CN112582586B - Preparation process of lead-acid battery suitable for high-temperature use - Google Patents

Preparation process of lead-acid battery suitable for high-temperature use Download PDF

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Publication number
CN112582586B
CN112582586B CN202011271141.9A CN202011271141A CN112582586B CN 112582586 B CN112582586 B CN 112582586B CN 202011271141 A CN202011271141 A CN 202011271141A CN 112582586 B CN112582586 B CN 112582586B
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lead
charging
stirring
percent
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CN112582586A (en
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刘长来
夏诗忠
李斌
高国兴
孙龙
汪展
李国清
阮佳飞
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Yangzhou Apollo Battery Co ltd
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Camel Group Storage Battery Academy Co
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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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H01M4/16—Processes of manufacture
    • H01M4/20—Processes of manufacture of pasted electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H01M4/16—Processes of manufacture
    • H01M4/22—Forming of electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
    • H01M4/57—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead of "grey lead", i.e. powders containing lead and lead oxide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

A lead-acid battery preparation process suitable for high-temperature use, 715-735-lead powder; 170-; 101-111 deionized water; 92-96 sulfuric acid solution with density of 1.38g/cm3(ii) a 2.5-2.6 additive, 6.15-6.354 BS crystal seed and 0.8-1.0 polyester fiber; the lead plaster is prepared by a plaster mixing process, the lead plaster is uniformly coated and filled on the surface of a lead screen to produce a single wet polar plate, and a reverse internal formation process is carried out after the single wet polar plate is cured by a curing process, namely, the reverse formation is added before the battery is charged and formed. The invention adopts 4BS lead plaster, optimizes the curing process and uses the reverse formation process, and the high-temperature service life of the battery is improved by 60 percent compared with a comparative case. After 4BS lead plaster is adopted and the curing process is optimized, the connection between the grid and the active substance is strengthened, and the falling of the active substance does not become a main failure mode of the high-temperature service life of the battery any more.

Description

Preparation process of lead-acid battery suitable for high-temperature use
Technical Field
The invention belongs to the technical field of lead-acid storage batteries, and particularly relates to a preparation process of a lead-acid battery suitable for high-temperature use.
Background
At present, the storage battery on the market is mainly a maintenance-free lead-acid storage battery for starting an automobile, and the lead-acid storage battery mainly comprises a battery shell, electrolyte, a current collector, an active substance and other lead parts. Wherein the current collector is produced by using an expanded net pulling mode. When the storage battery is used for starting an automobile, the storage battery is generally arranged near an automobile engine, and the use environment temperature is high.
The surface of the current collector produced by the expansion net-pulling mode is smooth, but fine cracks which cannot be observed by naked eyes exist at nodes, and gaps exist at the connecting part of the current collector and the active substance due to the fact that the surface of the current collector is smooth. The addition of the fine cracks at the junctions makes the current collectors highly susceptible to attack by the electrolyte (sulfuric acid solution) during cell formation and use. Resulting in structural damage to the current collector and failure of the battery. This is particularly evident at high temperatures.
The method is not a main failure mode of the expanded grid lead-acid battery under the condition of low temperature or normal temperature, but is immediately raised to be the main failure mode in the high-temperature environment.
Disclosure of Invention
The invention aims to improve the lead-acid battery preparation process aiming at the failure mode of the lead-acid battery in the high-temperature use environment so as to achieve the purpose of prolonging the service life of the lead-acid battery under the high-temperature condition and be suitable for the high-temperature use.
The lead-acid battery high-temperature main failure mode is that the positive grid is corroded and grows, the corrosion directly causes battery failure, and the positive grid is in contact with the negative busbar after growing to generate short circuit so as to cause battery failure. The invention improves the formula of the 4BS lead plaster and the processes of plaster mixing, curing and internal formation, and can relieve the corrosion of the positive grid of the lead plaster.
The technical scheme of the invention comprises the following steps:
the 4BS lead plaster comprises the following components in parts by mass: 715-735kg of lead powder; 170-180kg red lead; 101-111kg deionized water; 92-96kg of sulfuric acid solution with a density of 1.38g/cm3(ii) a 2.5-2.6kg sodium perborate, 6.15-6.35kg4BS (PbSO4 x 4PbO) seed crystal, 0.8-1.0kg polyester fiber;
the paste mixing process comprises the following steps:
a: adding lead powder and deionized water into a stirring kettle of the paste mixer in sequence, and stirring at a constant speed for 320 +/-5 seconds;
b: stirring for 240 +/-5 seconds, adding 1 minute of sulfuric acid solution in the amount of 5 min at constant speed and stirring simultaneously;
c: adding the additive, the 4BS seed crystal, the polyester fiber and the red lead, and stirring for 300 +/-5 seconds;
d: stirring for 1260 plus or minus 5 seconds, adding the rest 4 minutes of sulfuric acid solution at constant speed, and stirring at constant speed;
e: stirring at constant speed for 480 +/-5 seconds;
the lead plaster is transferred into a plaster coating hopper and is uniformly coated and filled on the surface of a lead net through a plaster coating machine, then the lead net is cut to produce a single wet polar plate, the single wet polar plate is transferred to a curing chamber after being rapidly dried by a drying kiln, and is cured by a curing process to carry out a reverse internal formation process, wherein the reverse internal formation process is to add reverse formation before battery charging formation.
The curing process of the invention comprises the following steps: the first stage is as follows: the temperature is 75 +/-2 ℃; relative humidity: 98 plus or minus 2 percent; time: 7 +/-0.1 h;
and a second stage: the temperature is 50 +/-2 ℃; relative humidity: 50 +/-2%; time: 10 plus or minus 0.1 h;
and a third stage: the temperature is 55 +/-2 ℃; relative humidity: 98 plus or minus 2 percent; time: 7 +/-0.1 h;
a fourth stage: the temperature is 70 plus or minus 2 ℃; relative humidity: 30 plus or minus 2 percent; time: 8 plus or minus 0.1 h;
the fifth stage: the temperature is 75 +/-2 ℃; relative humidity: 20 plus or minus 2 percent; time: 4 plus or minus 0.1 h;
the sixth stage: the temperature is 80 +/-2 ℃; relative humidity: 10 plus or minus 2 percent; time: 12 plus or minus 0.1 h;
the heating mode adopts electric heating, the humidification adopts atomized water, and the relative humidity control is controlled by a circulating fan system.
The first stage of the inversion is the reverse charging stage.
The reverse internal formation process comprises the following steps:
the first stage is as follows: carrying out constant current reverse charging at 10A for 30 +/-2 min, and standing for 20 +/-2 min;
and a second stage: charging at constant current of 10A for 20 plus or minus 2 min;
and a third stage: charging at 24A current constant current forward direction for 4+ -0.1 h, and standing for 10 + -2 min;
a fourth stage: charging at a constant current of 17A for 2 +/-0.1 h in a forward direction, and standing for 10 +/-2 min;
the fifth stage: discharging at constant current of 20A for 30 + -2 min, and standing for 2 + -2 min;
the sixth stage: charging positively for 3 + -0.1 h at constant current of 24A, and standing for 10 + -2 min;
a seventh stage: charging at a constant current of 17A for 6 +/-0.1 h in a forward direction, and standing for 30 +/-2 min;
an eighth stage: and charging the battery for 4 +/-0.1 h at a constant current of 10A in a positive direction.
The lead powder is 73% of alpha-PbO +27% of Pb.
The red lead of the invention is 65 percent of PbO and 35 percent of PbO2。
The additive is sodium perborate.
According to the 4BS lead plaster formula, the positive and negative components before battery formation are mainly lead sulfate, when the battery formation is carried out, the positive electrode has electrochemical reaction PbSO4-2e → PbO2, PbSO4+2e → Pb, the Pb substance state is far more stable than that of PbO2, and the activation energy of the positive electrode reaction is far higher than that of the negative electrode, so that the main control step of the battery formation is in the positive electrode. The completion of the electrochemical reaction of the positive electrode needs to output electrons, PbSO4 has no conductivity, the positive electrode electrons cannot be output in time to reduce the reaction speed, the formation potential of the positive electrode rises, the temperature of the electrolyte rises, and the corrosion of the positive grid is aggravated. Therefore, red lead is added into the lead plaster, and the red lead contains PbO2, and has positive effects: reducing the formation electric quantity; b: the PbO2 has certain conductive capability, can reduce the positive electrode formation potential and reduce the corrosion of a positive grid. c: PbO2 is dispersed in the active material, and PbO2 generated during the formation of the battery anode is gathered on the conventional PbO2 to form an active material skeleton with a wider coverage area.
Because PbO2 in red lead and Pb in lead powder can generate chemical reaction under acidic condition to generate PbSO 4. Aiming at the problem, the paste mixing process of the invention firstly adds a small amount of acid before adding red lead to reduce Pb in lead powder to the minimum.
In order to increase the bonding strength between the positive grid and the active substance, strengthen the conductivity between the grid and the active substance and reduce the corrosion of the grid in the battery formation process, the invention prolongs the 3 rd and 4 th stage time of the curing process and adjusts the corresponding temperature and humidity process to enhance the bonding strength between the positive grid and the active substance;
the reverse internal formation process is to adjust and optimize the conventional internal formation of the battery and change the first stage (the first stage) into the reverse charging stage.
The reverse internal formation process comprises the following steps: the reverse formation is increased for 30min before the normal charge formation, a small amount of Pb is generated in the positive active material by the reverse formation, the Pb conductivity is strong, the positive formation potential is effectively reduced in the subsequent forward formation stage, and the electrolyte corrosion borne in the positive grid formation process is reduced.
The invention adopts 4BS lead plaster, optimizes the curing process and uses the reverse formation process, and the high-temperature service life of the battery is improved by 60 percent compared with a comparative case. After 4BS lead plaster is adopted and the curing process is optimized, the connection between the grid and the active substance is strengthened, and the falling of the active substance does not become a main failure mode of the high-temperature service life of the battery any more.
Detailed Description
Example 1
The formula of the 4BS lead plaster comprises: 725kg of lead powder (73% of alpha-PbO +27% of Pb) and 175kg of red lead (65% of PbO +35% of PbO)2) 106kg of deionized water, 96kg of a sulfuric acid solution (density: 1.38g/cm3) 2.6kg of sodium perborate, 6.25kg of 4BS (PbSO4 x 4PbO) seed crystal, 1.0kg of polyester fiber;
the paste mixing process comprises the following steps:
a: adding 725kg of lead powder and 106kg of deionized water into a stirring kettle of the paste mixing machine, and stirring at a constant speed for 320 seconds;
b: stirring for 240 seconds, and adding 20kg of sulfuric acid solution (density of 1.38 g/cm) at constant speed3) Stirring simultaneously;
c: adding 2.6kg of additive, 6.25kg of 4BS seed crystal, 1.0kg of polyester fiber and 175kg of red lead, and stirring for 300 seconds;
d: stirring for 1260 seconds, and adding 76kg of sulfuric acid solution (density of 1.38 g/cm) at constant speed3) Stirring at constant speed;
e: stirring at a constant speed for 480 seconds;
the curing process comprises the following steps: the first stage is as follows: the temperature is 75 ℃; relative humidity: 98 percent; time: 7 h;
and a second stage: the temperature is 50 ℃; relative humidity: 50 percent; time: 10 h;
and a third stage: the temperature is 55 ℃; relative humidity: 98 percent; time: 7 h;
a fourth stage: the temperature is 70 ℃; relative humidity: 30 percent; time: 8 h;
the fifth stage: the temperature is 75 ℃; relative humidity: 20 percent; time: 4 h;
the sixth stage: the temperature is 80 ℃; relative humidity: 10 percent; time: 12 h;
in total: 48h, adopting electric heating in a heating mode, adopting atomized water for humidification, and controlling relative humidity through a circulating fan system
The reverse internal formation process comprises the following steps:
the first stage is as follows: carrying out constant current reverse charging at a current of 10A for 30min, and then standing for 20 min;
and a second stage: charging at constant current of 10A for 20 min;
and a third stage: carrying out constant current forward charging for 4h at a current of 24A, and standing for 10 min;
a fourth stage: carrying out constant current forward charging for 2h at a current of 17A, and then standing for 10 min;
the fifth stage: discharging at constant current of 20A for 30min, and standing for 2 min;
the sixth stage: carrying out constant current forward charging for 3h at a current of 24A, and standing for 10 min;
a seventh stage: carrying out constant current forward charging for 6h at a current of 17A, and then standing for 30 min;
an eighth stage: charging for 4h at a constant current and a positive direction of 10A current;
total time: 21.7h, total charge: 227.2Ah
Example 2
The formula of the 4BS lead plaster comprises: 730kg of lead powder (73% of alpha-PbO +27% of Pb) and 180kg of red lead (65% of PbO +35% of PbO)2) 106kg of deionized water, 96kg of a sulfuric acid solution (density: 1.38g/cm3) 2.6kg of sodium perborate, 6.3kg of 4BS (PbSO4 x 4PbO) seed crystal, 1.0kg of polyester fiber;
the paste mixing process comprises the following steps:
a: adding lead powder and deionized water into a stirring kettle of the paste mixing machine in sequence, and stirring at a constant speed for 320 seconds;
b: stirring for 240 seconds, and adding 20kg of sulfuric acid solution (density of 1.38 g/cm) at constant speed3) Stirring simultaneously;
c: adding 2.6kg of additive, 6.25kg of 4BS seed crystal, 1.0kg of polyester fiber and 175kg of red lead, and stirring for 300 seconds;
d: stirring for 1260 seconds, and adding 76kg of sulfuric acid solution (density of 1.38 g/cm) at constant speed3) Stirring at constant speed;
e: stirring at a constant speed for 480 seconds;
the curing process comprises the following steps: the first stage is as follows: the temperature is 75 ℃; relative humidity: 98 percent; time: 7 h;
and a second stage: the temperature is 50 ℃; relative humidity: 50 percent; time: 10 h;
and a third stage: the temperature is 55 ℃; relative humidity: 98 percent; time: 7 h;
a fourth stage: the temperature is 70 ℃; relative humidity: 30 percent; time: 8 h;
the fifth stage: the temperature is 75 ℃; relative humidity: 20 percent; time: 4 h;
the sixth stage: the temperature is 80 ℃; relative humidity: 10 percent; time: 12 h;
in total: 48h, adopting electric heating in a heating mode, adopting atomized water for humidification, and controlling relative humidity through a circulating fan system
The reverse internal formation process comprises the following steps:
the first stage is as follows: carrying out constant current reverse charging at a current of 10A for 30min, and then standing for 20 min;
and a second stage: charging at constant current of 10A for 20 min;
and a third stage: carrying out constant current forward charging for 4h at a current of 24A, and standing for 10 min;
a fourth stage: carrying out constant current forward charging for 2h at a current of 17A, and then standing for 10 min;
the fifth stage: discharging at constant current of 20A for 30min, and standing for 2 min;
the sixth stage: carrying out constant current forward charging for 3h at a current of 24A, and standing for 10 min;
a seventh stage: carrying out constant current forward charging for 6h at a current of 17A, and then standing for 30 min;
an eighth stage: charging for 4h at a constant current and a positive direction of 10A current;
total time: 21.7h, total charge: 227.2Ah
Comparative example 1
The formula of the common lead plaster comprises: 1000kg of lead powder (76% of. alpha. -PbO + 24% of Pb), 110kg of deionized water, and 103.4kg of a sulfuric acid solution (density: 1.38 g/cm)3) 2.2kg of sodium perborate and 0.8kg of polyester fiber;
the paste mixing process comprises the following steps:
a: adding lead powder and deionized water into a stirring kettle of the paste mixer in sequence, and stirring at a constant speed for 280 seconds;
b: adding 2.2kg of sodium perborate and 0.8kg of polyester fiber, and stirring for 300 seconds;
c: stirring for another 120 s, adding 103.4kg sulfuric acid solution (density 1.38 g/cm) at uniform speed3) Stirring simultaneously;
d: stirring at constant speed for 480 seconds after the sulfuric acid solution is added;
the curing process comprises the following steps: the first stage is as follows: the temperature is 45 ℃; relative humidity: 98 percent; time: 8 h;
and a second stage: the temperature is 50 ℃; relative humidity: 50 percent; time: 12 h;
and a third stage: the temperature is 55 ℃; relative humidity: 98 percent; time: 5 h;
a fourth stage: the temperature is 70 ℃; relative humidity: 30 percent; time: 3 h;
the fifth stage: the temperature is 75 ℃; relative humidity: 16 percent; time: 4 h;
the sixth stage: the temperature is 80 ℃; relative humidity: 5 percent; time: 20 h;
in total: 52h, heating by steam, humidifying by atomized water, and controlling relative humidity by a circulating fan system
Formation process:
the first stage is as follows: charging for 1.5h at a constant current and a positive direction of 10A current;
and a second stage: charging at a constant current of 22A for 4.5h in a forward direction, and standing for 10 min;
and a third stage: carrying out constant current forward charging for 2h at a current of 10A, and then standing for 10 min;
a fourth stage: discharging with constant current of 20A for 10min, and standing for 2 min;
the fifth stage: carrying out constant current forward charging for 2h at a current of 24A, and then standing for 10 min;
the sixth stage: carrying out constant current forward charging for 4h at a current of 17A, and standing for 30 min;
a seventh stage: charging for 2h at a constant current and a positive direction of 10A current;
total time: 17h, total electric quantity: 270Ah
Comparative example 2
The formula of the common lead plaster comprises: 1000kg of lead powder (76% of. alpha. -PbO + 24% of Pb), 110kg of deionized water, and 103.4kg of a sulfuric acid solution (density: 1.38 g/cm)3) 2.2kg of sodium perborate and 0.8kg of polyester fiber;
the paste mixing process comprises the following steps:
a: adding lead powder and deionized water into a stirring kettle of the paste mixer in sequence, and stirring at a constant speed for 280 seconds;
b: adding 2.2kg of sodium perborate and 0.8kg of polyester fiber, and stirring for 300 seconds;
c: stirring for another 120 s, adding 103.4kg sulfuric acid solution (density 1.38 g/cm) at uniform speed3) Stirring simultaneously;
d: stirring at constant speed for 480 seconds after the sulfuric acid solution is added;
the curing process comprises the following steps: the first stage is as follows: the temperature is 75 ℃; relative humidity: 98 percent; time: 7 h;
and a second stage: the temperature is 50 ℃; relative humidity: 50 percent; time: 10 h;
and a third stage: the temperature is 55 ℃; relative humidity: 98 percent; time: 7 h;
a fourth stage: the temperature is 70 ℃; relative humidity: 30 percent; time: 8 h;
the fifth stage: the temperature is 75 ℃; relative humidity: 20 percent; time: 4 h;
the sixth stage: the temperature is 80 ℃; relative humidity: 10 percent; time: 12 h;
in total: 48h, adopting electric heating in a heating mode, adopting atomized water for humidification, and controlling relative humidity through a circulating fan system
The formation process comprises the following steps:
the first stage is as follows: charging for 1.5h at a constant current and a positive direction of 10A current;
and a second stage: charging at a constant current of 22A for 4.5h in a forward direction, and standing for 10 min;
and a third stage: carrying out constant current forward charging for 2h at a current of 10A, and then standing for 10 min;
a fourth stage: discharging with constant current of 20A for 10min, and standing for 2 min;
the fifth stage: carrying out constant current forward charging for 2h at a current of 24A, and then standing for 10 min;
the sixth stage: carrying out constant current forward charging for 4h at a current of 17A, and standing for 30 min;
a seventh stage: charging for 2h at a constant current and a positive direction of 10A current;
total time: 17h, total electric quantity: 270Ah
Comparative example 3
The formula of the 4BS lead plaster comprises: 730kg of lead powder (73% of alpha-PbO +27% of Pb) and 180kg of red lead (65% of PbO +35% of PbO)2) 106kg of deionized water, 96kg of a sulfuric acid solution (density: 1.38g/cm3) 2.6kg of sodium perborate, 6.3kg of 4BS (PbSO4 x 4PbO) seed crystal, 1.0kg of polyester fiber;
the paste mixing process comprises the following steps:
a: adding lead powder and deionized water into a stirring kettle of the paste mixing machine in sequence, and stirring at a constant speed for 320 seconds;
b: stirring for 240 seconds, and adding 20kg of sulfuric acid solution (density of 1.38 g/cm) at constant speed3) Stirring simultaneously;
c: adding 2.6kg of additive, 6.25kg of 4BS seed crystal, 1.0kg of polyester fiber and 175kg of red lead, and stirring for 300 seconds;
d: stirring for 1260 seconds, and adding 76kg of sulfuric acid solution (density of 1.38 g/cm) at constant speed3) Stirring at constant speed;
e: stirring at a constant speed for 480 seconds;
the curing process comprises the following steps: the first stage is as follows: the temperature is 75 ℃; relative humidity: 98 percent; time: 7 h;
and a second stage: the temperature is 50 ℃; relative humidity: 50 percent; time: 10 h;
and a third stage: the temperature is 55 ℃; relative humidity: 98 percent; time: 7 h;
a fourth stage: the temperature is 70 ℃; relative humidity: 30 percent; time: 8 h;
the fifth stage: the temperature is 75 ℃; relative humidity: 20 percent; time: 4 h;
the sixth stage: the temperature is 80 ℃; relative humidity: 10 percent; time: 12 h;
in total: and (3) 48h, adopting electric heating for heating, adopting atomized water for humidifying, and controlling the relative humidity through a circulating fan system.
The formation process comprises the following steps: the first stage is as follows: charging for 1.5h at a constant current and a positive direction of 10A current;
and a second stage: charging at a constant current of 22A for 4.5h in a forward direction, and standing for 10 min;
and a third stage: carrying out constant current forward charging for 2h at a current of 10A, and then standing for 10 min;
a fourth stage: discharging with constant current of 20A for 10min, and standing for 2 min;
the fifth stage: carrying out constant current forward charging for 2h at a current of 24A, and then standing for 10 min;
the sixth stage: carrying out constant current forward charging for 4h at a current of 17A, and standing for 30 min;
a seventh stage: charging for 2h at a constant current and a positive direction of 10A current;
total time: 17h, total electric quantity: 270Ah
In order to show the effect of the invention, the applicant commissions the detection center of Apollo storage battery, Yangzhou, to carry out the detection of 'improving the grid corrosion resistance' on the product of the invention and the product of the comparative example, and the detection method adopts the standards of GB/T5008.1-2013 and SAE2801, and the results are shown in the report number of detection report 'S2019-0019 and the report number of detection report' S2019-0153. The results are shown in the following table:
Figure BDA0002777683180000081
description of the test:
comparative example 1 is a prior art rich liquid battery of my company, with a service life at high temperature characterized as 10 units using SAE J2801 life; see test results of the experimental battery number A9020202 in the report number S2019-0019 of detection report.
Comparative example 2 the curing process of the present invention was applied to the plate curing process of the prior art of our company, which improves the conductivity between the active material and the grid (current collector), and reduces the positive electrode potential, thereby slightly increasing the high temperature life of the battery (SAE life is increased from 10 units to 11 units, see the experimental result of experimental battery number a9020205 in test report number S2019-0019.
Comparative example 3 the 4BS lead paste of the present invention (including formulation and paste mixing process) was used in place of the prior art lead paste on the basis of comparative example 2 to further improve the high temperature life of the battery (SAE life was improved from 11 units to 12 units). See test results of test battery number A9020207 in test report number S2019-0019.
Examples 1 and 2 are processes of the present invention, in which a first stage (first stage) is changed to a reverse charging stage in a battery container formation process. In the reverse charging stage, partial metal Pb is formed in the positive lead paste in a formal charging mode, the Pb has high conductivity, the positive formation potential is effectively reduced in the subsequent forward formation stage, the electrolyte corrosion borne in the positive grid formation process is reduced, the positive grid is not easily corroded by the electrolyte in the subsequent cycle use process, and the high-temperature service life of the battery is greatly prolonged (the SAE service life is prolonged from 12 units to 16 units). The experimental results of the experimental battery number A9090302 in the report number of detection report S2019-0153 in example 1 and the experimental battery number A90306 in the report number of detection report S2019-0153 in example 2 are shown in the report number of detection report S2019-0153.
The accessory 1 is a report number S2019-0153 of detection report;
the accessory 2 is a report number S2019-0019 of detection report.
Figure BDA0002777683180000101
Figure BDA0002777683180000111
Figure BDA0002777683180000121
Figure BDA0002777683180000131
Figure BDA0002777683180000141
Figure BDA0002777683180000151
Figure BDA0002777683180000161
Figure BDA0002777683180000171
Figure BDA0002777683180000181
Figure BDA0002777683180000191
Figure BDA0002777683180000201
Figure BDA0002777683180000211
Figure BDA0002777683180000221
Figure BDA0002777683180000231
Figure BDA0002777683180000241

Claims (7)

1. A preparation process of a grid lead-acid battery suitable for high-temperature use is characterized by comprising the following steps:
the 4BS lead plaster comprises the following components in parts by mass: 715-735kg of lead powder; 170-180kg red lead; 101-111kg deionized water; 92-96kg of sulfuric acid solution with a density of 1.38g/cm3；
2.5-2.6kg of additive, 6.15-6.35kg of 4BS seed crystal and 0.8-1.0kg of polyester fiber;
the paste mixing process comprises the following steps:
a: adding lead powder and deionized water into a stirring kettle of the paste mixer in sequence, and stirring at a constant speed for 320 +/-5 seconds;
b: stirring for 240 +/-5 seconds, adding 1 minute of sulfuric acid solution in the amount of 5 min at constant speed and stirring simultaneously;
c: adding the additive, the 4BS seed crystal, the polyester fiber and the red lead, and stirring for 300 +/-5 seconds;
d: stirring for 1260 plus or minus 5 seconds, adding the rest 4 minutes of sulfuric acid solution at constant speed, and stirring at constant speed;
e: stirring at constant speed for 480 +/-5 seconds;
the lead plaster is transferred into a plaster coating hopper and is uniformly coated and filled on the surface of a lead net through a plaster coating machine, then the lead net is cut to produce a single wet polar plate, the single wet polar plate is transferred to a curing chamber after being rapidly dried by a drying kiln, and is cured by a curing process to carry out a reverse internal formation process, wherein the reverse internal formation process is to add reverse formation before battery charging formation.
2. The process for preparing a expanded grid lead-acid battery suitable for high temperature use according to claim 1, wherein the process comprises the following steps:
the curing process comprises the following steps: the first stage is as follows: the temperature is 75 +/-2 ℃; relative humidity: 98 percent; time: 7 +/-0.1 h;
and a second stage: the temperature is 50 +/-2 ℃; relative humidity: 50 percent; time: 10 plus or minus 0.1 h;
and a third stage: the temperature is 55 +/-2 ℃; relative humidity: 98 percent; time: 7 +/-0.1 h;
a fourth stage: the temperature is 70 plus or minus 2 ℃; relative humidity: 30 percent; time: 8 plus or minus 0.1 h;
the fifth stage: the temperature is 75 +/-2 ℃; relative humidity: 20 percent; time: 4 plus or minus 0.1 h;
the sixth stage: the temperature is 80 +/-2 ℃; relative humidity: 10 percent; time: 12 plus or minus 0.1 h;
the heating mode adopts electric heating, the humidification adopts atomized water, and the relative humidity control is controlled by a circulating fan system.
3. The process for preparing a expanded grid lead-acid battery suitable for high temperature use according to claim 1, wherein the process comprises the following steps: the first stage of the reverse charging formation is the reverse charging stage.
4. The process for preparing a expanded grid lead-acid battery suitable for high temperature use according to claim 1, wherein the process comprises the following steps: the reverse internal formation process comprises the following steps:
the first stage is as follows: carrying out constant current reverse charging at 10A for 30 +/-2 min, and standing for 20 +/-2 min;
and a second stage: charging at constant current of 10A for 20 plus or minus 2 min;
and a third stage: charging at 24A current constant current forward direction for 4+ -0.1 h, and standing for 10 + -2 min;
a fourth stage: charging at a constant current of 17A for 2 +/-0.1 h in a forward direction, and standing for 10 +/-2 min;
the fifth stage: discharging at constant current of 20A for 30 + -2 min, and standing for 2 + -2 min;
the sixth stage: charging positively for 3 + -0.1 h at constant current of 24A, and standing for 10 + -2 min;
a seventh stage: charging at a constant current of 17A for 6 +/-0.1 h in a forward direction, and standing for 30 +/-2 min;
an eighth stage: and charging the battery for 4 +/-0.1 h at a constant current of 10A in a positive direction.
5. The process for preparing a expanded grid lead-acid battery suitable for high temperature use according to claim 1, wherein the process comprises the following steps: the lead powder is 73% of alpha-PbO +27% of Pb.
6. The process for preparing a expanded grid lead-acid battery suitable for high temperature use according to claim 1, wherein the process comprises the following steps: the red lead is 65 percent of PbO and 35 percent of PbO2。
7. The process for preparing a expanded grid lead-acid battery suitable for high temperature use according to claim 1, wherein the process comprises the following steps: the additive is sodium perborate.
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