CN109148815B - Acidification formation method for long-life lead storage battery - Google Patents
Acidification formation method for long-life lead storage battery Download PDFInfo
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- CN109148815B CN109148815B CN201810790806.3A CN201810790806A CN109148815B CN 109148815 B CN109148815 B CN 109148815B CN 201810790806 A CN201810790806 A CN 201810790806A CN 109148815 B CN109148815 B CN 109148815B
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- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000003860 storage Methods 0.000 title claims abstract description 32
- 230000020477 pH reduction Effects 0.000 title claims description 16
- 239000002253 acid Substances 0.000 claims abstract description 147
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000010521 absorption reaction Methods 0.000 claims abstract description 17
- 230000005484 gravity Effects 0.000 claims abstract description 13
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 11
- 238000007600 charging Methods 0.000 claims description 39
- 239000003792 electrolyte Substances 0.000 claims description 14
- 238000010277 constant-current charging Methods 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 4
- 229910006529 α-PbO Inorganic materials 0.000 abstract description 5
- 230000010287 polarization Effects 0.000 abstract description 2
- 239000007774 positive electrode material Substances 0.000 abstract description 2
- 230000005611 electricity Effects 0.000 description 21
- 238000007599 discharging Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 7
- 239000011555 saturated liquid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910006531 α-PbO2 Inorganic materials 0.000 description 6
- 239000013543 active substance Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 239000011265 semifinished product Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910006654 β-PbO2 Inorganic materials 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011505 plaster Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 230000010412 perfusion Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
- H01M10/446—Initial charging measures
-
- 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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- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开了一种长寿命铅蓄电池加酸化成方法，包括以下步骤：(1)第一次加酸，向待加酸铅蓄电池中加入密度为1.05～1.25g/cm3的低比重硫酸溶液，加入体积为铅蓄电池饱和吸酸量的90％～105％；(2)第一阶段化成，充电，充电总电量为3.5C～5.0C；(3)第二次加酸，加入密度为1.25～1.65g/cm3的高比重硫酸溶液，加满；(4)第二阶段化成，先放电后再充电，放电深度为25％～80％，充电总电量为3.5C～5.0C；(5)抽净余酸。本发明通过分两次加酸，有效提升正极活性物质α‑PbO2/β‑PbO2比值，从而延长电池使用寿命，同时还可有效的降低极化提升化成效率，缩短化成周期。The invention discloses a method for forming a long-life lead storage battery by adding acid, comprising the following steps: (1) adding acid for the first time, adding a low specific gravity sulfuric acid solution with a density of 1.05-1.25 g/cm 3 to the lead storage battery to be added acid , the added volume is 90% to 105% of the saturated acid absorption of the lead-acid battery; (2) The first stage is formed, charged, and the total charge is 3.5C to 5.0C; (3) The second acid is added, and the added density is 1.25 ～1.65g/cm 3 of high specific gravity sulfuric acid solution, fill up; (4) The second stage is formed, first discharge and then charge, the depth of discharge is 25% to 80%, and the total charge is 3.5C to 5.0C; (5 ) to extract the residual acid. The invention effectively improves the ratio of the positive active material α-PbO 2 /β-PbO 2 by adding acid twice, thereby prolonging the service life of the battery, and at the same time, it can effectively reduce the polarization, improve the formation efficiency, and shorten the formation period.
Description
Technical Field
The invention relates to the technical field of lead storage battery production, in particular to a long-life lead storage battery acidification forming method.
Background
Lead storage batteries have been used for over 150 years and have a wide range of applications. In recent years, electric vehicles have been rapidly developed in China by virtue of their better mobility, lower storage space requirements and excellent price advantages, and the storage battery industry has also been rapidly developed.
The lead accumulator belongs to reversible DC power supply, and can convert chemical energy into electric energy and also convert electric energy into chemical energy. The lead storage battery mainly comprises electrolyte, a tank cover and a polar group, the electrolyte of the lead storage battery is sulfuric acid solution, the polar group mainly comprises a positive plate, a negative plate and a partition plate, and the partition plate mainly stores the electrolyte and serves as a gas channel for compounding oxygen to prevent active substances from falling off and prevent short circuit between the positive and negative electrodes.
The charging process converts electric energy into chemical energy to be stored in the active substance; upon discharge, the chemical energy stored in the active material is converted into electrical energy. During charging, the lead plaster of the positive plate is converted into lead dioxide, the lead plaster on the negative plate is converted into spongy lead, sulfuric acid components in the lead plaster are released into electrolyte, the concentration of sulfuric acid in the electrolyte is increased continuously, the voltage of the battery is increased, and energy is accumulated; when the battery discharges, the active substances of the positive plate are converted into lead sulfate, the active substances of the negative plate are also converted into lead sulfate and absorb sulfuric acid in the electrolyte, the concentration of the sulfuric acid in the electrolyte is continuously reduced, the voltage of the battery is reduced, and the battery outputs energy outwards.
The formation of a charge in the production process of lead acid batteries is one of the key processes affecting the performance of the batteries. During formation, the method has extremely complicated formation phase transformation process, and the alpha-PbO of the anode substance2And beta-PbO2The ratio is always a hot point of concern in the industry, and how to create alpha-PbO2Generating environmental enhancement alpha-PbO2And beta-PbO2The ratio is the goal of improving the cycle life when the initial performance is satisfied.
Chinese patent with publication number CN101673843A discloses a formation method of lead-acid storage battery, which comprises the steps of battery assembly, electrolyte perfusion and electrochemical formation, wherein after improvement, in the step of electrolyte perfusion, the density of the lead-acid storage battery prepared at 25 ℃ is 1.200-1.300g/cm3The dilute sulfuric acid electrolyte is cooled to 5-20 ℃, then the cooled dilute sulfuric acid is quantitatively filled with acid, and the cooled dilute sulfuric acid electrolyte is put into cooling circulating water for water bath cooling after acid filling. And the electrochemical formation is carried out within 1.5 hours after the battery is filled with acid.
The Chinese patent publication No. CN102315489A discloses a method for forming a colloid storage battery for an electric vehicle, which is used for solving the problems of long time consumption and long production period of formation in the colloid storage battery for the electric vehicle. The method comprises a plurality of charging and discharging steps and two times of vacuumizing steps, wherein the first vacuumizing step is as follows: standing the storage battery filled with the mixed acid liquor for 0.5 hour, and performing primary vacuum pumping, wherein the vacuum degree is 0.06 MPa-0.08 MPa, and the vacuum pumping time is 5-8 s; the second evacuation is performed after two times of charging and one time of discharging: the vacuumizing time is 2-5 s, and the vacuum degree is 0.06-0.08 MPa.
In the prior art, acid is generally added firstly, and the formation is carried out after standing for a period of time after the acid addition is finished, so that the problems that the positive plate is easy to argillization in the early stage and the service life of the battery is short are solved.
Disclosure of Invention
The invention provides a method for acidifying a long-life lead storage battery, aiming at the problems of early argillization, short service life and the like of a positive plate material of the lead storage battery in the prior art.
A long-life lead storage battery acidification forming method comprises the following steps:
(1) adding acid for the first time, wherein the adding density of the acid is 1.05-1.25 g/cm3The volume of the low specific gravity sulfuric acid solution is 90-105 percent of the saturated acid absorption amount of the lead storage battery;
(2) the first stage of formation and charging, wherein the total charging electric quantity is 3.5-5.0C;
(3) adding acid for the second time, wherein the adding density is 1.25-1.65 g/cm3The high-specific gravity sulfuric acid solution is fully added;
(4) the second stage formation, discharging first and then recharging, wherein the discharging depth is 25-80%, and the total charging electric quantity is 3.5-5.0 ℃;
(5) and (5) pumping out the residual acid.
The saturated acid absorption amount (saturated acid absorption amount) is the amount of acid liquid required by the pole group part in the battery to fully absorb the acid liquid, after the low-specific-gravity sulfuric acid solution with the saturated acid absorption amount of 100% by volume is added, the pole group is basically in a state of fully absorbing the acid liquid, and residual acid which is free from the pole group in the battery is basically not existed. When the acid is added for the first time, if the volume of the added acid is less than 90% of the saturated liquid absorption amount, the interior of the polar group is in an imminent dry state, the water loss during formation can enable the formation to be in a dry state in the middle and later stages so that ion transmission is blocked, and the formation is abnormal due to the too fast temperature rise. Therefore, the first acid addition should not be less than 90% of the saturated liquid absorption. Meanwhile, in order to reduce water loss in the formation process, the battery is subjected to valve control sealing and then is subjected to power supply formation.
The step (3) of filling refers to that after the high-specific gravity sulfuric acid solution is added, the acid solution is fully absorbed by the pole group, and the rest empty spaces of the battery are also fully filled with the acid solution. The residual acid in the step (5) is acid liquid which is dissociated outside the polar group after the formation is finished.
Preferably, the density of the low specific gravity sulfuric acid solution in the step (1) is 1.10-1.20 g/cm3。
Preferably, the volume of the low specific gravity sulfuric acid solution in the step (1) is 95-100% of the saturated acid absorption amount of the lead storage battery.
Preferably, the density of the high specific gravity sulfuric acid solution in the step (3) is 1.35-1.50 g/cm3。
Preferably, after the acidification formation is finished, the final density of the electrolyte is controlled to be 1.34-1.38 g/cm3. During the formation process, the water in the battery is partially evaporated, so the density of the acid solution after formation is increased compared with that before formation, the density and the adding amount of the high specific gravity sulfuric acid solution subjected to secondary acid addition are related to the situation of primary acid addition, and after the density and the adding volume of the low specific gravity sulfuric acid solution subjected to primary acid addition are determined, the approximately required density of the high specific gravity sulfuric acid solution subjected to secondary acid addition can be obtained through experiments according to the density of the acid solution required by the final battery.
Preferably, the vacuum pumping is carried out for 2 to 4 times after the acid is added for the second time, and the vacuum degree is between-0.06 and-0.1 MPa. The purpose of vacuumizing after the acid is added for the second time is to fully and uniformly mix the acid liquor. Negative vacuum values represent negative pressure.
Preferably, the residual acid is extracted in the step (5) by adopting charged acid extraction, and the current is 0.01-0.02C during the charged acid extraction. For example, a conventional 6-DZM-20 battery has a rated capacity of 20AH, and the corresponding acid pumping current is 0.2A-0.4A.
Preferably, in the first stage formation and the second stage formation, constant current charging is adopted for charging, and the current density is 2.5mA/cm2～7.5mA/cm2。
Further preferably, the charging current density in the first and second stages is 5mA/cm2。
Preferably, after the first acid addition, the mixture is kept stand for 0.5 to 1.5 hours and then is subjected to the first-stage formation.
The method for the long-life lead storage battery acidification formation comprises the steps of adding low-density dilute sulfuric acid for the first time in a mode of quantitative acidification and formation twice, carrying out pickling and formation for a period of time, and then carrying out acidification and formation for the second time, wherein in low-density electrolyte, the polar plate is soaked in acid, the temperature rise and the reaction are more uniform, and the earlier stage of formation is promoted to be more beneficial to alpha-PbO2Is generated in a longer period, and is alpha-PbO2//β-PbO2The ratio comparison is obviously improved. By adding acid twice, alpha-PbO is created2The growth environment of the anode active substance alpha-PbO is effectively improved2/β-PbO2The ratio value, thereby prolonging the service life of the battery, effectively reducing the polarization, improving the formation efficiency and shortening the formation period.
Detailed Description
Example 1
The method is adopted to perform acidification and formation on the semi-finished product of the 6-DZM-20 battery, and the sample preparation process is as follows:
1) adding acid for the first time, and adding the acid to a lead storage battery to be added with acid to the lead storage battery with the density of 1.05g/cm3The volume of the sulfuric acid solution is 148ml (the unit lattice saturated liquid absorption volume is 163-165 ml, namely about 90% of the saturated acid absorption volume), the vacuum acid addition is carried out in a vacuum degree of-0.08 MPa for 1-2 times.
2) After the battery after the first acid addition was allowed to stand for 1 hour, a safety valve was installed and the first stage formation process was started at 3.6A (current density 5 mA/mm)2) And constant current charging for 21h (charging amount 75.6Ah, 3.78C).
3) After the first-stage formation is finished, the battery is subjected to secondary acid addition in a vacuum acid addition mode (vacuum degree is minus 0.08MPa, vacuum is carried out for 2-4 times), the acid density is 1.65g/ml, and the acid addition volume is 62 ml. The determination of the acid adding amount of the battery is related to the total water loss amount and the total required amount of the formation, the total acid adding volume and the acid adding volume of two stages are determined after the weight of the battery in each process is weighed during the process determination to obtain water loss data, the total acid adding volume requirement of the 6-DZM-20 adopting the technology of the invention is 210mL, and therefore the acid adding volume of the second stage is 210-148-62 mL.
4) Before the second-stage formation is started, the acid liquor can be obviously seen in the acid kettle, so that the exhaust pipe still needs to be inserted into the acid kettle (the process is the same as the conventional process), and then the machine can be started for formation without standing. Formation process: discharging at 10A for 1h (50% depth of discharge), and then at 3.6A (current density of 5 mA/mm)2) And constant current charging is carried out for 24h (charging amount 86.4Ah, 4.32C).
5) After the second-stage formation is finished, continuously charging for 2 hours by using a current of 0.2A (corresponding to 0.01C), stopping the machine after the residual acid is completely extracted, discharging the battery, and processing the battery by a finished product to obtain the finished battery.
Example 2
The method is adopted to perform acidification and formation on the semi-finished product of the 6-DZM-20 battery, and the sample preparation process is as follows:
1) adding acid for the first time, and adding the acid into the lead storage battery to be added with acid to obtain the lead storage battery with the density of 1.10g/cm3The volume of the sulfuric acid solution is 155ml (the unit saturated liquid absorption volume is 163-165 ml, namely about 94% of the saturated acid absorption volume), the vacuum acid addition is carried out in a vacuum degree of-0.06 MPa for 1-2 times.
2) After the battery after the first acid addition was allowed to stand for 1.5 hours, a safety valve was installed and the first stage formation process was started at 1.8A (current density 2.5 mA/mm)2) And constant current charging is carried out for 38.9h (charging amount 70Ah, 3.5C).
3) And after the first-stage formation is finished, performing secondary acid addition on the battery by adopting a vacuum acid addition mode (vacuum degree is minus 0.08MPa, vacuum is performed for 2-4 times), wherein the acid density is 1.58g/ml, and the acid addition volume is 55 ml. The determination of the acid adding amount of the battery is related to the total water loss amount and the total required amount of the formation, the total acid adding volume and the acid adding volume of two stages are determined after the weight of the battery in each process is weighed to obtain water loss data during the process determination, and the total acid adding volume requirement of the 6-DZM-20 adopting the technology of the invention is 210mL, so the acid adding volume of the second stage is 210-155-55 mL.
4) Before the second-stage formation is started, the acid liquor can be obviously seen in the acid kettle, so that the exhaust pipe still needs to be inserted into the acid kettle (the process is the same as the conventional process), and then the machine can be started for formation without standing. Formation process: discharging at 10A for 1h (50% depth of discharge), and then at 5.5A (current density of 7.5 mA/mm)2) And (4) constant-current charging for 16.4h (charging quantity 90Ah, 4.5C).
5) After the second-stage formation is finished, continuously charging for 2 hours by using a current of 0.3A (corresponding to 0.015C), stopping the machine after the residual acid is completely extracted, taking the machine off the line, and treating a finished product to obtain a finished battery.
Example 3
The method is adopted to perform acidification and formation on the semi-finished product of the 6-DZM-20 battery, and the sample preparation process is as follows:
1) adding acid for the first time, and adding the acid into the lead storage battery to be added with acid to obtain the lead storage battery with the density of 1.20g/cm3Adding 165ml of acid into the sulfuric acid solution (the unit lattice saturated liquid absorption amount is 163-165 ml, namely about 100% of the saturated acid absorption amount), and performing vacuum acid addition in a vacuum degree of-0.1 MPa for 1-2 times.
2) After the battery after the first acid addition is allowed to stand for 0.5 hour, a safety valve is installed and the first-stage formation process is started to control the current density to be 3.6A (the current density is 5 mA/mm)2) Constant current charging 22.2h (charge 80Ah, 4.0C).
3) And after the first-stage formation is finished, performing secondary acid addition on the battery by adopting a vacuum acid addition mode (vacuum degree is minus 0.08MPa, vacuum is performed for 2-4 times), wherein the acid density is 1.4g/ml, and the acid addition volume is 45 ml. The determination of the acid adding amount of the battery is related to the total water loss amount and the total required amount of the formation, the total acid adding volume and the acid adding volume of two stages are determined after the weight of the battery in each process is weighed to obtain water loss data during the process determination, and the total acid adding volume requirement of the 6-DZM-20 adopting the technology of the invention is 210mL, so the acid adding volume of the second stage is 210-165-45 mL.
4) Before the second-stage formation is started, the acid liquor can be obviously seen in the acid kettle, so that the exhaust pipe still needs to be inserted into the acid kettle (the process is the same as the conventional process), and then the machine can be started for formation without standing. Formation process: to be provided withDischarging at 10A for 1.5h (75% depth of discharge), and discharging at 3.6A (current density of 5 mA/mm)2) And constant current charging is carried out for 24h (charging amount 86.4Ah, 4.3C).
5) After the second-stage formation is finished, continuously charging for 1.5 hours by using a current of 0.4A (corresponding to 0.02C), stopping the machine after the residual acid is completely extracted, discharging the battery, and processing the battery by a finished product to obtain the finished battery.
Example 4
The method is adopted to perform acidification and formation on the semi-finished product of the 6-DZM-20 battery, and the sample preparation process is as follows:
1) adding acid for the first time, and adding the acid to a lead storage battery to be added with acid to the lead storage battery with the density of 1.25g/cm3The volume of the sulfuric acid solution is 170ml (the unit lattice saturated liquid absorption volume is 163-165 ml, namely about 103% of the saturated acid absorption volume), the vacuum acid addition is carried out in a vacuum degree of-0.08 MPa for 1-2 times.
2) After the battery after the first acid addition was allowed to stand for 1 hour, a safety valve was installed and the first stage formation process was started at 5.5A (current density 7.5 mA/mm)2) And (4) constant-current charging for 16.4h (charging quantity 90Ah, 4.5C).
3) And after the first-stage formation is finished, performing secondary acid addition on the battery by adopting a vacuum acid addition mode (vacuum degree is minus 0.08MPa, vacuum is performed for 2-4 times), wherein the acid density is 1.25g/ml, and the acid addition volume is 40 ml. The determination of the acid adding amount of the battery is related to the total water loss amount and the total required amount of the formation, the total acid adding volume and the acid adding volume of two stages are determined after the weight of the battery in each process is weighed to obtain water loss data during the process determination, and the total acid adding volume requirement of the 6-DZM-20 adopting the technology of the invention is 210mL, so the acid adding volume of the second stage is 210-170-40 mL.
4) Before the second-stage formation is started, the acid liquor can be obviously seen in the acid kettle, so that the exhaust pipe still needs to be inserted into the acid kettle (the process is the same as the conventional process), and then the machine can be started for formation without standing. Formation process: discharging at 10A for 0.5h (25% depth of discharge), and then at 1.8A (current density of 2.5 mA/mm)2) And constant current charging is carried out for 38.9h (charging amount 70Ah, 3.5C).
5) After the second-stage formation is finished, continuously charging for 2 hours by using a current of 0.2A (corresponding to 0.01C), stopping the machine after the residual acid is completely extracted, discharging the battery, and processing the battery by a finished product to obtain the finished battery.
Comparative example 1
Taking a semi-finished product of the 6-DZM-20 battery, and performing acidification and formation by adopting a conventional production method, wherein the sample preparation process comprises the following steps:
1) adding acid, adding into the lead accumulator to be added with acid with a density of 1.25g/cm3Adding 225ml of acid into the sulfuric acid solution, and performing vacuum acid addition for 3-4 times at a vacuum degree of-0.08 MPa;
2) and (4) after the acid is added, inserting the exhaust pipe into an acid kettle, standing for 1 hour, and then starting to form. Formation process: the total net charge of the chemical composition is 199.8Ah, and the total time is 70 h. Specifically, the results are shown in Table 1.
TABLE 1
| Step (ii) of | Procedure | Electric current | Hour(s) |
| 1 | Charging of electricity | 3 | 2 |
| 2 | Charging of electricity | 5 | 10 |
| 3 | Discharge of electricity | -7 | 1 |
| 4 | Charging of electricity | 5 | 5 |
| 5 | Discharge of electricity | -8 | 0.5 |
| 6 | Charging of electricity | 5 | 5 |
| 7 | Discharge of electricity | -8 | 1 |
| 8 | Charging of electricity | 5 | 4 |
| 9 | Discharge of electricity | -8 | 1 |
| 10 | Charging of electricity | 5 | 4 |
| 11 | Discharge of electricity | -10 | 1 |
| 12 | Charging of electricity | 5 | 4 |
| 13 | Discharge of electricity | -10 | 1.7 |
| 14 | Charging of electricity | 5 | 5 |
| 15 | Charging of electricity | 4.5 | 4 |
| 16 | Charging of electricity | 4 | 5.8 |
| 17 | Discharge of electricity | -10 | 2 |
| 18 | Charging of electricity | 5 | 5 |
| 19 | Charging of electricity | 3 | 4 |
| 20 | Charging of electricity | 2 | 2 |
| 21 | Charging of electricity | 0.3 | 2 |
3) And in the last step of the formation process, charging for 2 hours at 0.3A current, stopping the machine after the residual acid is completely pumped out, taking the battery off the line, and treating the battery finished product to obtain the finished battery.
Example 5
And (3) dissecting the finished batteries of the embodiment 1-4 and the comparative example 1, taking out the positive plates with the same cells and the same positions, soaking to remove acid liquor in the positive plates, and then performing vacuum drying to obtain a polar plate sample. Then, XRD phase analysis (diffraction angle 8-90 DEG, scanning speed 4 DEG/min) was performed on the plate sample, and the results of the measurements were as shown in Table 2, with the same sampling position.
TABLE 2
From the data obtained by XRD, it can be seen that the conversion rates of the active materials of examples 1 to 4 and comparative example 1 are consistent, and the formation effect is good. Further, it was found that the α -PbO used in examples 1 to 4 of the present invention2The amount of formed alpha-PbO is significantly higher than that of comparative example2The positive electrode active material serves as a skeleton structure and is the basis of the long life of the battery. alpha-PbO2The generation amount is closely related to the control of the formation process, and the technology of the invention is favorable for alpha-PbO2The pH value of the growth is neutral to slightly alkaline environment.
Example 6
The finished batteries of the embodiment 1-4 and the comparative example 1 were tested for initial capacity and cycle life, and each of the batteries was tested in 4 batteries.
The cycle life testing method comprises the following steps:
discharging: discharging 10A to 42V;
charging: charging for 5 hours at constant voltage of 59.2V and current limiting of 8A;
and thirdly, circulating the first step and the second step until the capacity is lower than 80% of the rated capacity for three times, namely ending the circulation, and counting the circulation times for the three times.
The test results are shown in table 3.
TABLE 3
As can be seen from the data in the table, the initial capacity of examples 1-4 is slightly lower than that of comparative example 1, but the initial capacity completely meets the standard requirement. The cycle life is seen, the cycle life of the embodiments 1 to 4 adopting the technology of the invention is obviously superior to that of the comparative example, and the promotion ratio reaches more than 126%.
Example 7
Table 4 summarizes the time-consuming and formation results of the processes of examples 1 to 4 and comparative example 1.
TABLE 4
As can be seen from the data in the above table, the conversion rates of the active materials in examples 1 to 4 are consistent with that in comparative example 1, but the total net charge amount of formation and the total time of formation are obviously less than that in comparative example 1, which indicates that the formation efficiency is obviously improved by using the technology of the present invention.
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| CN110504495B (en) * | 2019-08-12 | 2021-04-09 | 天能电池集团股份有限公司 | Acidification formation method of storage battery |
| CN111029671B (en) * | 2019-12-10 | 2022-06-21 | 天能电池(芜湖)有限公司 | Acid-adding charging process capable of reducing charging energy consumption |
| WO2021142853A1 (en) * | 2020-01-19 | 2021-07-22 | 超威电源集团有限公司 | Fabrication method for lead-acid storage battery |
| CN111916848A (en) * | 2020-01-19 | 2020-11-10 | 超威电源集团有限公司 | Method for manufacturing lead-acid storage battery |
| WO2021142852A1 (en) * | 2020-01-19 | 2021-07-22 | 超威电源集团有限公司 | Method for manufacturing lead-acid battery |
| CN111916849A (en) * | 2020-01-19 | 2020-11-10 | 超威电源集团有限公司 | Method for manufacturing lead-acid storage battery |
| CN111354984A (en) * | 2020-01-19 | 2020-06-30 | 超威电源集团有限公司 | Method for manufacturing lead-acid storage battery |
| CN111403825A (en) * | 2020-01-19 | 2020-07-10 | 超威电源集团有限公司 | Method for manufacturing lead-acid storage battery |
| CN111916847A (en) * | 2020-01-19 | 2020-11-10 | 超威电源集团有限公司 | Acid adding method for lead-acid storage battery |
| CN111628230A (en) * | 2020-01-19 | 2020-09-04 | 超威电源集团有限公司 | Method for manufacturing lead-acid storage battery |
| CN111883856A (en) * | 2020-01-19 | 2020-11-03 | 超威电源集团有限公司 | Method for manufacturing lead-acid storage battery |
| CN111446507A (en) * | 2020-01-19 | 2020-07-24 | 超威电源集团有限公司 | Method for manufacturing lead-acid storage battery |
| CN111600085A (en) * | 2020-01-19 | 2020-08-28 | 超威电源集团有限公司 | Method for manufacturing lead-acid storage battery |
| CN111628229A (en) * | 2020-01-19 | 2020-09-04 | 超威电源集团有限公司 | Method for manufacturing lead-acid storage battery |
| CN111600079A (en) * | 2020-01-19 | 2020-08-28 | 超威电源集团有限公司 | Method for manufacturing storage battery |
| CN111446506A (en) * | 2020-01-19 | 2020-07-24 | 超威电源集团有限公司 | Method for manufacturing lead-acid storage battery |
| CN111682273B (en) * | 2020-05-15 | 2021-09-07 | 天能电池集团股份有限公司 | Lead storage battery formation method |
| CN112103573B (en) * | 2020-08-07 | 2021-10-22 | 天能电池集团股份有限公司 | Method for determining acid absorption saturation of valve-controlled lead storage battery |
| CN112103579B (en) * | 2020-08-07 | 2021-10-22 | 天能电池集团股份有限公司 | Lead storage battery container formation process |
| CN112331943B (en) * | 2020-11-04 | 2021-09-24 | 浙江天能电池(江苏)有限公司 | Formation, screening and matching process for power lead storage battery |
| CN112786976B (en) * | 2021-02-02 | 2022-06-21 | 天能电池集团股份有限公司 | Formation method of AGM valve-controlled lead storage battery |
| CN113285184A (en) * | 2021-04-16 | 2021-08-20 | 安徽超威电源有限公司 | Acid adding method for improving acid specific gravity of valve-controlled lead-acid storage battery separator |
| CN116008825B (en) * | 2022-04-21 | 2023-10-27 | 骆驼集团襄阳蓄电池有限公司 | High-temperature life pre-judging method for valve-regulated lead-acid storage battery |
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Application publication date: 20190104 Assignee: Changxing Taibo Intellectual Property Service Co.,Ltd. Assignor: TIANNENG BATTERY GROUP Co.,Ltd. Contract record no.: X2024980029488 Denomination of invention: A method for acidification of long-life lead-acid batteries Granted publication date: 20211228 License type: Common License Record date: 20241129 |