CN111416126A - Preparation method of lead-calcium alloy positive plate - Google Patents
Preparation method of lead-calcium alloy positive plate Download PDFInfo
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- CN111416126A CN111416126A CN202010228554.2A CN202010228554A CN111416126A CN 111416126 A CN111416126 A CN 111416126A CN 202010228554 A CN202010228554 A CN 202010228554A CN 111416126 A CN111416126 A CN 111416126A
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- lead
- calcium alloy
- grid
- positive plate
- coating
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- 239000002142 lead-calcium alloy Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000001723 curing Methods 0.000 claims abstract description 52
- 238000005507 spraying Methods 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 33
- 239000006255 coating slurry Substances 0.000 claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 28
- 238000011282 treatment Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 230000003647 oxidation Effects 0.000 claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 24
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002002 slurry Substances 0.000 claims abstract description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 claims abstract description 11
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000010301 surface-oxidation reaction Methods 0.000 claims abstract description 7
- 238000007664 blowing Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 5
- 239000002253 acid Substances 0.000 description 23
- 238000007751 thermal spraying Methods 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 11
- 238000001514 detection method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000005498 polishing Methods 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011505 plaster Substances 0.000 description 6
- 229910052787 antimony Inorganic materials 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 229910000882 Ca alloy Inorganic materials 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- QTWBKNVNGVYTNZ-UHFFFAOYSA-N 4-amino-n-[4-(benzyloxy)phenyl]butanamide Chemical compound C1=CC(NC(=O)CCCN)=CC=C1OCC1=CC=CC=C1 QTWBKNVNGVYTNZ-UHFFFAOYSA-N 0.000 description 3
- 229910001245 Sb alloy Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052924 anglesite Inorganic materials 0.000 description 1
- 229910001439 antimony ion Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—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
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/73—Grids for lead-acid accumulators, e.g. frame plates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a lead-calcium alloy positive plate, and belongs to the technical field of lead storage batteries. The preparation method comprises the following steps: (1) mixing phosphoric acid, tetrabasic lead sulfate seed crystal, antimony trioxide and lead powder, adding water, stirring and heating to 75-85 ℃ to obtain wrapping slurry; (2) suspending a lead-calcium alloy grid on a curing frame of a curing chamber, carrying out surface oxidation treatment, adjusting the circulating air speed of the curing chamber to 80-100% and the relative humidity to 75-90%, spraying the coating slurry obtained in the step (1) into the curing chamber, and blowing coating slurry drops through the circulating air and coating the coating slurry drops on the surface of the grid; (3) and carrying out oxidation treatment on the grid with the wrapping slurry, drying to obtain a positive grid, and coating lead paste to obtain the lead-calcium alloy positive plate. The method improves the conductivity of the system, improves the over-discharge performance of the battery and prolongs the cycle charge and discharge life of the battery by improving the interface of the lead-calcium alloy grid/lead paste.
Description
Technical Field
The invention relates to the technical field of lead storage batteries, in particular to a preparation method of a lead-calcium alloy positive plate.
Background
The traditional flooded battery generally adopts Pb-Sb alloy (Sb percent is more than or equal to 2 percent) to manufacture a positive plate grid, has good cycle life, and particularly has the cycle life far superior to that of a positive plate manufactured by the Pb-Ca alloy in deep use. However, batteries made of Pb-Sb alloy have more defects, such as acid overflow in the charging process, equipment corrosion and great environmental pollution; after the battery is charged, pure water needs to be supplemented periodically when the water loss is serious. For the reasons, production enterprises adopt Pb-Ca alloy to replace Pb-Sb alloy grids when producing maintenance-free storage batteries.
However, in the battery manufactured by using the Pb-Ca alloy as the positive grid, the positive active material of the battery is degraded rapidly in the deep cycle use, and the battery is characterized in that the softening and the falling of the positive active material are not observed at the end of the service life, the grid is not obviously corroded, the open circuit voltage of the battery is normal, and the capacity of the battery is obviously reduced only during the discharge, namely the early capacity loss (PC L-1).
The early capacity loss of the battery (PC L-1) occurs at the interface of the outer layer of the grid corrosion layer and the active material when the battery is deeply discharged, PbSO is applied to the corrosion layer near the active material4The crystallization is concentrated to make the solution near the grid side alkaline, resulting in PbSO4The etch layer under the layer yielded α -PbO, and the conductance of the etch layer decreased, resulting in a barrier layer.
In the process of manufacturing the maintenance-free battery, antimony is added into a positive electrode Pb-Ca alloy, so that the conductivity of an interface between a grid and a corrosion layer can be improved, and the generation of PC L-1 is retarded, for example, patent document CN 109698353A discloses a storage battery positive alloy for avoiding early capacity loss, which consists of lead, calcium, tin, antimony and aluminum, wherein the content ratio of the positive alloy is 0.07-0.09% of calcium, 1.2-1.3% of tin, 1-1.2% of antimony and 0.02-0.05% of aluminum, and the balance is lead.
Patent document CN 107507966A discloses a formula for enhancing the strength and the battery capacity of a storage battery pole plate, which comprises 1.5-3.0 wt% of graphite, 0.8-1.5 wt% of sulfate, 0.8-1.5 wt% of antimony trioxide, 1.5-3.0 wt% of sodium sulfate, 1.5-2.5 wt% of tetrabasic lead sulfate and 0.08-1.0 wt% of polyester fiber.
Although the addition of antimony to lead-calcium alloys can improve the early capacity loss of batteries, the deep cycle life is still not ideal.
Disclosure of Invention
The invention aims to provide a preparation method of a lead-calcium alloy positive plate, which improves the conductivity of a system, improves the over-discharge performance of a battery and prolongs the cycle charge and discharge life by improving a lead-calcium alloy plate grid/lead paste interface.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a lead-calcium alloy positive plate comprises the following steps:
(1) taking phosphoric acid, tetrabasic lead sulfate seed crystal, antimony trioxide and lead powder according to the mass ratio of 1: 1-1.2: 1.5-2: 3-4, adding water into the mixture according to the mass ratio of the mixture to the water of 1: 15-19, stirring and heating to 75-85 ℃ to obtain wrapping slurry;
(2) suspending the lead-calcium alloy grid prepared after the sheet pouring process on a curing frame of a curing chamber, carrying out surface oxidation treatment, adjusting the circulating air speed of the curing chamber to 80-100% and the relative humidity to 75-90%, spraying the coating slurry obtained in the step (1) into the curing chamber, and blowing the coating slurry drops through the circulating air and coating the surface of the grid;
(3) and carrying out oxidation treatment on the grid with the wrapping slurry, drying to obtain a positive grid, and coating lead paste to obtain the lead-calcium alloy positive plate.
In the step (1), the thermal spraying coating slurry is prepared by high-speed stirring and mixing.
Preferably, the particle sizes of the tetrabasic lead sulfate seed crystal, the antimony trioxide and the lead powder are all less than 200 meshes.
Preferably, the stirring conditions are as follows: the rotating speed is 800-1500 r/min, and the time is more than or equal to 15 min.
In the step (2), the lead-calcium alloy grid is prepared by adopting a conventional sheet pouring process, and specifically, the formula of the lead-calcium alloy grid comprises 0.07-0.085% of calcium, 0.9-1.3% of tin, 0.02-0.04% of aluminum and the balance of lead.
After the sheet pouring process is finished, the grids are directly hung on the curing frame in sequence, and preferably, the distance between the lead-calcium alloy grids hung on the curing frame is 2-3 mm.
Firstly, the positive grid is cured at ultrahigh temperature, and the outer layer of the corrosion layer of the produced grid is easier to generate tetrabasic lead sulfate after charging and discharging.
Preferably, the conditions of the surface oxidation treatment are as follows: the relative humidity is 85-95%; temperature: setting the temperature to be 100-120 ℃ firstly, and then converting to be 70-80 ℃ after 2 hours; the wind speed is 10-30%; the oxidation time is 4-8 h.
Then, by using a special process (thermal spraying of the coating slurry in high-speed stirring), the coating slurry is sprayed into a curing chamber and the grid is coated by circulating air. 4BS in the wrapping slurry is thermally combined with an oxide layer generated by the previous step of ultra-high temperature curing and forms a new lead oxide layer through the action of phosphoric acid, and the strength is high. After formation, a framework between interfaces is formed, and the conductive performance is excellent. And (4) permeating the antimony ions into the grid surface corrosion layer through subsequent high-temperature and high-humidity treatment. Antimony trioxide is doped in the corrosion layer, and a lead-calcium-tin-antimony mixture is formed on the interface of the grid.
The wind speed is adjusted by controlling the frequency of the fan. 100% wind speed refers to full fan speed operation.
Preferably, the diameter of the wrapping slurry drop is 100-120 mu m, the spraying speed of the wrapping slurry per cubic meter of the curing chamber is 2-5L/min, the time is controlled within 3-5 min, and the occupied amount of the pole plate in the curing chamber is required to be more than 2/3 according to the existing process requirements.
More preferably, the wrapping pulp is sprayed for one time after 5-15 min.
In the step (3), the grid with the wrapping pulp is subjected to two high-temperature oxidation treatments, preferably, the oxidation treatment conditions sequentially comprise: a. oxidizing for 3-5 hours in an environment with a circulating air speed of 10-30%, a temperature of 70-80 ℃ and a relative humidity of 70-90%; b. and oxidizing for 3-5 hours in an environment with a circulating air speed of 50-70%, a temperature of 50-70 ℃ and a relative humidity of 50-80%.
The oxidation corrosion layer formed by the two high-temperature oxidation treatments and the subsequent curing process after plate coating is far superior to the pole plate corrosion layer prepared by common curing.
And (3) drying after high-temperature oxidation to obtain the positive grid, preferably, wherein the drying temperature is 80 ℃.
After the positive grid is prepared, coating and compacting lead paste within 72 hours, performing surface drying treatment after acid spraying, and transferring the plate into a curing chamber again to perform curing and drying according to a conventional curing process. The prepared polar plate can obtain a lead-calcium alloy grid/lead plaster interface meeting the requirements.
Preferably, the positive lead paste is coated within 24 hours.
The invention has the following beneficial effects:
(1) the method comprises the steps of firstly carrying out ultra-high temperature solidification on a lead-calcium alloy grid, then bringing wrapping slurry to the surface of the grid, and carrying out subsequent high-temperature medium-high humidity treatment to generate a transition interface between a grid corrosion layer and an active substance. Antimony trioxide as an interface dopant is extremely hydrophilic and readily forms water compounds in the interface. At the inside and outside of the interface H+And OH-There is a concentration gradient of H in the electrolyte+Can diffuse into the inner layer through the outer lead sulfate semi-permeable membrane, and α -PbO becomes unstable along with the increase of acidity of the inner layer, thereby generating higher order oxide and improving the conductivity of the interface of the inner layer of the corrosion layer.
(2) The positive plate manufactured by the method of the invention is assembled, added with acid and charged, and then the battery capacity is kept stable at the initial cycle stage, and the single discharge capacity in the service life is obviously higher than that of the similar batteries. The phenomenon that a single battery lags behind in the deep cycle process of the battery pack is improved, the battery is over-discharged, and the cycle life is prolonged.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited thereto.
The formula of the lead-calcium alloy positive grid in the following embodiment is as follows: 0.08 percent of calcium, 1.0 percent of tin, 0.02 percent of aluminum and the balance of lead.
The preparation method adopts the conventional process except for special specification.
Example 1:
1. compounding hot spraying coating pulp
a. Selecting 4BS (tetrabasic lead sulfate seed crystal) and lead powder, sieving with a 200-mesh sieve, and discarding the sieve residue;
b. mixing phosphoric acid, 4BS, antimony trioxide and lead powder according to a mass ratio of 1:1:1.5:4, adding pure water according to a mass ratio of the mixture to the pure water of 1:15, and stirring at a high speed of 1200 revolutions per minute for 15 minutes;
c. the thermal spray coating slurry should be heated to a specified value prior to use.
2. Oxidation treatment of grid surface
The positive grid of the 6-DZF-20 battery of the product which finishes the sheet pouring process is sequentially hung on a curing frame, the distance between sheets is 2-3 mm, then the grid is placed into a curing chamber, and the control parameters of the curing chamber are set: humidity is 85%; the temperature is 100 ℃ in the first 2h, and is changed to 70 ℃ after 2 h; the wind speed is 10%; the oxidation time was 4 h.
3. Wrapped thermal spray wrapping slurry
Adjusting parameters of a curing chamber, namely adjusting the air speed to 90 percent and setting the humidity to 85 percent, heating the high-speed stirred thermal spraying coating slurry in the step 1 to 82 ℃, spraying the slurry into the curing chamber through a nozzle, wherein the maximum diameter of the formed liquid drop is 100 mu m, the thermal spraying coating slurry is blown by circulating air and coated on the surface of a positive grid, the spraying speed of the coating slurry is 3L/min per cubic meter of the curing chamber, the time is controlled to be 4min, and the thermal spraying coating slurry is sprayed once after 10 min.
4. High temperature oxidation and drying
(1) Adjusting parameters of a curing chamber: a. the circulating air speed is 20%, the temperature is 75 ℃, the humidity is 80%, and the oxidation time is 4 h; b. the circulating wind speed is 60%, the temperature is 60 ℃, and the humidity is 70% for 4 h.
(2) Reducing the relative humidity to 0, and drying at 80 ℃.
5. Coated sheet
Cooling the treated grid for 4 hours, coating the plate, compacting lead paste, and performing surface drying treatment after acid spraying; the positive plate meeting the requirements is prepared by solidifying, drying and polishing the plate in a slicing way.
6. Assembly
Coating the negative lead plaster on a 6-DZF-20 negative grid which is naturally stored for 2d and has finished aging, and preparing the negative plate after rolling, acid spraying, surface drying, curing and drying, slicing and polishing.
And assembling the prepared positive green plate and the prepared negative green plate, and then adding acid for charging and finishing to finish the preparation of the battery.
7. Performance detection
The single battery is tested to have an internal resistance value of 9.63m omega at the ambient temperature of 25 +/-2 ℃.
Discharging to 10.5V by 10A, converting to constant voltage by 14.7V, current limiting, charging by 5A for 8h, and standing for 2h to obtain a test period. The discharge capacities of the reactor are respectively 21.0Ah, 21.8Ah, 22.2Ah, 22.3Ah, 22.4Ah, 22.3Ah, 21.3Ah and 18.2Ah in 1, 10, 50, 100, 200, 300, 400 and 500 cycles.
The end of life was taken as the discharge capacity below 16Ah, for a total of 532 cycles.
Example 2:
1. compounding hot spraying coating pulp
a. Selecting 4BS (tetrabasic lead sulfate seed crystal) and lead powder, sieving with a 200-mesh sieve, and discarding the sieve residue;
b. mixing phosphoric acid, 4BS, antimony trioxide and lead powder according to a mass ratio of 1:1:2:3.5, adding pure water according to a mass ratio of the mixture to the pure water of 1:18, and stirring at a high speed of 1500 revolutions per minute for 15 minutes;
c. the thermal spray coating slurry should be heated to a specified value prior to use.
2. Oxidation treatment of grid surface
The positive grid of the 6-DZF-20 battery of the product which finishes the sheet pouring process is sequentially hung on a curing frame, the distance between sheets is 2-3 mm, then the grid is placed into a curing chamber, and the control parameters of the curing chamber are set: the humidity is 95%; the temperature is 120 ℃ in the first 2h, and is changed to 80 ℃ after 2 h; wind speed is 30%; the oxidation time is 8 h.
3. Wrapped thermal spray wrapping slurry
Adjusting the parameters of a curing chamber, namely adjusting the air speed to 100 percent and setting the humidity to 90 percent, heating the high-speed stirred thermal spraying coating slurry in the step 1 to 85 ℃, spraying the slurry into the curing chamber through a nozzle, wherein the maximum diameter of the formed liquid drop is 120 mu m, the thermal spraying coating slurry is blown by circulating air and coated on the surface of a positive grid, the spraying rate of the coating slurry is 5L/min per cubic meter of the curing chamber, the time is controlled to be 5min, and the thermal spraying coating slurry is sprayed once after 15 min.
4. High temperature oxidation and drying
(1) Adjusting parameters of a curing chamber: a. the circulating wind speed is 30%, the temperature is 80 ℃, the humidity is 90%, and the oxidation time is 5 h; b. the air speed of the circulation is 70 percent, the temperature is 70 ℃, and the humidity is 80 percent.
(2) The grid is directly dried at 80 ℃ and humidity of 0.
5. Coated sheet
Cooling the treated grid for 10 hours, coating the plate, compacting lead paste, and performing surface drying treatment after acid spraying; the positive plate meeting the requirements is prepared by solidifying, drying and polishing the plate in a slicing way.
6. Assembly
Coating the negative lead plaster on a 6-DZF-20 negative grid which is naturally stored for 5 days and has finished aging, and preparing the negative plate after rolling, acid spraying, surface drying, curing and drying, slicing and polishing.
And assembling the prepared positive green plate and the prepared negative green plate, and then adding acid for charging and finishing to finish the preparation of the battery.
7. Performance detection
The single cell battery is tested to have an internal resistance of 9.67m omega at an ambient temperature of 25 +/-2 ℃.
And continuously discharging for 2d by using a fixed resistor of 0.5 omega, charging for 24h by using a constant-voltage 15V current-limiting 5A, standing for 2h, and testing the 2h rate capacity of the battery, wherein the above is a test period. The battery discharges capacities of 22.2Ah, 21.6Ah and 20.3Ah in 1, 5 and 10 cycles respectively.
Example 3:
1. compounding hot spraying coating pulp
a. Selecting 4BS (tetrabasic lead sulfate seed crystal) and lead powder, sieving with a 200-mesh sieve, and discarding the sieve residue;
b. mixing phosphoric acid, 4BS, antimony trioxide and lead powder according to a mass ratio of 1:1:1.5:4, adding pure water according to a mass ratio of the mixture to the pure water of 1:15, and stirring at a high speed of 800 revolutions per minute for 15 minutes;
c. the thermal spray coating slurry should be heated to a specified value prior to use.
2. Oxidation treatment of grid surface
The positive grid of the 6-DZF-20 battery of the product which finishes the sheet pouring process is sequentially hung on a curing frame, the distance between sheets is 2-3 mm, then the grid is placed into a curing chamber, and the control parameters of the curing chamber are set: humidity is 90%; the temperature is 110 ℃ in the first 2h, and is changed to 75 ℃ after 2 h; the wind speed is 20%; the oxidation time was 6 h.
3. Wrapped thermal spray wrapping slurry
Adjusting the parameters of a curing chamber, namely adjusting the air speed to 80 percent and setting the humidity to 75 percent, heating the high-speed stirred thermal spraying coating slurry in the step 1 to 82 ℃, spraying the slurry into the curing chamber through a nozzle, wherein the maximum diameter of the formed liquid drop is 120 mu m, the thermal spraying coating slurry is blown by circulating air and coated on the surface of a positive grid, the spraying speed of the coating slurry is 2L/min per cubic meter of the curing chamber, the time is controlled to be 3min, and the thermal spraying coating slurry is sprayed once after 5 min.
4. High temperature oxidation and drying
(1) Adjusting parameters of a curing chamber: a. the circulating wind speed is 10%, the temperature is 70 ℃, the humidity is 70%, and the oxidation time is 3 h; b. the circulating wind speed is 50%, the temperature is 50 ℃, and the humidity is 50% for 3 h.
(2) The grid is directly dried at 80 ℃ and humidity of 0.
5. Coated sheet
Cooling the treated grid for 20 hours, coating the grid, compacting lead paste, and performing surface drying treatment after acid spraying; the positive plate meeting the requirements is prepared by solidifying, drying and polishing the plate in a slicing way.
6. Assembly
Coating the negative lead plaster on a 6-DZF-20 negative grid which is naturally stored for 3d and has finished aging, and preparing the negative plate after rolling, acid spraying, surface drying, curing and drying, slicing and polishing.
And assembling the prepared positive green plate and the prepared negative green plate, and then adding acid for charging and finishing to finish the preparation of the battery.
7. Performance detection
At the ambient temperature of 25 +/-2 ℃, the battery pack is tested to have internal resistance values of 9.61m omega, 9.82m omega, 9.56m omega and 9.75m omega. Then the batteries are connected in series and discharged to 42V by 10A, the constant voltage is 58.8V, the current is limited by 10A, the charging is carried out for 4h, a test cycle is adopted, and the current discharging termination voltage difference is as follows at 1, 50, 100, 200 and 300 cycles, namely 0.23V, 0.19V, 0.32V, 0.51V and 0.59V.
Comparative example 1
1. Battery assembly
Naturally storing the 6-DZF-20 battery grid for 2 days, then finishing aging, then coating the plate and compacting lead paste, and performing surface drying treatment after acid spraying; and (4) assembling the battery after the polar plates are solidified, dried and sliced, and then adding acid for charging and finishing to finish the manufacture of the battery.
2. Performance detection
The single battery is tested to have the internal resistance value of 10.63m omega at the ambient temperature of 25 +/-2 ℃.
Then the battery is discharged to 10.5V at 10A, current-limited 5A at constant voltage of 14.7V is charged for 8h, and the battery is kept still for 2h, wherein the battery respectively discharges the capacities of 21.3Ah, 23.4Ah, 20.1Ah, 20.4Ah, 19.3Ah and 16.3Ah at 1, 10, 50, 100, 200 and 300 cycles.
The end of life was taken to be a discharge capacity below 16Ah, for a total of 305 cycles.
Comparative example 2
1. Battery assembly
Naturally storing the 6-DZF-20 battery grid for 5 days, then finishing aging, coating the plate, compacting lead paste, and performing surface drying treatment after acid spraying; and (4) assembling the battery after the polar plates are solidified, dried and sliced, and then adding acid for charging and finishing to finish the manufacture of the battery.
2. Performance detection
Under the environment temperature of 25 +/-2 ℃, the internal resistance value of a single battery is 11.07m omega through testing; and then the battery is over-discharged for 2d continuously by a constant resistance of 0.5 omega, charged for 24h by a constant voltage 15V current limiting 5A, and the 2h rate capacity of the battery is tested after the battery is kept stand for 2h, wherein the above is a test period, and the battery discharges capacities of 22.8Ah, 19.6Ah and 12.2Ah in 1, 5 and 10 periods respectively.
Comparative example 3
1. Battery assembly
Naturally storing the 6-DZF-20 battery grid for 3 days, then finishing aging, coating the plate, compacting lead paste, and performing surface drying treatment after acid spraying; and (4) assembling the battery after the polar plates are solidified, dried and sliced, and then adding acid for charging and finishing to finish the manufacture of the battery.
2. Performance detection
The internal resistance values of the battery pack are 10.99m omega, 10.88m omega, 11.06m omega and 11.42m omega under the test at the ambient temperature of 25 +/-2 ℃; then the batteries are connected in series and discharged to 42V by 10A, the constant voltage is 58.8V, the current is limited by 10A, the charging is carried out for 4h, a test cycle is carried out, and the current discharging termination voltage difference is as follows at 1, 50, 100 and 200 cycles, namely 0.23V, 0.69V, 1.39V and 2.76V.
Comparative example 4
1. A thermal spray coating slip was formulated as in example 1.
2. The 6-DZF-20 battery grid is not naturally aged and the surface of the grid is oxidized, and thermal spraying wrapping slurry is directly sprayed into a curing chamber, and the steps 3 and 4 of the embodiment 1 are the same.
3. After 3 days, coating a plate and compacting the lead plaster, and performing surface drying treatment after acid spraying; and (4) assembling the battery after the polar plates are solidified, dried and sliced, and then adding acid for charging and finishing to finish the manufacture of the battery.
4. Performance detection
The internal resistance value of the battery is 10.54m omega when the battery is tested at the ambient temperature of 25 +/-2 ℃; then the battery is discharged to 10.5V with a constant voltage of 14.7V at 10A, charged for 8h at a limited current of 5A, and kept still for 2h, wherein the battery respectively discharges 21.3Ah, 21.7Ah, 22.2Ah, 22.2Ah, 22.0Ah, 21.0Ah and 18.3Ah at 1, 10, 50, 100, 200, 300 and 400 cycles, and the service life is finished with the discharge capacity of less than 16Ah, thereby totally completing 412 cycles.
Comparative example 5
1. Compounding hot spraying coating pulp
a. Selecting 4BS (tetrabasic lead sulfate seed crystal) and sieving with a 200-mesh sieve, and discarding the sieve residue;
b. mixing phosphoric acid and 4BS according to the mass ratio of 1:4, adding pure water according to the mass ratio of 1:18 of the mixture to the pure water, and stirring at a high speed of 1200 revolutions per minute for 15 minutes;
c. the thermal spray coating slurry should be heated to a specified value prior to use.
2. The grid surface oxidation treatment was the same as in example 3.
3. Coating the slurry by hot spraying, high-temperature oxidation and drying, coating plates and assembling the battery are the same as the battery in the embodiment 2.
4. Performance detection
The cell has an internal resistance of 9.69m omega when tested at ambient temperature of 25 +/-2 ℃.
And then the battery is over-discharged for 2d continuously by a constant resistance of 0.5 omega, the battery is charged for 24h by a constant voltage 15V current limiting 5A, the 2h rate capacity of the battery is tested after the battery is kept stand for 2h, the above is a test period, and the battery discharges the capacities of 22.2Ah, 20.6Ah and 17.1Ah in 1, 5 and 10 periods respectively.
Comparative example 6
1. The coating slip was formulated as in example 3.
2. The grid surface oxidation treatment was the same as in example 3.
3. Wrapping pulp
The high-speed stirred coating paste was sprayed directly through the nozzle into the curing chamber without heating, and the other parameters were the same as in example 3.
4. After 7 days, coating a plate, compacting the lead paste, and performing surface drying treatment after acid spraying; the positive plate meeting the requirements is prepared by solidifying, drying and polishing the plate in a slicing way.
Coating the negative lead plaster on a 6-DZF-20 negative grid which is naturally stored for 3d and has finished aging, and preparing the negative plate after rolling, acid spraying, surface drying, curing and drying, slicing and polishing.
And assembling the prepared positive green plate and the prepared negative green plate, and then adding acid for charging and finishing to finish the preparation of the battery.
5. Performance detection
The battery has an internal resistance value of 10.18m omega when tested at an ambient temperature of 25 +/-2 ℃.
Then the battery is discharged to 10.5V at 10A, current-limited 5A at constant voltage of 14.7V is charged for 8h, and the battery is kept still for 2h, wherein the battery respectively discharges the capacities of 21.5Ah, 22.2Ah, 21.6Ah, 22.0Ah, 21.3Ah and 19.6Ah in 1, 10, 50, 100, 200 and 300 cycles.
The end of life was defined as the discharge capacity of less than 16Ah, which amounted to 371 cycles.
Claims (10)
1. The preparation method of the lead-calcium alloy positive plate is characterized by comprising the following steps of:
(1) taking phosphoric acid, tetrabasic lead sulfate seed crystal, antimony trioxide and lead powder according to the mass ratio of 1: 1-1.2: 1.5-2: 3-4, adding water into the mixture according to the mass ratio of the mixture to the water of 1: 15-19, stirring and heating to 75-85 ℃ to obtain wrapping slurry;
(2) suspending the lead-calcium alloy grid prepared after the sheet pouring process on a curing frame of a curing chamber, carrying out surface oxidation treatment, adjusting the circulating air speed of the curing chamber to 80-100% and the relative humidity to 75-90%, spraying the coating slurry obtained in the step (1) into the curing chamber, and blowing the coating slurry drops through the circulating air and coating the surface of the grid;
(3) and carrying out oxidation treatment on the grid with the wrapping slurry, drying to obtain a positive grid, and coating lead paste to obtain the lead-calcium alloy positive plate.
2. The method for preparing the lead-calcium alloy positive plate according to claim 1, wherein in the step (1), the particle sizes of the tetrabasic lead sulfate seed crystal, the antimony trioxide and the lead powder are all less than 200 meshes.
3. The method for preparing a lead-calcium alloy positive plate according to claim 1, wherein in the step (1), the stirring conditions are as follows: the rotating speed is 800-1500 r/min, and the time is more than or equal to 15 min.
4. The method for preparing the lead-calcium alloy positive plate according to claim 1, wherein in the step (2), the spacing between the lead-calcium alloy grids hung on the curing frame is 2-3 mm.
5. The method for preparing a lead-calcium alloy positive plate according to claim 1, wherein in the step (2), the conditions of the surface oxidation treatment are as follows: the relative humidity is 85-95%; temperature: setting the temperature to be 100-120 ℃ firstly, and then converting to be 70-80 ℃ after 2 hours; the wind speed is 10-30%; the oxidation time is 4-8 h.
6. The method for preparing the lead-calcium alloy positive plate according to claim 1, wherein in the step (2), the diameter of the coating slurry drop is 100-120 μm, the spraying rate of the coating slurry per cubic meter of the curing chamber is 2-5L/min, and the time is controlled to be 3-5 min.
7. The method for preparing the lead-calcium alloy positive plate as claimed in claim 6, wherein the coating slurry is repeatedly sprayed once after 5-15 min.
8. The method for preparing a lead-calcium alloy positive plate according to claim 1, wherein in the step (3), the oxidation treatment conditions sequentially include: a. oxidizing for 3-5 hours in an environment with a circulating air speed of 10-30%, a temperature of 70-80 ℃ and a relative humidity of 70-90%; b. and oxidizing for 3-5 hours in an environment with a circulating air speed of 50-70%, a temperature of 50-70 ℃ and a relative humidity of 50-80%.
9. The method for preparing a lead-calcium alloy positive plate according to claim 1, wherein the drying temperature in the step (3) is 80 ℃.
10. The method for preparing a lead-calcium alloy positive plate according to claim 1, wherein in the step (3), the positive lead paste is coated within 24 hours.
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| WO2022174585A1 (en) * | 2021-02-22 | 2022-08-25 | 天能电池集团股份有限公司 | Method for preparing positive plate and lead storage battery |
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