CN111342149B - A kind of lead-acid battery negative electrode desulfurization repair method - Google Patents
A kind of lead-acid battery negative electrode desulfurization repair method Download PDFInfo
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- CN111342149B CN111342149B CN202010119422.6A CN202010119422A CN111342149B CN 111342149 B CN111342149 B CN 111342149B CN 202010119422 A CN202010119422 A CN 202010119422A CN 111342149 B CN111342149 B CN 111342149B
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- 230000008439 repair process Effects 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000002253 acid Substances 0.000 title description 19
- 238000006477 desulfuration reaction Methods 0.000 title 1
- 230000023556 desulfurization Effects 0.000 title 1
- 239000003792 electrolyte Substances 0.000 claims abstract description 36
- 238000003860 storage Methods 0.000 claims abstract description 27
- 238000004073 vulcanization Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000001514 detection method Methods 0.000 claims description 8
- 238000004146 energy storage Methods 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000007600 charging Methods 0.000 abstract description 60
- 238000005987 sulfurization reaction Methods 0.000 abstract description 2
- 238000012216 screening Methods 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 229910052793 cadmium Inorganic materials 0.000 description 8
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 8
- 238000005086 pumping Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010277 constant-current charging Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000005837 radical ions Chemical class 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 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
- 238000004140 cleaning Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
Classifications
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4242—Regeneration of electrolyte or reactants
-
- 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
- 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
-
- 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 & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
Abstract
本发明公开了一种铅蓄电池负极去硫化修复方法，属于蓄电池修复技术领域。所述修复方法包括：(1)负极硫化电池筛选，选择充电后电解液无明显黑色混浊的电池进入下一工序；(2)将筛选的电池置入45～65℃环境下存放，使电池内部温度与环境保持一致，再转移至45～65℃、0.2～0.5Mpa环境下，0.1CA充电9～12h；(3)容量检测，容量大于或等于额定容量90％的电池判定为合格，否则为不合格；(4)不合格的电池重复步骤(2)‑(3)。采用本发明的修复方法能去除顽固性负极硫化，硫化电池容量能恢复至额定容量的90％以上，修复成功率达到97％以上，无需采用修复液或充电脉冲专用设备，修复充电用时间短。The invention discloses a method for removing vulcanization and repairing a negative electrode of a lead storage battery, and belongs to the technical field of repairing storage batteries. The repair method includes: (1) screening the negative electrode vulcanization battery, and selecting the battery with no obvious black turbidity in the electrolyte after charging to enter the next process; (2) placing the screened battery in an environment of 45 to 65 ° C for storage, so that the inside of the battery is stored. The temperature is consistent with the environment, and then transferred to the environment of 45~65℃, 0.2~0.5Mpa, 0.1CA charging for 9~12h; (3) Capacity testing, the battery with a capacity greater than or equal to 90% of the rated capacity is judged to be qualified, otherwise it is Unqualified; (4) Repeat steps (2)‑(3) for unqualified batteries. The repairing method of the invention can remove the stubborn negative electrode sulfuration, the capacity of the sulfurized battery can be restored to more than 90% of the rated capacity, the repairing success rate is more than 97%, no repairing liquid or special equipment for charging pulse is needed, and the repairing and charging time is short.
Description
Technical Field
The invention relates to the technical field of storage battery repair, in particular to a method for removing and vulcanizing a negative electrode of a lead storage battery.
Background
Lead-acid batteries are classified into starting batteries, backup batteries, energy storage batteries, power batteries, and the like according to their uses. Under normal use conditions, the cycle life of the battery is controlled by the anode, for example, the power battery is set with a higher charging voltage (the unit cell is between 2.46 and 2.5V) in the actual charging process, the charging is continuously carried out, the undercharge is avoided, the cathode is not easy to vulcanize, and the active material of the anode is softened or the grid is corroded after the cycle life of the battery is finished. The charging voltage of other batteries is relatively low (the charging voltage is controlled to be 2.25-2.40V/grid), and the negative electrode of the battery is easy to generate vulcanization under the following conditions: frequent starting of the vehicle, short driving mileage, night driving and the like; the standby class: the urban network has frequent power failure and no power generation equipment area; a battery for energy storage: short illumination time, rainy weather, and wind-force deficient area.
The conventional repair method is to add quantitative repair liquid (or dilute acid) into the battery, and perform overcharge or pulse operation for a long time under low current, for example, patent document CN 102157757 a discloses a vulcanization repair method for lead-acid storage batteries, which comprises the following steps: firstly, high current of 0.4C is applied10-0.6C10Discharging to 50% of the current capacity, and then discharging at a low current of 0.1C10Discharging to the final voltage, and then discharging with small current of 0.1C10-0.3C10Charging to 125% of the current capacity with a small current of 0.05C10And charging until the capacities of the storage batteries in the storage battery pack are balanced.
Under the conventional conditions, the solubility of lead sulfate of the cathode of the sulfide battery is very low, and only a few acid radical ions participate in the reaction when the battery is charged, so that the water is decomposed mainly by the charging of the battery as a side reaction, and the side reaction at this stage is as follows: 2H2O＝2H2↑+O2×) the charging voltage is high. Therefore, the battery needs to be repaired many times over a long period of time. For cells with particularly severe vulcanization, the above method has little practical repairing effect.
Patent document CN 105990615 a discloses a method for regenerating and repairing an industrial storage battery, which applies instantaneous high voltage to a storage battery pack through a positive-negative pulse frequency conversion repairing circuit, limits a current value, sets a sufficiently short pulse width and a sufficiently large duty ratio, and achieves a repairing time of 20-60h, wherein the repaired battery pack reaches more than 85% of the nominal capacity of the battery. However, the pulse equipment has high cost, and the control of the current and the pulse frequency is complicated in the repair process, which undoubtedly increases the manufacturing cost of the lead storage battery.
Compared with other batteries, the standby and energy storage batteries have large capacity and higher battery repair value. Therefore, the discharge capacity of the battery is improved by repairing the cathode vulcanization phenomenon, and the method has great significance for standby and energy storage valve-controlled batteries.
Disclosure of Invention
The invention aims to provide a method for removing and repairing the cathode of a lead storage battery by vulcanization, which aims to solve the problem of cathode vulcanization caused by low charging voltage control during working of valve-regulated lead storage batteries such as starting, standby and energy storage batteries.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for removing sulfuration and repairing a negative electrode of a lead storage battery comprises the following steps:
(1) adding electrolyte into the battery to be repaired, standing, charging for 3-5 hours by limiting the voltage by 2.50-2.55V/grid and limiting the current by 0.2CA, then charging for 3 hours by 0.10-0.15 CA constant current, then checking the electrolyte of the battery, and selecting the battery without obvious black turbidity of the electrolyte to enter the next procedure;
(2) placing the screened batteries in an environment of 45-65 ℃ for storage, keeping the internal temperature of the batteries consistent with the environment, transferring the batteries to an environment of 45-65 ℃ and 0.2-0.5 Mpa, and charging the batteries for 9-12 hours by 0.1 CA;
(3) taking out the battery which is charged, detecting the capacity, judging that the battery with the capacity more than or equal to 90% of the rated capacity is qualified, and otherwise, judging that the battery is unqualified;
(4) charging unqualified batteries for 5 hours by limiting the voltage to 2.50-2.55V/grid and limiting the current to 0.20-0.25 CA, checking the electrolyte of the batteries, selecting the batteries without obvious black turbidity for the batteries, repeating the steps (2) - (3), and scrapping the unqualified batteries.
Taking a battery with a rated capacity of 100Ah as an example, the current corresponding to 0.2C is 20A.
In the step (1), the batteries with poor capacity returned in the market are screened, and the batteries with the negative pole having the vulcanization problem are selected for repairing. Specifically, the battery is detected whether the electrolyte of the battery is clear after being charged, and if the electrolyte of the battery is obviously black and turbid, the electrolyte is determined as the positive electrode problem and is discarded; if the electrolyte has no obvious black turbidity, the battery enters the next repairing process.
And removing a cover plate of the battery to be repaired or screwing off a safety plug, opening a safety valve, and replenishing electrolyte, wherein 0.5-1.0 mL of electrolyte is replenished according to the rated capacity of the battery per ampere hour as the optimal selection.
Preferably, the density of the electrolyte is 1.03-1.05 g/cm3。
After the electrolyte is added, the solution is allowed to stand to be sufficiently absorbed by the electrode plate, and preferably, in the step (1), the solution is replenished and then allowed to stand for 2 hours.
In the step (2), the battery with the problem of cathode vulcanization is kept stand for 5-10 hours at the temperature of 45-65 ℃, and the solubility of lead sulfate can be increased at a slightly higher temperature; the solubility of the lead sulfate is correspondingly increased under the high voltage of the battery, and the two factors are superposed to accelerate the dissolution of the lead sulfate of the negative electrode. Meanwhile, lead sulfate is reduced to lead under the action of current. In addition, the battery is charged under high pressure, a pressure critical point exists, and as the gas pressure in the sealed container increases, hydrogen and oxygen generated by side reaction electrolyzed water cannot smoothly leave the surface of the electrode, so that the decomposition of water is inhibited, and more current is used for the reduction of lead sulfate.
Preferably, in the step (2), the internal temperature of the battery is raised to 45 to 65 ℃, and then the battery is transferred to a sealed high-pressure container with the temperature of 45 to 65 ℃ within 5 min. The connection between the outgoing line of the charging equipment and the pile head of the battery is reliable.
More preferably, the battery is placed in an environment of 55 ℃ and is kept stand for 10h, and then the battery is transferred to an environment of 55 ℃ and 0.3Mpa and is charged by 0.1CA for 10 h.
And (3) after the battery is repaired, taking out the battery from the high-pressure container, and carrying out capacity detection at normal temperature and normal pressure, wherein the normal temperature and normal pressure are conditions known in the field, namely 20-25 ℃ and 0.1MPa of atmospheric pressure. Specifically, a 10h rate capacity check may be employed.
And (4) sequentially charging, acid pumping, cleaning, finishing and packaging the battery judged to be qualified, thereby completing the repair.
Preferably, step (3) further comprises: and charging the battery judged to be qualified, wherein the charging comprises the following steps: charging at 0.1CA for 12-15 hr, charging at 0.03CA for 2-3 hr, and pumping acid after charging at 0.03CA for 2 hr.
And performing the repairing process and the capacity detection again on the battery judged to be unqualified, and scrapping or otherwise processing the battery which still cannot meet the requirement.
Preferably, the lead storage battery is a starting battery, a backup battery, or a valve-regulated battery for energy storage.
The invention has the following beneficial effects:
(1) the battery is placed in a high-temperature and high-pressure environment, the dissolution of the negative lead sulfate is accelerated, the initial state of the battery is changed, and more acid radical ions participating in the reaction are obtained; when the electrode is charged under high pressure, the gas generated by the side reaction of electrolyzed water can not smoothly leave the surface of the electrode, the decomposition of water is inhibited, and more current is used for the reduction of lead sulfate.
The repairing method can remove the intractable cathode vulcanization, the capacity of the vulcanized battery can be recovered to more than 90% of the rated capacity, and the repairing success rate can reach more than 97%.
(2) The repairing method provided by the invention does not need to adopt repairing liquid or special charging pulse equipment, and the time for repairing and charging is relatively short.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited thereto.
Example 1
The 10h rate capacity of 50 poor batteries with 6-CN-100 capacity is detected to be within the range of 10-30 Ah.
The battery repair process comprises the following steps:
1. removing the cover plate and the safety valve of the battery, wherein the density of each unit cell of the battery is 1.03g/cm350ml of sulfuric acid electrolyte. After the battery is kept stand for 2 hours, the voltage is limited to 15.0V/battery, the current is limited to 20A for charging for 3 hours, and then the battery is turned to 15A for constant current charging for 3 hours. The cell electrolyte was examined and 3 were found to be visibly black and cloudy, and the remaining 47 cells were left to stand at 45 ℃ for 5 hours.
2. After standing, the battery was immediately transferred to a closed high-pressure vessel at a temperature of 45 ℃ and charged for 9 hours under a high-pressure environment of 0.2 Mpa.
3. The rate capacity of 10h is detected under the normal temperature and the normal pressure after the batteries are taken out, and the rate capacity of 10h of 40 batteries is more than or equal to 90 Ah.
Continuously repairing 7 batteries with the capacity of less than 90Ah once, limiting the voltage to 15V/battery, limiting the current to 20A, charging for 5h, and detecting the electrolyte to find that the electrolyte of 2 batteries is obviously black and turbid and is abandoned; and in addition, 5 batteries are stood for 5 hours in the environment of 45 ℃ and then immediately transferred into a closed high-pressure container with the temperature of 45 ℃, the batteries 10A are charged for 9 hours in the environment of 0.2Mpa, the batteries are taken out and then the rate capacity of 10 hours is detected under normal temperature and normal pressure, wherein the rate capacity of 10 hours of 2 batteries is more than 90 Ah. The cadmium electrode test of 3 unqualified batteries confirms that the positive electrodes of 2 batteries have faults, and 1 battery has insufficient capacity due to the negative electrode.
4. And after the qualified 42 batteries are charged for 12 hours at 10A, 3A charging is carried out, acid pumping and finishing are carried out, and the repair is finished.
The total battery repair rate was 84%, with the cured battery (negative cause battery) repair rate being 97.67%.
Comparative example 1
The 10h rate capacity of 50 poor batteries with 6-CN-100 capacity is detected to be within the range of 10-35 Ah.
1. Removing the cover plate and the safety valve of the battery, wherein the density of each unit cell of the battery is 1.03g/cm350ml of sulfuric acid electrolyte containing 1% of repair liquid. The battery is kept stand for 2h, and then is charged for 3h under the normal temperature and pressure limited by 15V/battery and current limited by 20A, and then is continuously charged for 36h at 5A.
2. The rate capacity of 10h is detected under the normal temperature and the normal pressure after the batteries are taken out, and the rate capacity of 10h of the total 31 batteries is more than or equal to 90 Ah.
After 19 batteries with the capacity of less than 90Ah are charged for 5h under the conditions of normal temperature and normal pressure, the voltage limitation is 15V/current limitation 20A, and the electrolyte of 6 batteries is obviously discarded in a black turbidity manner through examination; in addition, 13 batteries are continuously charged at 5A for 36h and are repaired again, and 10 batteries still can not reach 90Ah through detection. The cadmium electrode test of the 10 batteries confirms that the positive electrodes of the 2 batteries have faults, and 8 batteries only cause insufficient capacity due to the negative electrode.
3. And after charging for 12 hours at 10A, charging for 3A to extract acid, and finishing to finish repairing, wherein 34 qualified batteries are obtained.
The total repair rate of the battery is 68%, wherein the repair rate of the vulcanized battery (the battery with the negative electrode reason) is 80.95%.
Comparative example 2
The 10h rate capacity of 50 poor batteries with 6-CN-100 capacity is detected to be within the range of 15-30 Ah.
1. Removing the cover plate and the safety valve of the battery, wherein the density of each unit cell of the battery is 1.03g/cm3The battery is kept still for 2 hours, then the voltage is limited by 15V/current limited 20A for charging for 3 hours at normal temperature and normal pressure, and then the continuous charging is carried out for 36 hours by alternately carrying out 5A positive pulse 2s and negative pulse 1 s.
2. The rate capacity of 10h is detected under the normal temperature and the normal pressure after the batteries are taken out, and the rate capacity of 10h of 34 batteries is more than or equal to 90 Ah.
After 16 batteries with the capacity of less than 90Ah are charged for 5h under the normal temperature and pressure limited by 15V/limited current 20A, the electrolyte of the 5 batteries is detected to have obvious black turbidity and is discarded. In addition, 11 batteries are continuously charged for 36h by 5A positive pulse 2s negative pulse 1s alternately for one time of restoration, and 10 batteries still can not reach 90Ah through detection. The cadmium electrode test of the 10 batteries confirms that the positive electrodes of the 3 batteries have faults, and the negative electrodes of the 7 batteries only cause insufficient capacity.
3. And after charging for 12 hours at 10A, charging for 3A to extract acid, and finishing to finish repairing, wherein 35 qualified batteries are charged for 12 hours at 10A.
The total repair rate of the battery is 70%, wherein the repair rate of the vulcanized battery (the battery with the negative electrode reason) is 83.33%.
Example 2
The 20h rate capacity of 30 batteries with poor 6-FM-40 capacity is detected to be within the range of 5-20 Ah.
1. Removing the cover plate and the safety valve of the battery, wherein the density of each unit cell patch of the battery is 1.05g/cm340ml of sulfuric acid electrolyte. After the battery is kept stand for 2 hours, the voltage is limited by 15.3V/battery, the current is limited by 8A, the battery is charged for 5 hours, and then the battery is charged for 3 hours by 4A constant current. The electrolyte 5 of the cell is checked to be only obviously black and turbid, and the other 25 cells are placed in an environment with the temperature of 65 ℃ for standing for 10 hours.
2. After standing, the battery was immediately transferred to a sealed high-pressure vessel at a temperature of 65 ℃ and charged for 12 hours under a high-pressure of 0.5 Mpa.
3. The 20h rate capacity of the 24 batteries is detected at normal temperature and normal pressure, and the 20h rate capacity of the 24 batteries is more than or equal to 36 Ah.
The voltage of 1 battery with the capacity lower than 36Ah is limited to 15.3V, and the battery is detected to have obvious black turbidity when being charged for 5h under the current limiting 10A.
4. After 24 qualified batteries are charged for 15 hours at 4A, 1.2A charging acid pumping and finishing are carried out to finish the repair.
The total repair rate of the battery is 80%, wherein the repair rate of the vulcanized battery (the battery with the negative electrode reason) is 100%.
Comparative example 3
The 20h rate capacity of 30 batteries with poor 6-FM-40 capacity is detected to be within the range of 5-25 Ah.
1. Removing the cover plate and the safety valve of the battery, wherein the density of each unit cell patch of the battery is 1.05g/cm340ml of sulfuric acid electrolyte containing 1% of repair liquid, standing the battery for 2 hours, limiting the pressure to 15.3V/battery at normal temperature and normal pressure, limiting the current, charging for 5 hours, and continuously charging for 36 hours at 2A.
2. The 20h rate capacity of 18 batteries is greater than or equal to 36 Ah.
After 12 batteries with the capacity lower than 36Ah are charged for 5h under the conditions of normal temperature and normal pressure, the voltage is limited by 15.3V/current limited by 10A, and the electrolyte of 6 batteries is detected to have obvious black turbidity and is discarded; in addition, 6 batteries are continuously charged for 36h at 2A for one more time to be repaired, and 5 batteries still can not meet the repair standard through detection. The 5 batteries were tested with cadmium electrodes to confirm that 1 battery had a failure in the positive electrode and 4 batteries had insufficient capacity due to the negative electrode.
3. After charging for 15h by 4A, charging by 1.2A, extracting acid, and finishing to finish repairing, wherein 19 qualified batteries are obtained.
The total repair rate of the battery is 63.3%, wherein the repair rate of the vulcanized battery (the battery with the negative electrode reason) is 82.61%.
Comparative example 4
The 20h rate capacity of 30 batteries with poor 6-FM-40 capacity is detected to be within the range of 5-20 Ah.
1. Removing the cover plate and the safety valve of the battery, wherein the density of each unit cell patch of the battery is 1.05g/cm3The battery is kept still for 2 hours, the lower limit pressure is 15.3V/battery at normal temperature and normal pressure, the current is limited for 10A charging for 5 hours, and then 2A positive 2s negative 1s pulse is used for alternately and continuously charging for 36 hours.
2. The 20h rate capacity of 18 batteries is greater than or equal to 36 Ah.
12 batteries with the capacity of lower than 36Ah are subjected to lower limit pressure of 15.3V/battery at normal temperature and normal pressure, and 5 batteries with electrolyte are detected to be obviously black and turbid to be abandoned after being charged for 5 hours under the condition of current limiting 10A. In addition, 7 batteries are alternately charged for 36h by 2A positive 2s negative 1s pulse for one-time repair, and 5 batteries still can not meet the repair standard after detection. The 5 batteries are tested by a cadmium electrode, and the positive electrodes of the 2 batteries are confirmed to have faults, and the negative electrodes of the 3 batteries only cause insufficient capacity.
3. After 12 hours of 4A charging, the qualified 20 batteries are changed into 1.2A charging, acid pumping and finishing to finish the repair.
The total repair rate of the battery is 66.7%, wherein the repair rate of the vulcanized battery (the battery with the negative electrode reason) is 87%.
Example 3
The 10h rate capacity of 48 batteries with poor GFM-300 capacity is detected to be within the range of 60-120 Ah.
1. Removing the safety valve of the battery, wherein the density of each unit cell of the battery is 1.03g/cm3The voltage of the battery is limited to 2.5V/cell after the battery is kept stand for 2 hours, the current is limited to 60A for charging for 5 hours, and then the battery is subjected to constant current charging for 3 hours at 30A. The electrolyte of the cell is checked to have no obvious black turbidity, and 48 cells are placed in an environment at the temperature of 55 ℃ for standing for 10 hours.
2. After standing, the battery was immediately transferred to a sealed high-pressure vessel at a temperature of 55 ℃ and charged for 10 hours at a high pressure of 0.3 Mpa.
3. The 20h rate capacity of the 41 batteries is detected at normal temperature and normal pressure, and the 20h rate capacity of the 41 batteries is more than or equal to 270 Ah.
The voltage of 7 batteries with the capacity lower than 270Ah is limited to 2.5V/battery, the current is limited to 60A, the batteries are charged for 5h, and the 2 batteries are detected to have obvious black turbidity and are discarded. After the battery which is checked to have no obvious black turbidity is kept stand for 10 hours in the environment of 55 ℃, the battery is immediately transferred into a closed high-pressure container with similar temperature, the battery 30A is charged for 10 hours in the environment of 0.3Mpa of high pressure, the battery is taken out and the 10-hour rate capacity is detected under normal temperature and normal pressure, and the 10-hour rate capacity of 6 batteries is larger than 270 Ah. The test of cadmium electrode confirmed that the capacity was insufficient for the negative electrode of 1 out-of-specification cell.
4. And (4) charging 47 qualified batteries for 12 hours by 30A, then charging 9A, extracting acid, finishing and completing the repair.
The total repair rate of the battery is 97.9%, wherein the repair rate of the vulcanized battery (the battery with the negative electrode reason) is 97.92%.
Comparative example 5
The 10h rate capacity of 48 batteries with poor GFM-300 capacity is detected to be within the range of 60-120 Ah.
1. Removing the safety valve of the battery, wherein the density of each unit cell of the battery is 1.03g/cm3150ml of sulfuric acid electrolyte containing 1% of repair liquid, after the battery is kept still for 2 hours, the voltage is limited to 2.5V/cell under normal temperature and normal pressure, and after the current is limited to 60A for charging for 5 hours, the battery is continuously charged for 36 hours at 15A.
2. The 10h rate capacity is detected under the normal temperature and the normal pressure after the batteries are taken out, and the 10h rate capacity of 32 batteries is more than or equal to 270 Ah.
The voltage of 16 batteries with the capacity lower than 270Ah is limited to 2.5V/battery under normal temperature and normal pressure, the current is limited to 60A, charging is carried out for 5h, the electrolyte is checked to have no obvious black turbidity, then continuous charging is carried out for 36h by 15A, and the primary repair is carried out again, and the detection shows that 10 batteries still can not reach the repair standard. The test of cadmium electrode confirmed that 10 unqualified batteries caused insufficient capacity due to negative electrode.
3. And after charging for 12 hours at 30A, charging for 9A, extracting acid, and finishing to finish repairing 38 qualified batteries.
The total repair rate of the battery is 79.2%, wherein the repair rate of the vulcanized battery (the battery with the reason of the negative electrode) is 79.2%.
Example 4
In comparative example 5, after 10 batteries which can not reach the repair standard are detected, the voltage is limited by 2.5V/battery and the current is limited by 60A, the batteries are charged for 5 hours and then are placed in an environment with the temperature of 55 ℃ for standing for 10 hours. After standing, the mixture was immediately transferred to a sealed high-pressure vessel at a temperature of 55 ℃ and charged for 10 hours in an environment of high pressure of 0.3 MPa.
The 20h rate capacity of 10 batteries is greater than 270Ah after the batteries are taken out and detected at normal temperature and normal pressure.
After charging 10 batteries for 12h by 30A, charging by 9A, extracting acid, and finishing to finish repairing.
And the 10 unqualified batteries meet the requirements after being repaired.
Comparative example 6
The 10h rate capacity of 48 batteries with poor GFM-300 capacity is detected to be within the range of 60-120 Ah.
1. Removing the safety valve of the battery, wherein the density of each unit cell of the battery is 1.03g/cm3After the battery is kept still for 2 hours, the voltage is limited to 2.5V/current limited 60A for charging for 5 hours at normal temperature and normal pressure, and then the battery is alternately charged for 36 hours by 15A positive 2s negative 1s pulses.
2. The rate capacity of 10h is detected under the normal temperature and the normal pressure after the batteries are taken out, and the rate capacity of 10h of the total 37 batteries is more than or equal to 270 Ah.
Charging 11 batteries with the capacity lower than 270Ah for 5h under the conditions of normal temperature and normal pressure, limiting the voltage by 2.5V/battery and limiting the current by 60A, checking that the electrolyte has no obvious black turbidity, then alternately and continuously charging for 36h by 15A positive 2s negative 1s pulses for once more repairing, and detecting that 7 batteries still can not reach the repairing standard. The test of cadmium electrode confirmed that the capacity of 7 unqualified batteries is insufficient due to the negative electrode.
3. And after charging for 12 hours by 30A, charging for 9A, extracting acid, and finishing to finish repairing, wherein the qualified 41 batteries are obtained.
The total repair rate of the battery is 85.4%, wherein the repair rate of the vulcanized battery (the battery with the reason of the negative electrode) is 85.4%.
Example 5
In comparative example 6, after 7 batteries still reach the voltage limit of 2.5V/current limit of 60A which can not meet the repair standard and are charged for 5 hours, the battery is placed in an environment with the temperature of 55 ℃ and is kept stand for 10 hours. After standing, the mixture was immediately transferred to a sealed high-pressure vessel at a temperature of 55 ℃ and charged for 10 hours in an environment of high pressure of 0.3 MPa.
The 20h rate capacity of the 7 batteries is detected at normal temperature and normal pressure, and the 20h rate capacity of the 7 batteries is larger than 270 Ah.
And 7 batteries are charged for 12 hours by 30A, and then 9A is charged, acid is extracted and finished to finish the repair.
And 7 unqualified batteries meet the requirements after repair.
Claims (8)
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