CN110797585B - Container formation method for lead-acid storage battery - Google Patents
Container formation method for lead-acid storage battery Download PDFInfo
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- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000002253 acid Substances 0.000 title claims abstract description 30
- 238000003860 storage Methods 0.000 title claims abstract description 26
- 238000007600 charging Methods 0.000 claims abstract description 83
- 229910001868 water Inorganic materials 0.000 claims abstract description 31
- 238000007599 discharging Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010277 constant-current charging Methods 0.000 claims abstract description 9
- 230000002441 reversible effect Effects 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims 4
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 36
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 35
- 229910052924 anglesite Inorganic materials 0.000 description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 34
- 230000008569 process Effects 0.000 description 20
- 230000005611 electricity Effects 0.000 description 18
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 17
- 230000002829 reductive effect Effects 0.000 description 17
- 238000007254 oxidation reaction Methods 0.000 description 15
- 238000003487 electrochemical reaction Methods 0.000 description 13
- 238000006722 reduction reaction Methods 0.000 description 13
- 239000013543 active substance Substances 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 12
- 235000011149 sulphuric acid Nutrition 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 230000010287 polarization Effects 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000009467 reduction Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011505 plaster Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910006529 α-PbO Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 230000006872 improvement Effects 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
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- -1 Pb2+ ion Chemical class 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910006531 α-PbO2 Inorganic materials 0.000 description 1
- 229910006654 β-PbO2 Inorganic materials 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
- 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
- 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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Abstract
The invention relates to the technical field of lead-acid storage batteries, in particular to a container formation method of a lead-acid storage battery, which comprises the following steps: a step (a): reverse charging: adding acid into the battery to be formed, placing the battery in warm water bath for 2 hours, and adding-0.02C 20 Charging for 55 minutes, and then intermitting for 5 minutes; step (b): multi-stage constant current charging: the multi-stage constant current charging at least comprises a first stage and a second stage in sequence, and the current of the second stage is greater than that of the first stage; the step (c) includes: intermittent operation is carried out for 3 hours; step (d): circulating charge and discharge: charging and discharging for multiple times are a charging and discharging cycle, an interval is arranged between every two times of charging, and the step (e) is carried out after multiple charging and discharging cycles; a step (e): and (3) constant-current intermittent charging: the storage battery is charged in a positive current and intermittent mode until the voltage is stable. The formation method has short formation period and low power consumption, and is beneficial to obtaining better results of the starting performance and deep cycle performance of the AGM start-stop battery and reducing energy consumption.
Description
Technical Field
The invention relates to the technical field of lead-acid storage batteries, in particular to a container formation method of a lead-acid storage battery.
Background
The novel environment-friendly automobile is designed with a set of start-stop system according to the principle that when the automobile meets the conditions of traffic lights and the like in urban driving, an engine stops working under the idling state of the automobile, and when the automobile needs to run, the storage battery is used as driving power for supplying power, and then the storage battery is automatically converted into the engine for supplying power. Therefore, unnecessary fuel consumption can be saved, the potential is particularly greater for urban working conditions, the fuel consumption can be reduced by 8% -15%, and the emission of waste tail gas can be reduced by about 5%, so that the novel emission standard is reached. The AGM start-stop lead-acid storage battery is a battery with a novel purpose, has higher requirements on the electrical performance due to the special purpose, and not only has good automobile starting performance, but also has the characteristic of being capable of being used as a power source to drive an automobile in a short time, namely deep cycle performance. Therefore, all countries develop and develop the product in competition, so as to occupy the high point of the technical field. The AGM start-stop lead-acid storage battery adopts the AGM ultrafine glass wool separator, so that the AGM start-stop lead-acid storage battery has the advantages that the electrolyte is absorbed in the AGM separator, and the generated hydrogen and oxygen are recombined into water in the storage battery to flow back to the electrolyte through the oxygen circulation principle in the use process of the storage battery, so that the storage battery has longer service life and is more environment-friendly. But internalization during production, such as with a battery, is more difficult than with a flooded battery.
The traditional formation method is generally formed by adopting a simple constant-current charging and discharging method, has the characteristics of high energy consumption and long formation period, and is formed into the battery by a traditional mode, the formation period is more than 60 hours, and the total electricity consumption is C 20 Over 7 times of ampere hours, formation consistency is not easy to control, low-temperature performance, deep cycle performance and other performances are easily influenced by formation effect, and the reject ratio is high.
Disclosure of Invention
In order to solve the technical problems of long formation period and high total power consumption in the formation of the lead-acid storage battery in the prior art, the application provides an internal formation method of the lead-acid storage battery,
the lead-acid storage battery internal formation method comprises the following steps of adding acid into a battery to be formed, placing the battery in a warm water bath, and sequentially carrying out the following steps:
step (b): multi-stage constant current charging: the multi-stage constant current charging at least comprises a first stage and a second stage in sequence, and the current of the second stage is greater than that of the first stage;
step (d): circulating charge and discharge: charging and discharging for multiple times are a charging and discharging cycle, an interval is arranged between every two times of charging, and the step (e) is carried out after multiple charging and discharging cycles;
a step (e): and (3) constant-current intermittent charging: the storage battery is charged in a positive current and intermittent mode until the voltage is stable.
Wherein, before step (b), further comprising: step (a): reverse charging: adding acid into the battery to be formed, placing the battery in warm water bath for 2 hours, and adding-0.02C 20 Charge for 55 minutes and pause for 5 minutes.
Wherein, in step (b), the first stage is performed at 0.13C 20 Charging for 55 minutes, and then intermitting for 5 minutes; the second stage adopts0.2C 20 Charging for 55 minutes, and then intermitting for 5 minutes, and repeating the steps for 6 times.
Wherein the multi-stage constant current charging further comprises a third stage performed after the second stage is finished, and the third stage is performed at 0.2C 20 After charging for 50 minutes, the charging is carried out at 0.3C 20 Charging was carried out for 5 minutes, followed by 5-minute intervals, and this was repeated 6 times.
Wherein a step (c) is further included, the step (c) being performed between the step (b) and the step (d), the step (c) including: the batch was 3 hours.
Wherein one charge-discharge cycle in the step (d) comprises: firstly, the temperature is 0.2C 20 Charging for 55min, intermittently charging for 5min, repeating the above steps for three times, and charging at-0.2C 20 Discharging for 5 minutes, and finally, intermitting for 5 minutes; and (e) after 3 charging and discharging cycles, the step (d) is performed.
Wherein, the constant current intermittent charging in the step (e) is firstly carried out at 0.2C 20 Charging for 55min, repeating for 5min, and repeating for five times at 0.13C 20 Charging for 55 minutes to complete formation.
Wherein the temperature of the warm water bath in the formation process is kept between 50 and 65 ℃.
Wherein the density of the acid added into the battery to be formed is 1.255 +/-0.005 g/cm 3 。
Wherein, the C 20 The table shows the number of ampere-hours of capacity of the battery at 20 hours rate.
According to the battery container formation method, the whole formation period is shortened from the existing 60 hours to 34 hours and 25 minutes, the production efficiency is improved, and the total electricity consumption is C 20 The safety time is about 5 times that of the prior art, and the electric energy is saved by 30 percent compared with the total power consumption in the prior art; meanwhile, AGM start-stop battery formation consistency is good, and the reject ratio is low. Meanwhile, after the whole formation is finished, the proportional relation between the alpha-PbO 2 and the beta-PbO 2 is optimal, and the reaction efficiency is improved, so that the AGM start-stop battery has better starting performance and deep cycle performance, and the energy consumption is reduced.
Drawings
Fig. 1 is a charging curve diagram of a formation method according to an embodiment of the present disclosure.
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and accompanying drawings.
The embodiment provides a container formation method for a lead-acid storage battery, which is particularly suitable for AGM start-stop series lead-acid storage batteries, as shown in FIG. 1, wherein a vertical axis in the drawing is current (A), and a battery C for current supply amplitude 20 Multiplying capacity by multiplying factor value, wherein the horizontal axis is time (h), positive current is arranged above the horizontal axis, negative current is arranged below the horizontal axis, three negative currents in the later period are discharge peak currents, the current amplitude is zero, the current in the time period is zero, and the whole formation completion time period is 34h25min, wherein C 20 The number of hours of 20 hours of rate of capacity ampere of the battery is shown.
The method sequentially comprises the following steps:
step 1: adding the solution into the battery to be formed to obtain the product with the density of 1.255 +/-0.005 g/cm 3 After the acid solution is prepared, the battery to be formed is placed in a formation tank column at the temperature of 50-65 ℃ for two hours;
step 2: with-0.02C 20 After charging for 55 minutes, the batch time is 5 minutes, and the step 3 is carried out;
and 3, step 3: by using 0.13C 20 Charging for 55 minutes, and after the intermittent operation for 5 minutes, switching to the step 4;
and 4, step 4: using 0.2C 20 Charging for 55 minutes, then intermitting for 5 minutes, repeating for 6 times, and then transferring to the step 5;
and 5: at 0.2C 20 After charging for 50 minutes, the charging is carried out at 0.3C 20 Charging for 5 minutes, then, intermitting for 5 minutes, repeating the steps for 6 times, and then, turning to the step 6;
step 6, after the intermittence time is 3 hours, the step 7 is carried out;
and 7: after three charging and discharging cycles, entering step 8, wherein one charging and discharging cycle comprises charging and discharging at 0.2C 20 Charging for 55min, repeating for 5min, and charging at-0.2C 20 Discharging for 5 minutes, and finally, intermitting for 5 minutes;
and step 8: at 0.2C 20 Charging for 55min, repeating for 5min, repeating for five times, and charging at 0.13C 20 Charging for 55 minutes, and finishingAnd (4) formation.
The battery container formation completed through the steps has the advantages that the whole formation period is shortened from the existing 60 hours to 34 hours and 25 minutes, the production efficiency is improved, and the total electricity consumption is C 20 The ampere hour is about 5 times, and compared with the total power consumption in the prior art, the electric energy is saved by 30 percent. Meanwhile, AGM start-stop battery formation consistency is good, the reject ratio is low, and better starting performance and deep cycle performance can be obtained.
In the step 1 and the step 2, the negative direction of the polar plate of the battery to be formed is-0.02C after being soaked in the electrolyte for 2 hours 20 And (3) feeding electricity for 55min to temporarily convert a small amount of active substances of the anode along the surface of the rib inside the anode into pure lead, and increasing the conductive surface to reduce the resistance of the anode due to the enlargement of the area of the pure lead to a certain extent, so that the improvement of the reaction efficiency of the anode after positive electricity feeding is more facilitated. During negative power supply, the reaction of current on the negative electrode is temporarily converted into (PbO2) in a negative electrode lead rib and a small amount of adjacent contact active substances, the reaction efficiency of the negative electrode after positive power supply is influenced to a certain extent, but because the negative electrode is reduced into pure lead (Pb) after positive charging is recovered, the electrochemical reaction efficiency of the negative electrode is far higher than that of the positive electrode, the influence on the formation efficiency of the negative electrode can be ignored, the negative electrode can be certainly completed as long as the positive electrode formation is completed in the total power supply amount designed by people, so that the key point of the step 1 design is how to improve the conversion efficiency of the positive electrode and the formation of a microstructure, and the result is found through a large number of experiments that the conversion efficiency of the positive electrode and the formation of a microstructure are improved at-0.02C 20 After charging for 55 minutes, the conversion rate of the positive electrode can reach the requirement.
In step 3, in order to convert the plate lead paste substance into the required active substances PbO2 and Pb, an external dc power supply is used to perform an oxidation-reduction reaction on the plates on the positive and negative electrodes by using an electrolysis principle (commonly called charging), so as to oxidize the plate active substance as the positive electrode, wherein the oxide is PbO2, and the plate active substance as the negative electrode is subjected to a reduction reaction, and the reduced substance is Pb. The electrolysis (charging) process is an electrochemical reaction process, so that the plate formation needs two reactions, namely a chemical reaction and an electrochemical reaction, to convert the active substance into a more ideal PbO2 and Pb phase structure.
Firstly, after acid with the density of 1.255 +/-0.005 g/cm3 is added into an AGM start-stop battery, a green plate is contacted and soaked in dilute sulfuric acid electrolyte, and an alkaline substance in an active substance and the dilute sulfuric acid solution generate a neutralization reaction, wherein the reaction formula is as follows:
PbO+H2SO4→PbSO4+H2O
PbO·PbSO4+H2SO4→PbSO4+H2O
3PbO·PbSO4·H2O+3H2SO4→4PbSO4+4H2O
4PbO·PbSO4+4H2SO4→5PbSO4+4H2O
the neutralization reaction is continued from the contact of the polar plate and the sulfuric acid solution to the formation process until the reaction substance is exhausted, and the neutralization reaction does not occur. As can be seen from the reaction equation, as a result of the chemical reaction, sulfuric acid (H2SO4) is consumed, water and lead sulfate are generated, and therefore, the concentration of acid in the formation housing is lowered, the PH is increased, and the temperature is raised (the reaction of PbO with H2SO4 is an exothermic reaction), and the lead paste material on the surface and in the micropores of the plate is gradually changed into the salt-like lead sulfate (PbSO4), and the speed of the change is related to the concentration and temperature of the sulfuric acid solution and the immersion time. In the whole formation process, according to the chemical reaction principle, the chemical reaction activity is reduced when the temperature is too low, the reaction efficiency is reduced, the temperature is too high, polarization and bubbles are easy to generate, and thermal runaway is easy to cause, so that the temperature is controlled to be between 50 and 65 ℃ in the whole formation process.
Starting time of electrochemical reaction: under the action of a direct current power supply, external current flows in from the positive electrode of the formation device and flows out from the negative electrode (the initial reverse feeding reaction is opposite to the initial reverse feeding reaction), oxidation reaction occurs on the positive electrode, reduction reaction occurs on the negative electrode, and the electrochemical reaction formula is as follows:
A. electrochemical reaction of the positive electrode:
the oxidation reaction at the initial stage of the formation and feeding of the positive electrode is as follows:
PbO+H2O－2e→α－PbO2+2H+
PbO·PbSO4+3H2O－4e→2α－PbO2+6H++SO42－
3PbO·PbSO4·H20+4H2O－8e→4α－PbO2+10H++SO42－
4PbO·PbSO4+5H2O－10e→5α—PbO2+10H++SO42－
the oxidation reaction in the later stage of the formation of the positive electrode is as follows:
PbSO4+2H2O－2e→β—PbO2+4H++SO42－
in the formation process of the positive electrode, the oxidation potential of the active substance in the system Pb-H2 SO 4-H2O is different, and the oxidation sequence is different.
Namely: the oxidation potential of Pb → PbO2 is + 0.667V;
the oxidation potential of PbO → PbO2 is + 1.107V;
4 PbO. PbSO4 → PbO2 has an oxidation potential of 1.172V;
the oxidation potential of PbO, PbSO4, H2O → PbO2 is + 1.285V;
PbO. PbSO4 → PbO2 has an oxidation potential of + 1.422V;
the oxidation potential of PbSO4 → PbO2 is + 1.690V;
therefore, the positive lead paste material is sequentially converted into PbO2 according to Pb, PbO, 4 PbO. PbSO4, 3PbO 2. PbSO 4. H2O, PbO. PbSO4 and PbSO4 in the oxidation process, and PbSO4 is most positive in oxidation potential and high in resistance, so that the positive lead paste material is easily oxidized into PbO2 in the middle and later stages of formation and when the formation tank pressure is high. In general, the product PbO2 formed by the positive electrode has two forms: α -PbO 2 and β -PbO 2, which affect the battery differently, α -PbO 2 acts like a skeleton in the positive active material, while β -PbO 2 acts like a feather. The two are interdependent, if the proportion of alpha-PbO 2 is large, the storage battery has longer service life but relatively smaller discharge energy, while the proportion of the beta-PbO 2 has stronger discharge capacity but is easy to loosen and collapse in the deep discharge process, the service life is shorter, and the start-stop battery has better starting capacity and better deep circulation capacity, so the proportion relation between the two is very important.
In general, the conditions for forming α -PbO 2 and β -PbO 2 are not the same, and the higher PH, higher Pb2+ ion concentration and lower current density of the solution are the conditions for promoting the formation of α -PbO 2, while the oxidation of PbSO4 in acidic solution and at higher current density is the condition for forming β -PbO 2. At the initial stage of formation, because the polar plate has soaked in dilute sulfuric acid solution for a period of time earlier, the lead plaster material of polar plate surface and polar plate downthehole surface takes place neutralization reaction with sulfuric acid this moment for the downthehole solution PH value of polar plate risees, and the hydration of lead plaster material makes inside lead plaster material be in alkaline medium in the polar plate dipping process in addition, if: PbO +
H2O → Pb2+ +2 OH-, because the oxidation of the lead paste material during the formation by electricity starts from the portion of the grid ribs closest to the electrolyte, then extends to the inside of the plate, and extends in an irregular network shape, and finally reaches the surface of the plate, the formation of initial PbO2 is formed in the internal alkaline medium, so that α -PbO 2 is more easily formed, and although the internal electrochemical reaction generates sulfuric acid at this stage, because the sulfuric acid is consumed by the chemical reaction at a speed higher than that of the internal electrochemical reaction, the electrolyte in the plate holes still has a higher pH value, and in addition, a larger amount of PbO and Pb exist in the plate, and these conditions make the electrochemical reaction mainly occur in the medium with a higher pH value in the plate during the formation, the product mainly α -PbO 2 is formed, and the reaction efficiency of the active material is not high at this stage, the surplus electricity can only be used as useless work, such as water decomposition, so 0.2C is designed for 3-9h in the initial stage of forward power supply 20 The current is charged in a mode of 6 times of intermittent power supply, the conversion of active substances is met with lower energy consumption, and the conversion amount of alpha-PbO 2 reaches the standard.
In step 4, some PbSO4 begins to be converted into β -PbO 2 due to the gradual PH decrease during the formation period of 10-16h, and according to the characteristic, 6 groups of special pulse peaks are designed during the charging period of 10h-16h, namely step 5: at 0.2C 20 After charging for 50 minutes, the charging is carried out at 0.3C 20 After 5 minutes of charging, 5 minutes of rest, and 6 repetitions in this way, the normal electrochemical process is modified and the impact is initiated on PbSO4 already present in the active mass, in order to maximize its conversion to α -PbO 2 or β -PbO 2 as far as possible at this stage. Reducing the existence of PbSO 4. This is advantageous for controlling the alpha-P after the completion of the whole formationThe optimum proportional relationship between bO2 and beta-PbO 2 improves the reaction efficiency, thereby facilitating the start-up performance and deep cycle performance of AGM start-stop batteries with better results and reduced power consumption.
B. Electrochemical reaction of the negative electrode:
reduction reaction in the initial stage of formation of negative electrode:
PbO+2H++2e→Pb+H2O
PbO·PbSO4+2H++4e→2Pb+SO42－+H2O
3PbO·PbSO4·H2O+6H++8e→4Pb+SO42－+4H2O
4PbO·PbSO4+2H++10e→5Pb+SO42－+H2O
reduction reaction in the later stage of formation of the negative electrode:
PbSO4+2e→Pb+SO42－
in the process of forming the negative electrode, the reduction potentials of the lead paste materials in a Pb-H2 SO 4-H2O system are different, and the reduction sequence is also different.
Namely: the reduction potential of PbO → Pb is + 0.248V;
4 PbO. PbSO4 → Pb has a reduction potential of + 0.115V;
the reduction potential of 3 PbO. PbSO 4. H2O → Pb is + 0.037V;
PbO. PbSO4 → reduction potential of Pb is-0.099V;
the reduction potential of PbSO4 → Pb is-0.356V;
therefore, the negative lead paste material is prepared according to PbO, 4 PbO. PbSO4 in the reduction process
3PbO, PbSO4, H2O, PbO, PbSO4 and PbSO4 are sequentially converted into Pb, and PbSO4 has the most negative reduction potential, so that PbSO4 begins to be reduced until the reduction reaction of various basic lead sulfates and oxides of lead is almost completed in the later stage of formation. Since the 6 groups of special pulse peaks in the step 5 are designed in the middle period of formation (10-16h period), the normal electrochemical process is changed, and part of PbSO4 is converted into Pb in advance. If a large current pulse peak is used at an inappropriate timing and for a long time, the negative electrode active material may be loosened, and if the pulse peak is added from the beginning, a disadvantage is easily caused. Therefore, 6 groups of pulse peaks are given only in the middle period of charging for 10-16h, namely the receiving capacity of the positive/negative plate, namely the best reaction efficiency, so that a better formation effect can be obtained, and negative effects are reduced.
In addition, during the whole formation process, the concentration of sulfuric acid (H2SO4) in the electrolyte participating in the reaction is constantly changed, and the concentration of H2SO4 in the electrolyte is reduced due to the consumption of H2SO4 and the generation of water due to the chemical reaction of the lead plaster and the sulfuric acid in the initial stage. After power is applied, the electrochemical reaction generates H2SO4, but the neutralization chemical reaction which is carried out at the same time still consumes H2SO4, and the consumption speed is higher than the generation speed, SO the concentration of H2SO4 in the initial stage of formation is reduced along with the increase of the formation time. Generally, the formation time is 10-16 h. The chemical neutralization reaction is completed, the electrochemical reaction is continued to generate H2SO4, the concentration of H2SO4 in the electrolyte is increased along with the increase of formation time, and the formation concentration change and concentration polarization have great influence on the formation effect.
In the later middle and later stages of the formation, a large amount of gas will be generated, mainly due to the decomposition of water by electric current, and the electrochemical reaction is:
2H2SO4→4H++2SO42－
in the negative electrode: 4H + +4e → 2H2
At the positive electrode: 2SO 42- +2H 2O-4 e → 2H2SO4+ O2
The general reaction formula of the two poles is as follows: 2H2SO4+2H2O → 2H2SO4+2H2 ≠ O2 ℃
What is actually decomposed is water: 2H2O → 2H2 ↓ + O2 ↓
As a result of the electrolysis of water, oxygen gas is evolved at the positive electrode and hydrogen gas is evolved at the negative electrode, resulting in strong gassing in the cell. At the moment, the temperature rises quickly, the concentration polarization phenomenon is aggravated, and the formation efficiency is seriously influenced. In order to eliminate the phenomenon, the formation curve is designed with longer-time static electricity after 6 groups of pulse peaks, namely step 3: the current is reduced to 0A, the duration is 3 hours, and at the moment, the temperature of the battery is also reduced due to the effects of stopping power supply and cooling circulating water, so that bubbles in active substances are reduced, acid liquid adsorbed in the AGM partition plate is diffused and permeated into the polar plate again as much as possible, the concentration polarization phenomenon is reduced, and the reaction efficiency after power supply is restarted is facilitated.
But at this time due toFormation has entered middle and later stages, the gas volume that the polarization produced still can constantly increase, the temperature can rise sooner, in addition, the particularity of AGM start-stop battery separator, make wherein the acidizing fluid in the AGM separator more difficult to the inside diffusion of polar plate, polarization phenomenon is more serious, so this middle and later stages have designed the mode of discontinuous static for electricity, at the most serious stage of formation later stage polarization, except stopping giving the electricity for the short-time, three groups of transient discharge pulse peaks have been designed again, make its effect of eliminating the polarization faster, in order to eliminate polarization phenomenon as far as possible, lay the basis for follow-up improvement charging formation effect, step 7 promptly: after three charging and discharging cycles, entering step 8, wherein one charging and discharging cycle comprises charging and discharging at 0.2C 20 Charging for 55min, intermittently charging for 5min, repeating the above steps for three times, and charging at-0.2C 20 Discharge for 5 minutes and finally pause for 5 minutes.
In the later period, because most of the active substances are converted, the curve is intermittently and pulse-charged again by using a current with a smaller multiplying power until the curve is finished, namely the step 8: at 0.2C 20 Charging for 55min, repeating for 5min, and repeating for five times at 0.13C 20 Charging for 55 minutes to complete formation. The design ensures that the acid liquor has more time to permeate into the polar plate, reduces the temperature rise in the charging process, inhibits the polarization phenomenon to a certain extent, considers the amplitude peak value and the duration of the power supply to provide active substances with enough conversion energy, and has better conversion effect, so that the whole conversion effect is satisfied.
The practical application method comprises the following steps:
1) in the circulating water tank, an acid (density: 1.255 +/-0.005 g/cm3) is connected with a charger, and then the current value, the power supply direction and the power supply time of the corresponding step are input into a charger computer according to the regular characteristic steps and the method of the curve shown in figure 1. The formation charging process can be completed.
2) The temperature of the battery in the formation process is controlled within 50-65 ℃, and the temperature detection points are based on the temperature of the middle two lattices of the battery. When the temperature is over 65 deg.C, it can be increased to form cooling water in the tank column, and when the battery liquid temperature is lower than 50 deg.C, it can have no need of circulating cooling water.
The conversion process and characteristics of the battery formation stages are fully analyzed according to the particularity of the AGM start-stop lead-acid storage battery and the electrochemical principle of the formation of the AGM start-stop lead-acid storage battery, the influence of beneficial factors and adverse factors of the stages is comprehensively considered, the static electricity (namely 0A current) time of battery plate impregnation and the initial special reverse electricity supply are carried out, the time of electricity supply, the amplitude peak value of electricity supply, the electricity supply time length, the static electricity time and the curve form of electricity supply in each stage are strictly designed and specified, and the whole process is combined into a set of complete formation curve mode, so that the AGM start-stop battery formation consistency is good, the reject ratio is low, the energy consumption is reduced, and the charging time is shortened. Compared with the traditional mode, the method can save more than 30% of electricity by using the formation charging, the formation period is shortened from more than 60 hours to 34 hours and 25 minutes, the production efficiency is improved, and better starting performance and deep cycle performance are obtained.
The present invention has been described in terms of specific examples, which are provided to aid understanding of the invention and are not intended to be limiting. Numerous simple deductions, modifications or substitutions may also be made by those skilled in the art in light of the present teachings.
Claims (4)
1. The internal formation method of the lead-acid storage battery is characterized in that the battery to be formed is placed in a warm water bath after being added with acid, and the following steps are sequentially carried out:
a step (a): reverse charging: adding acid into the battery to be formed, placing the battery in warm water bath for 2 hours, and adding-0.02C 20 Charging for 55 minutes, and then intermitting for 5 minutes;
a step (b): multi-stage constant current charging: the multi-stage constant current charging at least comprises a first stage and a second stage in sequence, and the current of the second stage is greater than that of the first stage;
step (c): intermittent operation is carried out for 3 hours;
a step (d): circulating charge and discharge: charging and discharging for multiple times are performed to form a charging and discharging cycle, an interval is formed between every two times of charging, and the step (e) is performed after multiple charging and discharging cycles;
a step (e): and (3) constant-current intermittent charging: charging the storage battery to a stable voltage by adopting a positive current and intermittent mode;
wherein, in step (b), the first stage is performed at 0.13C 20 Charging for 55 minutes, and then intermitting for 5 minutes; the second stage adopts 0.2C 20 Charging for 55 minutes, and then, intermittently charging for 5 minutes, and repeating the steps for 6 times;
the multi-stage constant current charging further comprises a third stage which is carried out after the second stage is finished, wherein the third stage is 0.2C 20 After charging for 50 minutes, the charging is carried out at 0.3C 20 Charging for 5 minutes, then intermittently charging for 5 minutes, and repeating the steps for 6 times;
one charge-discharge cycle in the step (d) comprises: firstly, 0.2C 20 Charging for 55min, repeating for 5min, and charging at-0.2C 20 Discharging for 5 minutes, and finally, intermittently discharging for 5 minutes;
after 3 charging and discharging cycles, the step (d) enters a step (e);
in the step (e), the constant current is discontinuously charged by firstly 0.2C 20 Charging for 55min, repeating for 5min, repeating for five times, and charging at 0.13C 20 Charging for 55 minutes to complete formation.
2. The chemical synthesis method of claim 1, wherein the temperature of the warm water bath is maintained at 50-65 ℃ during the chemical synthesis process.
3. The chemical synthesis method of claim 1, wherein the density of the acid added into the battery to be formed is 1.255 ± 0.005g/cm 3 。
4. The chemical synthesis method of claim 1, wherein C is 20 Indicating the 20 hour rate capacity ampere-hours of the battery.
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| CN112768789B (en) * | 2021-01-27 | 2022-03-01 | 天能电池集团股份有限公司 | Formation method for improving low-temperature capacity of lead storage battery |
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