CN107681204B - formation process of battery prepared by using recovered lead powder - Google Patents

formation process of battery prepared by using recovered lead powder Download PDF

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Publication number
CN107681204B
CN107681204B CN201710780567.9A CN201710780567A CN107681204B CN 107681204 B CN107681204 B CN 107681204B CN 201710780567 A CN201710780567 A CN 201710780567A CN 107681204 B CN107681204 B CN 107681204B
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battery
charging
constant current
stage
lead powder
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CN107681204A (en
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代少振
徐丹
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Chaowei Power Group Co Ltd
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Chaowei Power Supply 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H01M10/12—Construction or manufacture
    • 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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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

the invention discloses a formation process of a battery prepared by using recovered lead powder, which comprises the following steps: before charging, placing the battery prepared by using the recovered lead powder in a water bath and standing for 0.5-1 h; charging at 0.02-0.25 deg.C for the first stage; discharging the battery with a current of-0.25C; charging at the second stage with 0.02-0.25 deg.C current; discharging the battery with a current of-0.5C; charging at 0.12-0.25 deg.C for the third stage; charging at 0.02-0.025 deg.C for 2-3h, and pumping acid. The invention has the following beneficial effects: the formation process of a 3-charge-2-discharge mode is adopted, so that the initial capacity of the battery is high, and the cycle life is long; a large current and small current alternative charging formation method is adopted in the later stage of the first charging stage, so that the formation time is shortened; the internal formation method adopted by the invention is energy-saving and environment-friendly.

Description

formation process of battery prepared by using recovered lead powder
Technical Field
The invention relates to the technical field of battery formation processes, in particular to a battery formation process which is high in initial capacity, long in cycle life, short in internal formation time, energy-saving and environment-friendly and is prepared by using recycled lead powder.
background
The formation of the lead-acid storage battery is a very critical process in the manufacture of the lead-acid storage battery, and the performance and the service life of the lead-acid storage battery are directly influenced by the quality of the formation process. Even if the lead-acid storage batteries with the same formula, the same process and the same batch are used, the change of the particle size and the arrangement form of the active materials can be caused by different currents and different formation times in the formation process. At present, the Shimadzu lead powder with the oxidation degree of 70-80% prepared by electrolytic lead and a pyrogenic lead ingot is well-developed by acidification after being assembled into a battery by paste mixing and curing, and the battery directly prepared by using the lead powder with the oxidation degree of more than 90% of the recovered lead powder generally adopts a power battery internal formation process adopted by the Shimadzu lead powder, the formation process of the type generally needs 100 plus 120 hours, and the battery directly prepared by using the recovered lead powder not only can cause overcharge, but also influences the performance and the cycle life of the battery and greatly wastes time and energy.
disclosure of Invention
the invention provides a formation process of a battery prepared by using recycled lead powder, which has the advantages of high initial capacity, long cycle life, short internal formation time, energy conservation and environmental protection, and aims to overcome the defects of overcharge, short cycle life and time and energy waste in the prior art.
in order to achieve the purpose, the invention adopts the following technical scheme:
a formation process for a battery prepared by using recovered lead powder is in a 3-charge-2-discharge mode and comprises the following steps:
(1-1) placing the battery prepared by using the recovered lead powder in a water bath for standing for 0.5-1h before starting charging;
(1-2) a first charging stage: charging the battery in multiple stages at a current of 0.02-0.25C, wherein the charging amount is 5.675-9 times of the rated capacity of the battery;
(1-3) a first discharge phase: discharging the battery by a constant current of-0.25C until the voltage of the battery is 10.5 v/cell;
(1-4) a second charging stage: the battery is charged in multiple stages at a current of 0.02-0.25C, and the charged electric quantity is 2.74-4.34 times of the rated capacity of the battery;
(1-5) second discharge stage: discharging the battery by a constant current of-0.5C until the voltage of the battery is 10.5 v/cell;
(1-6) third charging stage: charging the battery in multiple stages at a current of 0.12-0.25 ℃, wherein the charging amount is 1.765-2.875 times of the rated capacity of the battery;
(1-7) acid extraction stage: charging the battery for 2-3h at a constant current of 0.02-0.025 ℃, and then starting acid extraction.
the invention adopts a three-charge and two-discharge mode to carry out formation on the battery prepared by using the recycled lead powder, simultaneously optimizes the charge current, the charge time and the discharge current of each charge and discharge stage, shortens the formation time, and ensures that the battery has high initial capacity and long cycle life.
preferably, the first charging phase comprises the steps of:
(2-1) charging the battery for 1-2 h at a constant current of 0.02-0.025 ℃;
(2-2) charging the battery for 1-2 h with a constant current of 0.12-0.125 ℃;
(2-3) charging the battery for 1-2 h with a constant current of 0.15-0.18C;
(2-4) charging the battery for 3-4 h at a constant current of 0.175-0.20C;
(2-5) charging the battery for 8-10 h with a constant current of 0.2-0.25 ℃;
(2-6) charging the battery for 1-2 h at a constant current of 0.02-0.025 ℃;
(2-7) charging the battery for 8-10 h with a constant current of 0.2-0.25 ℃;
(2-8) charging the battery for 1-2 h at a constant current of 0.02-0.025 ℃;
(2-9) charging the battery for 8-10 h with a constant current of 0.2-0.25 ℃;
(2-10) charging the battery for 1-2 h with a constant current of 0.02-0.025C.
preferably, the second charging phase comprises the steps of:
(3-1) charging the battery for 8-10 h with a constant current of 0.2-0.25 ℃;
(3-2) charging the battery for 4-5 h at a constant current of 0.175-0.20C;
(3-3) charging the battery for 2-3h with a constant current of 0.15-0.18C;
(3-4) charging the battery for 1-2 h at a constant current of 0.12-0.125 ℃;
(3-5) charging the battery for 1-2 h at a constant current of 0.02-0.025 ℃.
Preferably, the third charging phase comprises the steps of:
(4-1) charging the battery for 5-6 h with a constant current of 0.2-0.25 ℃;
(4-2) charging the battery for 3-5 h at a constant current of 0.175-0.20C;
(4-3) charging the battery for 2-3h with a constant current of 0.12-0.125 ℃.
preferably, the internal temperature of the battery prepared by using the recovered lead powder is controlled to be less than or equal to 55 ℃ in the formation process of the battery.
preferably, the acid density of the acid added at normal temperature is controlled to be 1.250-1.260 g/ml in the formation process of the battery prepared by using the recovered lead powder.
Preferably, the oxidation degree of the recovered lead powder is 90% to 100%.
therefore, the invention has the following beneficial effects: (1) the formation process of the 3-charge-2-discharge mode adopted by the invention ensures that the initial capacity of the battery is high and the cycle life is long; (2) a large current and small current alternative charging formation method is adopted in the later stage of the first charging stage, so that the formation time is shortened; (3) the internal formation method adopted by the invention is energy-saving and environment-friendly.
drawings
fig. 1 is a flowchart of embodiment 1 of the present invention.
Detailed Description
the invention is further described in the following detailed description with reference to the drawings in which:
Example 1
the embodiment shown in fig. 1 is a formation process of a battery prepared by using recycled lead powder, and the formation process is in a 3-charge-2-discharge mode and comprises the following steps:
(1-1) placing a battery prepared by using the recovered lead powder in a water bath for standing for 1h before starting charging;
(1-2) a first charging stage: the battery is charged in multiple stages at a current of 0.02-0.25C, and the charging quantity is 5.675-9 times of the rated capacity of the battery, and the specific steps are as follows;
(1-2-1) charging the battery for 2h with a constant current of 0.02C;
(1-2-2) charging the battery for 2h with a constant current of 0.12C;
(1-2-3) charging the battery for 2 hours at a constant current of 0.15C;
(1-2-4) charging the battery for 4h at a constant current of 0.175 ℃;
(1-2-5) charging the battery for 10 hours at a constant current of 0.2C;
(1-2-6) charging the battery for 2h with a constant current of 0.02C;
(1-2-7) charging the battery for 10 hours at a constant current of 0.2C;
(1-2-8) charging the battery for 2h with a constant current of 0.02C;
(1-2-9) charging the battery for 10 hours at a constant current of 0.2C;
(1-2-10) charging the battery for 2h with a constant current of 0.02C;
(1-3) a first discharge phase: discharging the battery by a constant current of-0.25C until the voltage of the battery is 10.5 v/cell;
(1-4) a second charging stage: the battery is charged in multiple stages at a current of 0.02-0.25C, and the charged quantity is 2.74-4.34 times of the rated capacity of the battery, and the specific steps are as follows;
(1-4-1) charging the battery for 10 hours at a constant current of 0.2;
(1-4-2) charging the battery for 5 hours at a constant current of 0.175;
(1-4-3) charging the battery for 3 hours at a constant current of 0.15C;
(1-4-4) charging the battery for 2h with a constant current of 0.12C;
(1-4-5) charging the battery for 2h at a constant current of 0.02C;
(1-5) second discharge stage: discharging the battery by a constant current of-0.5C until the voltage of the battery is 10.5 v/cell;
(1-6) third charging stage: the battery is charged in multiple stages at a current of 0.12-0.25C, and the charging quantity is 1.765-2.875 times of the rated capacity of the battery, and the specific steps are as follows;
(1-6-1) charging the battery for 6h with a constant current of 0.2C;
(1-6-2) charging the battery for 5 hours at a constant current of 0.175 ℃;
(1-6-3) charging the battery for 3 hours at a constant current of 0.12C;
(1-7) acid extraction stage: the cell was charged for 3h at a constant current of 0.02 and acid extraction was then started.
the charging capacity of the first charging stage is 5.675-9 times of rated capacity, and a large-current and small-current alternative charging formation method is adopted in 5-10 steps of the first charging stage, so that the formation time is shortened, the large amount of water loss in the formation process caused by high polarization due to long-time charging with large current is reduced, and meanwhile, most of lead sulfate of the positive plate is ensured to be converted into lead dioxide; the charging capacity of the second charging stage is 2.74-4.34 times of rated capacity, so that the lead sulfate on the surface of the positive plate is completely converted, and the phenomena that the effective area of the plate is gradually reduced, active materials fall off, the capacity of the battery is reduced or the battery cannot be charged due to the formation of PbSO4 crystals caused by the abnormal conversion of PbSO4 are avoided, and the battery is difficult to reach the designed service life and fails prematurely; the third charging stage is used for charging the rated capacity 1.765-2.875 times of the electric quantity; in the whole formation process, the internal temperature of the battery is not more than 55 ℃, and in the whole formation process, the acid density of the acid added at normal temperature is controlled to be 1.250-1.260 g/ml.
example 2
Example 2 includes all the steps of example 1, and example 2 replaces the corresponding steps in example 1 with the following steps:
(1-2) a first charging stage:
(1-2-1) charging the battery for 1h with a constant current of 0.025C;
(1-2-2) charging the battery for 1h with a constant current of 0.125C;
(1-2-3) charging the battery for 1h with a constant current of 0.18C;
(1-2-4) charging the battery for 3 hours at a constant current of 0.20C;
(1-2-5) charging the battery for 8 hours at a constant current of 0.25 ℃;
(1-2-6) charging the battery for 1h at a constant current of 0.025C;
(1-2-7) charging the battery for 8 hours at a constant current of 0.25 ℃;
(1-2-8) charging the battery for 1h at a constant current of 0.025C;
(1-2-9) charging the battery for 8 hours at a constant current of 0.25 ℃;
(1-2-10) charging the battery for 1h at a constant current of 0.025C;
(1-4) a second charging stage:
(1-4-1) charging the battery for 8 hours at a constant current of 0.25C;
(1-4-2) charging the battery for 4 hours at a constant current of 0.20C;
(1-4-3) charging the battery for 2 hours at a constant current of 0.18C;
(1-4-4) charging the battery for 1h with a constant current of 0.125C;
(1-4-5) charging the battery for 1h at a constant current of 0.025C;
(1-6) third charging stage:
(1-6-1) charging the battery for 5 hours at a constant current of 0.25C;
(1-6-2) charging the battery for 3 hours at a constant current of 0.20C;
(1-6-3) charging the battery for 2h with a constant current of 0.125C;
(1-7) acid extraction stage: the cell was charged for 2h at a constant current of 0.025C and acid extraction was then initiated.
example 3
example 3 includes all the steps of example 1, example 3 replacing the corresponding steps in example 1 with the following steps:
(1-2) a first charging stage:
(1-2-1) charging the battery for 1.5h at a constant current of 0.023C;
(1-2-2) charging the battery for 1.5h at a constant current of 0.123C;
(1-2-3) charging the battery for 1.5h at a constant current of 0.165C;
(1-2-4) charging the battery for 3.5h at a constant current of 0.187C;
(1-2-5) charging the battery for 9h with a constant current of 0.23C;
(1-2-6) charging the battery for 1.5h at a constant current of 0.023C;
(1-2-7) charging the battery for 9h with a constant current of 0.23C;
(1-2-8) charging the battery for 1.5h at a constant current of 0.023C;
(1-2-9) charging the battery for 9h with a constant current of 0.23C;
(1-2-10) charging the battery for 1.5h at a constant current of 0.023C;
(1-4) a second charging stage:
(1-4-1) charging the battery for 9h with a constant current of 0.23C;
(1-4-2) charging the battery for 4.5h with a constant current of 0.187C;
(1-4-3) charging the battery for 2.5h at a constant current of 0.165C;
(1-4-4) charging the battery for 1.5h at a constant current of 0.123C;
(1-4-5) charging the battery for 1.5h at a constant current of 0.023C;
(1-6) third charging stage:
(1-6-1) charging the battery for 5.5h with a constant current of 0.23C;
(1-6-2) charging the battery for 4 hours at a constant current of 0.87C;
(1-6-3) charging the battery for 2.5h at a constant current of 0.123C;
(1-7) acid extraction stage: the cell was charged at a constant current of 0.023C for 2.5h and then acid extraction was started.
it should be understood that this example is for illustrative purposes only and is not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.

Claims (6)

1. A formation process for a battery prepared by using recovered lead powder is characterized by being in a 3-charge-2-discharge mode and comprising the following steps of:
(1-1) placing the battery prepared by using the recovered lead powder in a water bath for standing for 0.5-1h before starting charging;
(1-2) a first charging stage: charging the battery in multiple stages at a current of 0.02-0.25C, wherein the charging amount is 5.675-9 times of the rated capacity of the battery;
(1-2-1) charging the battery for 1-2 h with a constant current of 0.02-0.025 ℃;
(1-2-2) charging the battery for 1-2 h with a constant current of 0.12-0.125 ℃;
(1-2-3) charging the battery for 1-2 h with a constant current of 0.15-0.18C;
(1-2-4) charging the battery for 3-4 h at a constant current of 0.175-0.20C;
(1-2-5) charging the battery for 8-10 h with a constant current of 0.2-0.25 ℃;
(1-2-6) charging the battery for 1-2 h at a constant current of 0.02-0.025 ℃;
(1-2-7) charging the battery for 8-10 h with a constant current of 0.2-0.25 ℃;
(1-2-8) charging the battery for 1-2 h at a constant current of 0.02-0.025 ℃;
(1-2-9) charging the battery for 8-10 h with a constant current of 0.2-0.25 ℃;
(1-2-10) charging the battery for 1-2 h with a constant current of 0.02-0.025 ℃;
(1-3) a first discharge phase: discharging the battery by a constant current of-0.25C until the voltage of the battery is 10.5 v/cell;
(1-4) a second charging stage: the battery is charged in multiple stages at a current of 0.02-0.25C, and the charged electric quantity is 2.74-4.34 times of the rated capacity of the battery;
(1-5) second discharge stage: discharging the battery by a constant current of-0.5C until the voltage of the battery is 10.5 v/cell;
(1-6) third charging stage: charging the battery in multiple stages at a current of 0.12-0.25 ℃, wherein the charging amount is 1.765-2.875 times of the rated capacity of the battery;
(1-7) acid extraction stage: charging the battery for 2-3h at a constant current of 0.02-0.025 ℃, and then starting acid extraction.
2. The process for forming batteries using recycled lead powders according to claim 1, characterized in that said second charging phase comprises the following steps:
(3-1) charging the battery for 8-10 h with a constant current of 0.2-0.25 ℃;
(3-2) charging the battery for 4-5 h at a constant current of 0.175-0.20C;
(3-3) charging the battery for 2-3h with a constant current of 0.15-0.18C;
(3-4) charging the battery for 1-2 h at a constant current of 0.12-0.125 ℃;
(3-5) charging the battery for 1-2 h at a constant current of 0.02-0.025 ℃.
3. The process for forming batteries using recycled lead powders according to claim 1, characterized in that said third charging phase comprises the following steps:
(4-1) charging the battery for 5-6 h with a constant current of 0.2-0.25 ℃;
(4-2) charging the battery for 3-5 h at a constant current of 0.175-0.20C;
(4-3) charging the battery for 2-3h with a constant current of 0.12-0.125 ℃.
4. the formation process of the battery prepared by using the recycled lead powder as claimed in claim 1, wherein the internal temperature of the battery is controlled to be less than or equal to 55 ℃ in the formation process of the battery prepared by using the recycled lead powder.
5. the formation process of a battery using recovered lead powder as claimed in claim 1, wherein the acid density of the acid added at normal temperature is controlled to be 1.250-1.260 g/ml during the formation of the battery using recovered lead powder.
6. The formation process of a battery using recovered lead powder according to claim 1, 2, 3, 4 or 5, wherein the oxidation degree of the recovered lead powder is 90% to 100%.
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CN111600079A (en) * 2020-01-19 2020-08-28 超威电源集团有限公司 Method for manufacturing storage battery
CN118318174A (en) * 2021-12-10 2024-07-09 古河电气工业株式会社 Lead storage battery system and degradation estimation method for lead storage battery
WO2023106301A1 (en) * 2021-12-10 2023-06-15 古河電気工業株式会社 Lead-acid battery system and lead-acid battery deterioration estimation method
CN116706262B (en) * 2023-06-30 2024-07-23 国网浙江省电力有限公司建设分公司 Preparation process of bipolar horizontal battery

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