embodiment are far higher than those of the comparative example, the positive plate of the invention has higher utilization rate of the active substances of the polar plate, and the storage battery manufactured by the invention has excellent low-temperature discharge performance from the aspects of charge acceptance and 50% DOD deep discharge cycle, the charge acceptance is higher than that of the conventional process by more than 30%, and the 50% cycle life is prolonged by more than 10%, so that the performance of the storage battery is remarkably excellent.
The embodiments described above are intended to illustrate the technical solutions and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modifications, additions and equivalents made within the scope of the principles of the present invention should be included in the scope of the present invention.
Claims (1)
1. A start-stop storage battery positive plate is characterized by comprising a positive plate grid alloy and positive lead plaster coated on two sides of the positive plate grid alloy, wherein the positive lead plaster is prepared by adopting a lead plaster formula;
the lead plaster comprises the following raw materials in percentage by weight: 0.06-0.1% of tin phosphate, 0.01-0.05% of lithium phosphate, 0.03-0.1% of basic antimony carbonate, 0.1-0.3% of 4BS seed crystal, 0.01-0.03% of sodium perborate, 0.03-0.05% of nano Keqin black, 0.01-0.05% of graphite, 9-10% of dilute sulfuric acid, 10-12% of pure water, 0.1-0.12% of carbon fiber and the balance of lead powder with the oxidation degree of 71-73%; the density of the dilute sulfuric acid is 1.4g/cm3；
The positive grid alloy comprises the following raw materials in percentage by weight: 1.2 to 1.5 percent of tin, 0.05 to 0.07 percent of calcium, 0.01 to 0.02 percent of aluminum, 0.3 to 0.5 percent of neodymium, 0.07 to 0.15 percent of rhenium, and the balance of lead;
the preparation method of the positive lead paste comprises the following steps:
(1) mixing and stirring tin phosphate, nano Ketjen black and sodium perborate according to the formula amount, keeping the temperature, shearing and stirring at a high speed of 2000-3000 r/min for 40-80 min, and cooling to normal temperature for later use;
(2) mixing lithium phosphate, basic antimony carbonate and graphite according to the formula amount, adding 20-40% of dilute sulfuric acid according to the formula amount, and mixing the mixture by a high-speed jet mixer at the speed of 10-11 r/m.s-1Speed of (2) allMixing and stirring the mixture for 15-25 min under the maximum pressure of the flow field of 110-140 Kpa, adding the substance prepared in the step (1), heating the mixture to 55-70 ℃, and then recovering the mixture to a normal temperature and normal pressure state;
(3) and (3) mixing and stirring the 4BS crystal seeds with the amount according to the formula with the substance prepared in the step (2), adding the lead powder with the amount according to the formula, mixing, stirring at the speed of 25-35 r/min for 8-12 min, adding the pure water with the amount according to the formula and the dilute sulfuric acid with the amount according to the rest formula, and performing paste mixing according to a paste mixing process, wherein the temperature of the lead paste in the paste mixing process is not more than 70 ℃.
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