CN111682166A - Positive plate for high-capacity battery, preparation method and high-capacity battery - Google Patents

Positive plate for high-capacity battery, preparation method and high-capacity battery Download PDF

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Publication number
CN111682166A
CN111682166A CN202010407227.3A CN202010407227A CN111682166A CN 111682166 A CN111682166 A CN 111682166A CN 202010407227 A CN202010407227 A CN 202010407227A CN 111682166 A CN111682166 A CN 111682166A
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Prior art keywords
positive
plate
lead
glass fiber
fiber layer
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CN202010407227.3A
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CN111682166B (en
Inventor
刘海凤
程艳青
李海彪
李越南
袁关锐
欧阳万忠
周文渭
庄建
房兆锟
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Tianneng Battery Group Co Ltd
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Tianneng Battery Group Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—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
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/68—Selection of materials for use in lead-acid accumulators
    • H01M4/685—Lead alloys
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a positive plate for a large-capacity battery, which comprises a positive plate grid and positive diachylon coated on the positive plate grid, wherein the positive plate grid comprises the following components in percentage by weight: 1.2-1.5 wt% of tin; 0.05 to 0.07 weight percent of calcium; 0.01-0.02 wt% of aluminum; 0.3 to 0.5 weight percent of antimony; 0.03-0.05 wt% of iridium; rhenium 0.07-0.15 wt%; the balance being lead; the positive lead plaster comprises the following components in percentage by weight: 0.1-0.3 wt% of magnesium plumbate; 0.1-0.3 wt% of stannous sulfate; 0.1-0.3 wt% of polyolefin; 0.1-0.3 wt% of 4BS seed crystal; 0.01-0.03 wt% of sodium perborate; 0.03-0.05 wt% of Keqin black; 9-10 wt% of dilute sulfuric acid; 10-12 wt% of pure water; 0.1-0.12 wt% of fiber, and the balance of lead powder with the oxidation degree of 71-73%; the invention also discloses a high-capacity battery which comprises a negative plate and a partition plate, wherein the partition plate is of a double-composite type and sequentially comprises a coarse glass fiber layer, a fine glass fiber layer, a PE layer, a fine glass fiber layer and a coarse glass fiber layer from left to right, and at least one positive plate adopting the formula is wrapped in the PE layer.

Description

Positive plate for high-capacity battery, preparation method and high-capacity battery
Technical Field
The invention relates to the technical field of storage batteries, in particular to a positive plate for a high-capacity battery, a preparation method and the high-capacity battery.
Background
The performance requirements of the lead-acid storage battery for the general vehicle are instantaneous starting discharge capacity and low-temperature starting performance, and the battery can not be used in deep charge and discharge occasions; the lead-acid storage battery for the vehicle adopting the start-stop system has the characteristic that the engine is frequently started in a shallow discharge state, so the battery cannot be suitable for occasions of starting the vehicle in a deep discharge state.
The battery of the truck for the parking air conditioner has the advantages that in winter and summer, when the truck stops and stops, the storage battery on the truck is used for starting the vehicle-mounted air conditioner to meet the rest condition of personnel on the truck, in the state, the battery can meet deep discharge performance, and the vehicle can be started after deep discharge, and the deep discharge capacity, the rapid recovery capacity after deep discharge and the high starting capacity are realized, so that the requirements of the conventional starting storage battery and the starting and stopping storage battery are difficult to meet.
The key for determining the deep discharge capacity, the rapid recovery capacity after deep discharge and the high starting capacity is the performance of the lead storage battery plate, the plate consists of a grid and lead plaster, and the capacity is difficult to achieve by the traditional mode for preparing the grid and the lead plaster.
For example, the patent with the publication number of CN107919476A discloses a lead paste formula of a circulating lead-acid storage battery for communication, which comprises a positive lead paste formula and a negative lead paste formula, wherein the positive lead paste formula comprises the following raw materials, by weight, 5.5-6.5% of dilute sulfuric acid, 10-11% of deionized water, 0.1-0.15% of short fibers, and the balance of lead powder; the negative lead plaster comprises, by weight, 6-7% of dilute sulfuric acid, 10-10.5% of deionized water, 1.0-1.3% of barium sulfate, 0.1-0.5% of sodium lignosulfonate, 0.1-0.15% of carbon black, 0.1-0.15% of short fibers, and the balance of lead powder.
For another example, patent publication No. CN102839296A discloses a grid alloy and lead paste formulation for a battery plate of an electric vehicle, the grid alloy of the plate includes a positive grid alloy and a negative grid alloy, the positive grid alloy comprises the following components in percentage by weight: 1.3 to 1.5 percent of tin, 0.07 to 0.09 percent of calcium and 0.01 to 0.03 percent of aluminum, wherein the negative plate comprises the following slab lattice alloy components in percentage by weight: 0.6 to 0.8 percent of tin, 0.09 to 0.11 percent of calcium and 0.01 to 0.03 percent of aluminum;
the formula and the weight percentage content of the lead plaster of the battery plate of the electric vehicle are as follows: main materials: 1000 kg of lead powder, additive auxiliary materials: 0.2 to 0.3 percent of active carbon, 0.1 to 0.12 percent of short fiber, 0.1 to 0.12 percent of stannous sulfate, 0.2 to 0.22 percent of antimony trioxide, and the ingredients in the blending process are as follows: 11.0 to 11.5 percent of pure water and 10.5 to 11.0 percent of sulfuric acid with the concentration of 1.40g/ml at 25 ℃.
The lead plaster and the slab lattice disclosed in the patent adopt conventional materials and proportions, have general performances, and are difficult to achieve deep discharge capacity, rapid recovery capacity after deep discharge and high starting capacity.
Disclosure of Invention
The invention provides a positive plate for a high-capacity battery, aiming at the defects of the prior art.
A positive plate for a large-capacity battery comprises a positive plate grid and positive lead paste coated on the positive plate grid;
the positive grid comprises the following components in percentage by weight: 1.2-1.5 wt% of tin; 0.05 to 0.07 weight percent of calcium; 0.01-0.02 wt% of aluminum; 0.3 to 0.5 weight percent of antimony; 0.03-0.05 wt% of iridium; rhenium 0.07-0.15 wt%; the balance being lead;
wherein:
iridium: the corrosion-resistant metal improves the corrosion-resistant capability of the alloy, improves the corrosion-resistant capability of the grid and prolongs the cycle charge and discharge service life of the storage battery;
antimony: the deep charge and discharge capacity of the maintenance-free storage battery is improved, the charge acceptance of the storage battery is improved, the antimony-free effect of the lead-calcium-tin alloy maintenance-free storage battery is avoided, and the low content of antimony cannot cause excessive water loss of the storage battery;
rhenium: the alloy crystal grains are refined, and the corrosion resistance of the grid is improved.
The positive lead plaster comprises the following components in percentage by weight: 0.1-0.3 wt% of magnesium plumbate; 0.1-0.3 wt% of stannous sulfate; 0.1-0.3 wt% of polyolefin; 0.1-0.3 wt% of 4BS seed crystal; 0.01-0.03 wt% of sodium perborate; 0.03-0.05 wt% of Keqin black; 9-10 wt% of mixed paste acid (dilute sulfuric acid) (density 1.4g/cm 3); 10-12 wt% of pure water; 0.1-0.12 wt% of fiber, and the balance of lead powder with the oxidation degree of 71-73%.
Wherein:
magnesium plumbate: the lead acid magnesium and the lead sulfate are mixed to form a lead oxide hydrate, and the lead oxide hydrate is bonded with the lead sulfate to form a lead oxide hydrate.
Stannous sulfate: the porosity and the discharge performance of the active material are improved, and the discharge recovery capability of the polar plate is improved;
polyolefin: the porosity of the positive active material and the charge and discharge performance of the storage battery are improved, the deep discharge performance and the charge acceptance of the storage battery are improved, for example, poly-1-butylene can be used as polyolefin.
4BS seed crystal: the production of tetrabasic lead sulfate is facilitated, the cycle life of the storage battery is prolonged, and the deep discharge recovery capability is improved;
sodium perborate: the corrosion and oxidation resistance 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;
ketjen black: the conductive material has a unique branched-chain form, and the form has the advantages that the conductive contact points of the conductor are more, the branched chains form more conductive paths, and the extremely high conductivity can be achieved with a small addition amount.
The invention also provides a preparation method of the positive plate for the high-capacity battery.
The preparation method of the positive electrode lead paste comprises the following steps:
(1) mixing and stirring the polyolefin and the sodium perborate according to the formula amount, and then cooling to normal temperature for later use;
(2) mixing ketjen black, magnesium plumbate and stannous sulfate according to the formula amount, adding into paste acid for stirring, then adding into the material obtained in the step (1), then heating, pressurizing and stirring, and finally recovering to the state of normal temperature and normal pressure;
(3) mixing seed crystals with the formula amount of 4BS with the material obtained in the step (2), stirring, and standing at normal temperature for later use;
(4) and (4) mixing the material obtained in the step (3) with lead powder, adding paste acid and water, and preparing the positive lead paste through a paste mixing process.
Preferably, the heating in step (2) is heating to 60 ℃, and the pressurizing pressure is 3 MPa.
Preferably, the amount of gypsic acid used in step (2) is 2.8kg and the amount of gypsic acid used in step (4) is 6.2 kg.
The invention also provides a high-capacity battery which has deep discharge capacity, rapid recovery capacity after deep discharge and high starting capacity.
A large-capacity battery comprising positive electrode plates and negative electrode plates alternately arranged, and a separator for separating the positive electrode plates from the negative electrode plates, the positive electrode plates being as defined in claim 1 or 2 for a large-capacity battery, the separator comprising a PE layer attached to one side of the positive electrode plates, a thick glass fiber layer attached to one side of the negative electrode plates, and a thin glass fiber layer provided between the PE layer and the thick glass fiber layer.
When the separator adopting the design is used, the positive plate is wrapped, and the lamination sequence after the pole group is assembled is as follows: negative plate, thick glass fiber layer, thin glass fiber layer, PE layer, positive plate, PE layer, thin glass fiber layer, thick glass fiber layer, negative plate … …; when producing storage batteries of different models, the pole group matching is carried out according to the performance requirements of the storage batteries.
Preferably, two positive plates are arranged between adjacent separators, the thickness of the positive plate tabs and the plate grids is 0.6-0.75mm, and the thickness of the positive plate grids after lead paste coating is 1.2 mm.
When the storage battery is assembled, the double-sheet positive plate and the single-sheet negative plate are assembled for use, the capacity of the double-sheet thin positive plate is equivalent to the capacity of a thick positive plate, the capacity of the double-sheet thin positive plate is equivalent to the capacity of two polar plates during discharging, compared with the discharging of the single-sheet thick polar plate, the internal conduction of active substances in the polar plates is more uniform, the utilization rate of the active substances is higher, the charge acceptance and the discharge capacity of the storage battery are improved, and the deep-cycle discharging and large-current discharging device is.
Preferably, the thickness of the coarse glass fiber layer is 0.3mm-0.4mm, the thickness of the fine glass fiber layer is 0.2mm-0.3mm, the thickness of the PE layer is 0.2-0.25mm, the total thickness of the separator is 0.7-0.8mm, and the compression ratio is 20%.
The thick glass fiber layer can provide high-strength elastic modulus, ensure the assembly pressure of the plate group, enable the inner polar plate of the storage battery to be used in a tightly assembled state, improve the vibration resistance of the storage battery and avoid the falling of active substances of the plate group;
the thin glass fiber layer prevents the polar plate from puncturing the partition plate due to the deformation of the polar plate when the polar plate is deeply discharged to a certain extent, and the short circuit of dendritic crystals of the active substance is avoided;
the fiber layer coats the PE clapboard, so that the PE clapboard is protected to a certain extent, the PE clapboard is prevented from being punctured by active substances or other metal objects, and the service life of the storage battery is prolonged.
The invention has the beneficial effects that:
the invention has the characteristics of excellent deep discharge performance, quick recovery capability after deep discharge and strong starting capability.
Drawings
Fig. 1 is a structural view of a separator-wrapped double positive plate of the present invention.
Detailed Description
The present invention will be described more clearly and completely through the manufacturing and assembling processes of the large capacity battery.
Example 1:
1. manufacturing a positive grid:
the positive grid comprises the following components in percentage by weight: 1.2 wt% of tin; 0.05 wt% of calcium; 0.01 wt% of aluminum; 0.3 wt% of antimony; 0.03 wt% of iridium; rhenium 0.07 wt%; the balance being lead; the positive plate grid of the embodiment adopts a stamped plate or a cast plate.
Manufacturing a negative grid:
the content of each component of the negative grid is 1.2 wt% of Sn; 0.03 wt% of calcium Ca and the balance of lead, and the negative grid adopts a punched plate or a cast plate.
2. Preparing positive lead paste:
the positive lead plaster comprises the following components in percentage by weight: 0.1kg of magnesium plumbate; 0.1kg of stannous sulfate; 0.1kg of poly-1-butene; 0.1kg of 4BS seed crystal; 0.01kg of sodium perborate; keqin black 0.03 kg; 9kg of mixed paste acid (dilute sulfuric acid) (density 1.4 g/cm)3) (ii) a 10kg of pure water; the balance is lead powder with the oxidation degree of 71-73%.
And (3) paste mixing process:
(1) mixing polyolefin and sodium perborate according to the formula amount, 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 nano Keqin black, magnesium plumbate and stannous sulfate according to the formula amount, adding into 2.8kg of cream acid, stirring at the speed of 100r/min for 20min, adding the substance prepared in the step (1), heating to the temperature of 60 ℃, pressurizing to the pressure of 3MPa, dispersing and stirring for 2h at the speed of 2500r/min by using a high-pressure high-speed shearing emulsifying machine, and then slowly stirring the mixture at the speed of 100r/min to recover to the state of normal temperature and normal pressure;
(3) mixing seed crystals with the formula amount of 4BS with the substance prepared in the step (2), stirring at the speed of 30r/min for 10min, and standing at normal temperature for later use;
(4) and (3) mixing the material prepared in the step (3) with 100kg of lead powder, adding 6.2kg of paste mixing acid and 10kg of water, and preparing the positive lead paste according to a paste mixing process, wherein the temperature of the paste mixing process is not more than 70 ℃.
Preparing negative lead plaster:
the negative lead plaster comprises the following components in percentage by weight: 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 8.4kg of pure dilute sulfuric acid (the density is 1.4 g/cm)3)。
And (3) paste mixing process:
adding the lead powder with the formula amount into a paste mixer, adding an additive, starting the mixer to stir for 1min, then opening a purified water valve to add the formula water at a uniform flow rate for about 3min, opening an acid inlet valve, simultaneously opening a cooling device to cool, uniformly spraying the formula acid into the paste mixer within 5-8min, continuously stirring for 15-18min, and obtaining the required negative lead paste, wherein the temperature in the paste mixing process is not more than 65 ℃.
3. Curing the green plate:
and coating the prepared positive lead plaster on an aged positive grid, pressing by an acid spraying roller, and vibrating and compacting to obtain a green plate.
And (3) a 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 55 ℃, and the relative humidity is 100%;
(2) the curing temperature is 80 ℃, the relative humidity is 95-100%, the time is 22h, the air speed and the air quantity of the circulating fan are set to be 30%, and the relative humidity and the temperature are controlled by heating and humidifying steam and water mist;
(3) the relative humidity is reduced to 35 percent, the temperature is controlled to be 65 ℃, the air speed and the air quantity of the circulating fan are set to be 60 percent, and the time is 5 hours.
(4) Heating to 70-80 deg.C, setting relative humidity to zero, fully opening circulating fan, and drying for 10-12 hr.
(5) And naturally cooling to normal temperature after the solidification and drying are finished.
4. Packaging and matching:
the positive plates to be packaged are placed on the plate frame, and a double-sided composite type partition plate is adopted to package and assemble the double positive plates through a partition plate packaging and assembling machine or manually pack the double positive plates, wherein the capacity of the single positive plate is half of that of the negative plates of the matched assembly.
The adjacent separators 1 are of an integral structure, and the structure of the adjacent separators 1 wrapped by the double positive plates 2 is shown in fig. 1, and the structure comprises a thick glass fiber 11-fiber layer, a thin glass fiber layer 12, a PE layer 13, the positive plates 2, the PE layer 13, the thin glass fiber layer 12 and the thick glass fiber layer 11 from left to right.
In this embodiment, the thick glass fiber layer 11, the thin glass fiber layer 12 and the PE layer 13 are integrally attached and bent to form a U-shaped structure, and the double positive plates 2 are disposed in the U-shaped cavity formed by bending the PE layer 13.
Specifically, the thickness of a positive plate lug and a plate grid is 0.6mm, and the thickness of the positive plate is 1.2 mm; the thickness of the thick glass fiber layer is 0.4mmmm, the thickness of the thin glass fiber layer is 0.2mm, the thickness of the PE layer is 0.2, the total thickness of the separator is 0.8mm, and the compression ratio is 20%.
And matching the encapsulated positive plate with the negative plate, and welding the plate group.
5. Assembling and injecting a storage battery:
assembling the storage battery by adopting an internal formation process, and pouring acid and adding acid for the second time by adopting a production mode of a pregnant solution battery after formation is finished, wherein the liquid level of the electrolyte is 10mm higher than the busbar; the density of the electrolyte is 1.275g/cm312g of sodium sulfate per liter of electrolyte was added.
Example 2:
only the differences from the above-described embodiment 1 will be described below.
In this embodiment, the positive grid comprises the following components in parts by weight: 1.5 wt% of tin; 0.07 wt% of calcium; 0.02 wt% of aluminum; 0.5 wt% of antimony; 0.05 wt% of iridium; rhenium 0.15 wt%; the balance being lead.
The positive lead plaster comprises the following components in percentage by weight: 0.1kg of magnesium plumbate; 0.1kg of stannous sulfate; 0.1kg of poly-1-butene; 0.1kg of 4BS seed crystal; 0.01kg of sodium perborate; keqin black 0.03 kg; 9kg of dilute sulfuric acid (density 1.4 g/cm)3) (ii) a Pure water 10kg; the balance is lead powder with the oxidation degree of 71-73%.
In the embodiment, the thickness of the lug and the grid of the positive plate is 0.7mm, and the thickness of the positive plate is 1.2 mm; the thickness of the thick glass fiber layer is 0.3mm, the thickness of the thin glass fiber layer is 0.3mm, the thickness of the PE layer is 0.2mm, the total thickness of the separator is 0.8mm, and the compression ratio is 20%.
Example 3:
only the differences from the above-described embodiment 1 will be described below.
In this embodiment, the positive grid comprises the following components in parts by weight: 1.2 wt% of tin; 0.05 wt% of calcium; 0.01 wt% of aluminum; 0.3 wt% of antimony; 0.03 wt% of iridium; rhenium 0.07 wt%; the balance being lead.
The positive lead plaster comprises the following components in percentage by weight: 0.3kg of magnesium plumbate; 0.3kg of stannous sulfate; 0.3kg of poly-1-butene; 0.3kg of 4BS seed crystal; 0.03kg of sodium perborate; keqin black 0.05 kg; 10kg of dilute sulfuric acid (density 1.4 g/cm)3) (ii) a 12kg of pure water; the balance is lead powder with the oxidation degree of 71-73%.
In the embodiment, the thickness of the positive plate electrode lug and the plate grid is 0.75mm, and the thickness of the positive plate is 1.2 mm; the thickness of the thick glass fiber layer is 0.3mm, the thickness of the thin glass fiber layer is 0.2mm, the thickness of the PE layer is 0.2mm, the total thickness of the separator is 0.7mm, and the compression ratio is 20%.
Example 4:
only the differences from the above-described embodiment 1 will be described below.
In this embodiment, the positive grid comprises the following components in parts by weight: 1.5 wt% of tin; 0.07 wt% of calcium; 0.02 wt% of aluminum; 0.5 wt% of antimony; 0.05 wt% of iridium; rhenium 0.15 wt%; the balance being lead.
The positive lead plaster comprises the following components in percentage by weight: 0.3kg of magnesium plumbate; 0.3kg of stannous sulfate; 0.3kg of poly-1-butene; 0.3kg of 4BS seed crystal; 0.03kg of sodium perborate; keqin black 0.05 kg; 10kg of dilute sulfuric acid (density 1.4 g/cm)3) (ii) a 12kg of pure water; the balance is lead powder with the oxidation degree of 71-73%.
In the embodiment, the thickness of the lug and the grid of the positive plate is 0.7mm, and the thickness of the positive plate is 1.2 mm; the thickness of the thick glass fiber layer is 0.3mm, the thickness of the thin glass fiber layer is 0.2mm, the thickness of the PE layer is 0.25mm, the total thickness of the separator is 0.75mm, and the compression ratio is 20%.
Comparative example:
1. the formula of the storage battery grid is as follows: 1.2 wt% of tin; 0.06 wt% of calcium and 0.02 wt% of aluminum; the balance being lead.
2. The lead plaster formula comprises:
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 (the density is 1.4 g/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 8.4kg of pure dilute sulfuric acid (the density is 1.4 g/cm)3)。
3. And (3) paste mixing process:
adding the lead powder with the formula amount into a paste mixer, adding an additive, starting the mixer to stir for 1min, then opening a purified water valve to add the formula water at a uniform flow rate for about 3min, opening an acid inlet valve, simultaneously opening a cooling device to cool, uniformly spraying the formula acid into the paste mixer within 5-8min, continuously stirring for 15-18min, 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 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 and matching:
and placing the positive plate to be packaged on the plate frame, automatically packaging the plate by a PE partition plate packaging and assembling machine, packaging the plate by a PE single-layer packaging plate, assembling the packaged positive plate and the negative plate, and welding the plate group.
6. And (6) injecting liquid.
Application example
The pole groups prepared in the comparative example and the example are manufactured into a maintenance-free storage battery (capacity: 180 Ah; low-temperature large-current discharge Icc 900A) with the model number of 6-QW-180 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 9A, stopping 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 voltage was recorded at 1000A for 30s, 10s, 30s, rest for 20s, at 600A for 40s, end voltage 10.5 + -0.05 v, recording time.
3. Rated capacity of 20h
The detection method comprises the following steps: discharging at 25 + -2 deg.C with 9A, stopping at 10.5 + -0.05 v, and recording time.
4. Low temperature detection at-41 deg.C
The detection method comprises the following steps: keeping the temperature at minus 41 +/-1 ℃ for not less than 24 h. The voltage was recorded at 800A for 30s, 10s, 30s, rest for 20s, at 480A for 40s, end voltage 10.5 + -0.05 v, recording time.
5. Charge acceptance capability
The detection method comprises the following steps: after the storage battery is completely charged, the storage battery is kept at the ambient temperature of 25 +/-2 ℃, is discharged for 5h by I0(18.3A), is placed at the ambient temperature of 0 +/-1 ℃ for 20h, is taken out for 1min and is charged according to the voltage of 14.4 +/-0.10 v, and the charging current Ica is recorded after 10 min.
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 50A 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 45A), and charging for 1 hour by using a constant current of 9A; 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 600A 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:
TABLE 1
Figure BDA0002491765470000141
The above table shows that the conventional formula is adopted in the comparative example 1, the process described in the invention is 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 dual-plate positive plate process is adopted in the embodiment of the invention, the utilization rate of the active substances of the polar plate is higher, 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 40%, so that the performance of the storage battery is remarkably excellent.

Claims (8)

1. The utility model provides a positive plate for large capacity battery, positive plate includes anodal grid and the anodal diachylon of coating on anodal grid, its characterized in that:
the positive grid comprises the following components in percentage by weight: 1.2-1.5 wt% of tin; 0.05 to 0.07 weight percent of calcium; 0.01-0.02 wt% of aluminum; 0.3 to 0.5 weight percent of antimony; 0.03-0.05 wt% of iridium; rhenium 0.07-0.15 wt%; the balance being lead.
2. The positive electrode plate for large capacity batteries according to claim 1, wherein: the positive lead plaster comprises the following components in percentage by weight: 0.1-0.3 wt% of magnesium plumbate; 0.1-0.3 wt% of stannous sulfate; 0.1-0.3 wt% of polyolefin; 0.1-0.3 wt% of 4BS seed crystal; 0.01-0.03 wt% of sodium perborate; 0.03-0.05 wt% of Keqin black; 9-10 wt% of cream acid; 10-12 wt% of pure water; 0.1-0.12 wt% of fiber, and the balance of lead powder with the oxidation degree of 71-73%.
3. A method for manufacturing a positive electrode plate for a large capacity battery using the positive electrode plate for a large capacity battery according to claim 2, characterized in that: the preparation method of the positive lead paste comprises the following steps:
(1) mixing and stirring the polyolefin and the sodium perborate according to the formula amount, and then cooling to normal temperature for later use;
(2) mixing ketjen black, magnesium plumbate and stannous sulfate according to the formula amount, adding into paste acid for stirring, then adding into the material obtained in the step (1), then heating, pressurizing and stirring, and finally recovering to the state of normal temperature and normal pressure;
(3) mixing seed crystals with the formula amount of 4BS with the material obtained in the step (2), stirring, and standing at normal temperature for later use;
(4) and (4) mixing the material obtained in the step (3) with lead powder, adding paste acid and water, and preparing the positive lead paste through a paste mixing process.
4. The positive electrode plate for large capacity batteries according to claim 3, wherein: the heating in the step (2) is heating to 60 ℃, and the pressurizing pressure is 3 MPa.
5. The positive electrode plate for large capacity batteries according to claim 3, wherein: the amount of the healing acid in step (2) was 2.8kg, and the amount of the healing acid in step (4) was 6.2 kg.
6. A large capacity battery comprising positive and negative electrode plates arranged alternately, and a separator for separating the positive and negative electrode plates, characterized in that: the positive electrode plate is the positive electrode plate for a large capacity battery as defined in claim 1 or 2, the separator comprising a PE layer attached to a side of the positive electrode plate, a thick glass fiber layer attached to a side of the negative electrode plate, and a thin glass fiber layer interposed between the PE layer and the thick glass fiber layer.
7. A large capacity battery as recited in claim 6, wherein: two positive plates are arranged between the adjacent separators, the thickness of the positive plate tabs and the plate grids is 0.6-0.75mm, and the thickness of the positive plates is 1.2 mm.
8. A large capacity battery as recited in claim 6, wherein: the thickness of the thick glass fiber layer is 0.3mm-0.4mm, the thickness of the thin glass fiber layer is 0.2mm-0.3mm, the thickness of the PE layer is 0.2-0.25mm, the total thickness of the clapboard is 0.7-0.8mm, and the compression ratio is 20%.
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