CN116031516A - Method for improving high-rate discharge performance of lead-acid battery - Google Patents

Method for improving high-rate discharge performance of lead-acid battery Download PDF

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CN116031516A
CN116031516A CN202310312408.1A CN202310312408A CN116031516A CN 116031516 A CN116031516 A CN 116031516A CN 202310312408 A CN202310312408 A CN 202310312408A CN 116031516 A CN116031516 A CN 116031516A
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charging
current
standing
lead
acid battery
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CN116031516B (en
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单颖会
吴涛
林双
战祥连
唐震
张进宇
王超
王英健
徐艳
李振铎
张兵
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Zibo Torch Energy Co ltd
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention belongs to the technical field of lead-acid batteries, and particularly relates to a method for improving high-rate discharge performance of a lead-acid battery. The method for improving the high-rate discharge performance of the lead-acid battery comprises the following steps of: (1) step-down current discharge: the method comprises the steps of discharging and standing sequentially, wherein the voltage after discharging is controlled to be 1.4-1.6V; thirdly, regulating the density of the electrolyte and then standing; (2) staged charging; (3) charge-discharge cycle: sequentially repeating the steps (1) and (2); (4) adjusting the density of the electrolyte to a prescribed value. The invention effectively improves the high-rate discharge performance of the lead-acid battery.

Description

Method for improving high-rate discharge performance of lead-acid battery
Technical Field
The invention belongs to the technical field of lead-acid batteries, and particularly relates to a method for improving high-rate discharge performance of a lead-acid battery.
Background
At present, lead-acid batteries still have larger markets in the fields of power, energy storage and the like due to higher safety. Some application fields have high requirements on the high-rate discharge performance of the lead-acid battery, so that the lead-acid battery applied to the conventional field cannot meet special discharge requirements. Because of relatively fewer customers with higher requirements on high-rate discharge, the market demand is small, and for lead-acid battery factories, the input and output of specially developed high-rate discharge lead-acid batteries with special requirements cannot be in direct proportion.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for improving the high-rate discharge performance of a lead-acid battery, which improves the aperture and the porosity of a polar plate of the lead-acid battery by an electrochemical method and effectively improves the high-rate discharge performance of the lead-acid battery.
The method for improving the high-rate discharge performance of the lead-acid battery comprises the following steps of:
(1) Current discharge is reduced in stages: the method comprises the steps of discharging and standing sequentially, wherein the voltage after discharging is controlled to be 1.4-1.6V; and the third step is to adjust the density of the electrolyte and then to stand.
(2) Charging in stages;
(3) Charge-discharge cycle: sequentially repeating the steps (1) and (2);
(4) And adjusting the density of the electrolyte to a specified value.
The step-down current discharge comprises the following steps:
the first step: at an I of 4-6 times 5 Discharging the current to a voltage1.4V-1.6V, and standing for 30-60 min;
the discharge in the first step is to make the active material on the surface layer of the polar plate and H 2 SO 4 Fast reaction to produce PbSO with larger particle 4 PbSO with larger particles 4 The stacks may form relatively large apertures to facilitate further current discharge reduction. If the discharge rate is too low, pbSO 4 The particles are relatively small, the stack is compact, the subsequent full discharge is not facilitated, and if the discharge rate is too high, the battery heats seriously, and the cycle life of the battery is influenced. Due to PbSO at the end of discharge 4 Layer barrier H 2 SO 4 Diffusion is carried out to reduce the diffusion rate, serious concentration polarization generated on the surface of the active substance can lead to rapid reduction of discharge voltage, at the moment, the discharge cut-off voltage is set too low, and if the discharge cut-off voltage is set too high, the subsequent current-reducing discharge generates relatively compact PbSO 4 The layer influences the deep discharge effect; the purpose of the rest in the first step is to let H in the electrolyte body 2 SO 4 Diffusion into the polar plate to eliminate the concentration difference of electrolyte inside and outside the polar plate, too short diffusion is insufficient, and too long diffusion can reduce PbSO in the polar plate 4 Activity of the negative electrode plate is easy to cause H 2 SO 4 Salinization, which reduces the capacity of the battery cathode;
and a second step of: 1 to 2 times of I 5 Discharging current until the voltage is 1.4V-1.6V, and standing for 30-60 min;
the discharging in the second step aims to further lead the active substances deep in the polar plate to be connected with H 2 SO 4 The reaction is carried out, the aperture and the porosity of the deep part of the polar plate are improved, and the parameter setting is carried out according to the same step as the first step; the standing function and parameter setting in the second step are the same as those in the first step;
and a third step of: adjusting the density of the electrolyte to 1.1365g/cm at 25 DEG C 3 ~1.2150g/cm 3 Standing for 10-30 min;
because the concentration of the electrolyte is low in the previous two discharges, the further discharge requirement is difficult to meet, the further discharge operation is facilitated by increasing the concentration of the electrolyte, the discharge depth is influenced by the too low concentration, and the subsequent electrolyte density callback is not facilitated by the too high concentration; in the third step, standing and acting as in the first step;
fourth step: with 0.1 to 0.25 times of I 5 Discharging current until the voltage is 1.4V-1.6V, and standing for 30-60 min;
the purpose of the fourth step of discharging is to allow the active substances of a deeper level to react with H 2 SO 4 The reaction and the discharge are more sufficient, the low discharge current can cause serious overdischarge, and partial active substances on the grid are converted into PbSO 4 The binding force between the grid and the active substance is reduced, the cycle life of the battery is influenced, and the PbSO 4 Is a hindrance to H 2 SO 4 Diffusion into the plate is difficult. The discharge current is too high, so that the discharge is finished due to concentration polarization in advance, the reaction of internal active substances is insufficient, and the internal aperture and the porosity are influenced; and in the fourth step, the standing function and the parameter setting are the same as those in the first step.
The staged charging comprises the following steps:
s1 is 0.05 to 0.1 times of I 5 Constant current charging is carried out for 10-20 min; the step is to activate the battery, the function is to build an ion channel in the polar plate, prepare for charging with large current, the activation effect is poor when the current is too small, and the microstructure of the polar plate is easily damaged when the current is too high;
s2 is 0.4 to 1 times of I 5 Charging the current to a voltage of 2.40V-2.45V; the current flows through the low charging rate, the treatment efficiency is affected, the local current density is too high due to the fact that the current is too high, gas is generated, the generated gas damages the polar plate structure, the cycle life of the battery is reduced, the charging electric quantity at the stage is low due to the fact that the charging cut-off voltage is too low, the subsequent small current charging time is prolonged, the treatment efficiency is reduced, the charging is violently sucked due to the fact that the cut-off voltage is too high, the polar plate structure is damaged, electric energy is wasted due to the fact that side reactions occur, and the current efficiency is reduced;
s3, standing for 30-60 min; the function is to make the electrolyte concentration inside and outside the polar plate diffuse to be consistent;
s4, adjusting the density of the electrolyte at 25 ℃ to 1.0640g/cm 3 ~1.0994g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the After S2 charging, the concentration of the electrolyte can be rapidly increased, and when the concentration of the electrolyte is too high, H generated during charging can be inhibited 2 SO 4 Diffusion into the electrolyte body, reducing the charging reactionThe rate, on the other hand, can lead to serious hydrogen evolution side reaction, and reduce the current efficiency;
s5, standing for 10-30 min; the action is the same as S3;
s6, the I is 0.2 to 0.35 times of that of the steel 5 Charging the current to a voltage of 2.65V-2.7V; after S2 is charged, the battery has higher charge state and is easy to generate gassing side reaction, so compared with S2, the step reduces current and increases voltage, the effect of reducing current is to reduce side reaction, and the effect of increasing voltage is to lead PbSO 4 More complete conversion to active;
s7, standing for 30-60 min; the action is the same as S3;
s8, the I is 0.1 to 0.15 times of that of the steel 5 Charging for 180-240 min at constant current; on the one hand, the effect can make the residual PbSO in a small amount 4 Converting into active substances, and keeping the ion channels inside the polar plate smooth until the microstructure inside the polar plate is stable;
s9, standing for 30-60 min; the action is the same as S3;
s10, adjusting the density of the electrolyte to the original density of the electrolyte of the lead-acid battery; the purpose is to ensure that the states of the battery at each stage are basically consistent in the cyclic treatment process;
s11, standing for 10-30 min; the action is the same as S3.
The lead-acid battery is a fully charged lead-acid battery which is well formed and meets the requirements of GB/T7403.1-2018.
In the step (3), the repetition times are 3-5 times, the circulation times are too small, the improvement of the aperture and the porosity in the polar plate cannot achieve the effect of improving the high-rate discharge performance of the battery, and the excessive circulation times can cause excessive expansion of the polar plate of the battery.
The specific steps of the step (4) are as follows: charging and discharging for 2-3 times for 5hr, and regulating the density of the electrolyte to a specified value within 30-60 min after each charging and discharging;
wherein, the charging and discharging steps for 5hr are as follows:
a. charging: at 20-25 ℃, I is 0.7 times of that of the mixture 5 Charging current to the average voltage of 2.4V, and adding 0.35 times of I 5 The voltage change of the single battery is not more than 0.02V within 2h of current charging;
b. discharging: battery cellI is used within 1-24 hours after charging 5 The current is discharged, the ambient temperature is 15-40 ℃, and the cut-off voltage is 1.7V.
The ambient temperature of the step (1) is 10-50 ℃.
The ambient temperature of the step (2) is 10-50 ℃.
According to the reaction principle of the lead-acid battery, the pore diameter and the porosity of the lead-acid battery polar plate are improved through the volume change of the active substances in the charging and discharging process of the lead-acid battery. The pore diameter is improved, which is favorable for the electrolyte to permeate into the deep part of the polar plate, and H is reduced 2 SO 4 Transmission resistance in the plate; the effect of improving the porosity is two aspects, namely, the surface area of the active substance is increased, and the active substance and H are facilitated 2 SO 4 And secondly, the content of electrolyte in the polar plate is improved, and concentration polarization caused by the concentration reduction of electrolyte on the surface of an active substance in the discharge process is relieved, so that the improvement of the aperture and the porosity is a reasonable means for improving the high-rate discharge performance of the lead-acid battery.
The lead-acid battery which is well formed and meets the requirements of GB/T7403.1-2018 is subjected to staged flow-down discharge in a full-charge state, the purpose of the staged flow-down discharge is to fully react active substances, and a positive electrode reactant PbO is utilized 2 Negative electrode reactant Pb and reaction product PbSO 4 The volume difference between the positive plate and the negative plate improves the aperture and the porosity of the positive plate and the negative plate.
The staged charging function is to charge PbSO in the deep discharge state battery plate 4 Is converted into active substance, the positive electrode active substance is PbO 2 The active material of the negative electrode is Pb, and the discharge process is caused by the reaction product PbSO 4 Volume-corrected positive electrode active material PbO 2 And the negative electrode active material Pb is large, the polar plate can be in an expansion state to a certain extent, and PbSO on the positive plate and the negative plate can be generated during charging 4 Conversion to PbO respectively 2 And Pb, the pore diameter and the porosity of the inside of the polar plate are improved due to the reduction of the volume of the active material.
Compared with the prior art, the invention has the beneficial effects that:
the aperture and the porosity of a polar plate of the lead-acid battery are improved by an electrochemical method, so that the high-rate discharge performance of the lead-acid battery is effectively improved;
the conventional lead-acid battery treated by the method can effectively improve the high-rate discharge performance, can meet the use requirement, and does not need to specially establish a high-rate discharge lead-acid battery production line.
Detailed Description
The technical scheme of the present invention will be clearly and completely described in the following examples.
Example 1
Untreated lead-acid batteries of 5PzS and 500 type (meeting the requirements of GB/T7403.1-2018, I thereof 5 The current is 100A), and the discharge of 500A is required to be not less than 40min at the temperature of 30 ℃. The battery is discharged for 38min at 500A before untreated, and the density of the battery electrolyte is 1.290g/cm 3 （25℃）。
Subjecting the lead acid battery to a process comprising the steps of:
(1) The ambient temperature is 10 ℃, and the battery is discharged by reducing the current in stages in the full-power state;
the step-down current discharge comprises the following steps:
the first step: discharging at 400A current to a voltage of 1.6V, and standing for 30min;
and a second step of: discharging with 100A current to a voltage of 1.6V, and standing for 30min;
and a third step of: adjusting the density of the electrolyte to 1.1365g/cm at 25 DEG C 3 Standing for 10min;
fourth step: discharging with 10A current to a voltage of 1.6V, and standing for 30min;
(2) The ambient temperature is 10 ℃, and the charging is carried out in stages;
the staged charging comprises the following steps:
s1, charging for 10min with 5A current constant current;
s2, charging to the voltage of 2.40V by using 40A current;
s3, standing for 30min;
s4, adjusting the density of the electrolyte at 25 ℃ to 1.0640g/cm 3 ；
S5, standing for 10min;
s6, charging to the voltage of 2.65V by using 20A current;
s7, standing for 30min;
s8, charging for 180min with 10A current constant current;
s9, standing for 30min;
s10, adjusting the density of the electrolyte to 1.290g/cm of the original density of the electrolyte of the lead-acid battery 3 ；
S11, standing for 20min;
(3) Charge-discharge cycle: sequentially repeating the steps (1) and (2) for 3 times;
(4) Regulating the density of the electrolyte to a specified value; charging and discharging for 5hr for 2 times after the charge and discharge cycle is completed, and regulating electrolyte density to 1.290g/cm at 30min after each cycle of charging 3 （25℃）；
Wherein, the charging and discharging steps for 5hr are as follows:
a. charging: at 20 ℃, at 0.7 times of I 5 Charging current to the average voltage of 2.4V, and adding 0.35 times of I 5 The voltage change of the single battery is not more than 0.02V within 2h of current charging;
b. discharging: i is used within 1-24 hours after the battery is charged 5 The current is discharged, the ambient temperature is 20 ℃, and the cut-off voltage is 1.7V.
After the treatment is finished, the battery is placed in a constant-temperature water bath box at 30 ℃ for 24 hours, and after the constant temperature is reached, the discharge time of 500A current is measured to be 40.5 minutes.
Example 2
Untreated lead-acid batteries of 5PzS and 500 type (meeting the requirements of GB/T7403.1-2018, I thereof 5 The current is 100A), and the discharge of 500A is required to be not less than 40min at the temperature of 30 ℃. The battery is discharged for 38min at 500A before untreated, and the density of the battery electrolyte is 1.290g/cm 3 （25℃）。
Subjecting the lead acid battery to a process comprising the steps of:
(1) The ambient temperature is 30 ℃, and the battery is discharged by reducing the current in stages in the full-power state;
the step-down current discharge comprises the following steps:
the first step: discharging at 500A current to a voltage of 1.5V, and standing for 45min;
and a second step of: discharging at 150A current to a voltage of 1.5V, and standing for 45min;
and a third step of: adjusting the density of the electrolyte to 1.1750g/cm at 25 DEG C 3 Static statePlacing for 20min;
fourth step: discharging with 15A current to a voltage of 1.5V, and standing for 45min;
(2) The ambient temperature is 30 ℃, and charging is carried out in stages;
the staged charging comprises the following steps:
s1, charging for 15min at a constant current of 7.5A;
s2, charging to the voltage of 2.42V by using 70A current;
s3, standing for 45min;
s4, adjusting the density of the electrolyte at 25 ℃ to 1.0851g/cm 3 ；
S5, standing for 20min;
s6, charging to the voltage of 2.67V by 28A current;
s7, standing for 45min;
s8, charging for 210min with 12A current constant current;
s9, standing for 45min;
s10, adjusting the density of the electrolyte to 1.290g/cm of the original density of the electrolyte of the lead-acid battery 3 ；
S11, standing for 20min;
(3) Charge-discharge cycle: sequentially repeating the steps (1) and (2) for 4 times;
(4) Regulating the density of the electrolyte to a specified value; after the charge and discharge cycle is finished, charging and discharging for 5hr for 3 times, and regulating the electrolyte density to 1.290g/cm at 45min after each charge and discharge 3 （25℃）；
Wherein, the charging and discharging steps for 5hr are as follows:
a. charging: at 25 ℃, at 0.7 times of I 5 Charging current to the average voltage of 2.4V, and adding 0.35 times of I 5 The voltage change of the single battery is not more than 0.02V within 2h of current charging;
b. discharging: i is used within 1-24 hours after the battery is charged 5 The current was discharged at 25℃and the cut-off voltage was 1.7V.
After the treatment, the battery was placed in a constant temperature water bath at 30℃for 24 hours, and after the constant temperature was reached, a 500A current discharge time of 41.1 minutes was measured.
Example 3
Untreated 5. 5PzS 500.500 leadAcid battery (meeting GB/T7403.1-2018 requirement, I thereof 5 The current is 100A), and the discharge of 500A is required to be not less than 40min at the temperature of 30 ℃. The battery is discharged for 38min at 500A before untreated, and the density of the battery electrolyte is 1.290g/cm 3 （25℃）。
Subjecting the lead acid battery to a process comprising the steps of:
(1) The ambient temperature is 50 ℃, and the battery is discharged by reducing the current in stages in a full-power state;
the step-down current discharge comprises the following steps:
the first step: discharging at 600A current to a voltage of 1.4V, and standing for 60min;
and a second step of: discharging with 200A current to a voltage of 1.4V, and standing for 60min;
and a third step of: adjusting the density of the electrolyte to 1.2150g/cm at 25 DEG C 3 Standing for 30min;
fourth step: discharging with 25A current to a voltage of 1.6V, and standing for 60min;
(2) The ambient temperature is 50 ℃, and the charging is carried out in stages;
the staged charging comprises the following steps:
s1, charging for 20min with 10A current constant current;
s2, charging to 2.45V at 100A current;
s3, standing for 60min;
s4, adjusting the density of the electrolyte at 25 ℃ to 1.0994g/cm 3 ；
S5, standing for 30min;
s6, charging to the voltage of 2.7V by using 35A current;
s7, standing for 60min;
s8, charging for 240min with 15A current constant current;
s9, standing for 60min;
s10, adjusting the density of the electrolyte to 1.290g/cm of the original density of the electrolyte of the lead-acid battery 3 ；
S11, standing for 30min;
(3) Charge-discharge cycle: sequentially repeating the steps (1) and (2) for 5 times;
(4) Regulating the density of the electrolyte to a specified value; after the charge-discharge cycle was completed, the process was carried out 2 timesCharging and discharging for 5hr, and regulating electrolyte density to 1.290g/cm at 60min after each charging and discharging 3 （25℃）；
Wherein, the charging and discharging steps for 5hr are as follows:
a. charging: at 25 ℃, at 0.7 times of I 5 Charging current to the average voltage of 2.4V, and adding 0.35 times of I 5 The voltage change of the single battery is not more than 0.02V within 2h of current charging;
b. discharging: i is used within 1-24 hours after the battery is charged 5 The current is discharged, the ambient temperature is 40 ℃, and the cut-off voltage is 1.7V.
After the treatment, the battery was placed in a constant temperature water bath at 30℃for 24 hours, and after the constant temperature was reached, a 500A current discharge time of 41.8 minutes was measured.
From examples 1-3, the lead-acid battery treated by the method provided by the invention has significantly improved high-rate discharge performance.

Claims (8)

1. A method of improving the high rate discharge performance of a lead acid battery, the lead acid battery being subjected to a process comprising the steps of:
(1) Current discharge is reduced in stages: the method comprises the steps of discharging and standing sequentially, wherein the voltage after discharging is controlled to be 1.4-1.6V; thirdly, regulating the density of the electrolyte and then standing;
(2) Charging in stages;
(3) Charge-discharge cycle: sequentially repeating the steps (1) and (2);
(4) And adjusting the density of the electrolyte to a specified value.
2. The method of improving the high rate discharge performance of a lead acid battery of claim 1, wherein the step-down current discharge comprises the steps of:
the first step: at an I of 4-6 times 5 Discharging current until the voltage is 1.4V-1.6V, and standing for 30-60 min;
and a second step of: 1 to 2 times of I 5 Discharging current until the voltage is 1.4V-1.6V, and standing for 30-60 min;
and a third step of: adjusting the density of the electrolyte to 1.1365g/cm at 25 DEG C 3 ~1.2150g/cm 3 Standing for 10-30 min;
fourth step: with 0.1 to 0.25 times of I 5 Discharging the current until the voltage is 1.4-1.6V, and standing for 30-60 min.
3. The method of improving the high rate discharge performance of a lead acid battery of claim 1, wherein the staged charging comprises the steps of:
s1 is 0.05 to 0.1 times of I 5 Constant current charging is carried out for 10-20 min;
s2 is 0.4 to 1 times of I 5 Charging the current to a voltage of 2.40V-2.45V;
s3, standing for 30-60 min;
s4, adjusting the density of the electrolyte at 25 ℃ to 1.0640g/cm 3 ~1.0994g/cm 3 ；
S5, standing for 10-30 min;
s6, the I is 0.2 to 0.35 times of that of the steel 5 Charging the current to a voltage of 2.65V-2.7V;
s7, standing for 30-60 min;
s8, the I is 0.1 to 0.15 times of that of the steel 5 Charging for 180-240 min at constant current;
s9, standing for 30-60 min;
s10, adjusting the density of the electrolyte to the original density of the electrolyte of the lead-acid battery;
s11, standing for 10-30 min.
4. The method of improving the high rate discharge performance of a lead acid battery of claim 1, wherein the lead acid battery is a fully charged state lead acid battery well formed to meet GB/T7403.1-2018 requirements.
5. The method for improving the high-rate discharge performance of a lead-acid battery according to claim 1, wherein in the step (3), the repetition number is 3 to 5.
6. The method for improving the high-rate discharge performance of a lead-acid battery according to claim 1, wherein the step (4) comprises the following specific steps: charging and discharging for 2-3 times for 5hr, and regulating the density of the electrolyte to a specified value within 30-60 min after each charging and discharging;
wherein, the charging and discharging steps for 5hr are as follows:
a. charging: at 20-25 ℃, I is 0.7 times of that of the mixture 5 Charging current to the average voltage of 2.4V, and adding 0.35 times of I 5 The voltage change of the single battery is not more than 0.02V within 2h of current charging;
b. discharging: i is used within 1-24 hours after the battery is charged 5 The current is discharged, the ambient temperature is 15-40 ℃, and the cut-off voltage is 1.7V.
7. The method for improving the high-rate discharge performance of a lead-acid battery according to claim 1, wherein the ambient temperature in the step (1) is 10-50 ℃.
8. The method for improving the high-rate discharge performance of a lead-acid battery according to claim 1, wherein the ambient temperature in the step (2) is 10-50 ℃.
CN202310312408.1A 2023-03-28 2023-03-28 Method for improving high-rate discharge performance of lead-acid battery Active CN116031516B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011181312A (en) * 2010-03-01 2011-09-15 Shin Kobe Electric Mach Co Ltd Method of chemical conversion in battery container for lead-acid battery
CN103579691A (en) * 2012-07-24 2014-02-12 南京捷翔能源科技有限公司 Storage battery restoration system and restoration method thereof
CN107732342A (en) * 2017-09-04 2018-02-23 中航锂电（洛阳）有限公司 A kind of charging method of electrokinetic cell
CN110797585A (en) * 2018-08-02 2020-02-14 肇庆理士电源技术有限公司 Container formation method for lead-acid storage battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011181312A (en) * 2010-03-01 2011-09-15 Shin Kobe Electric Mach Co Ltd Method of chemical conversion in battery container for lead-acid battery
CN103579691A (en) * 2012-07-24 2014-02-12 南京捷翔能源科技有限公司 Storage battery restoration system and restoration method thereof
CN107732342A (en) * 2017-09-04 2018-02-23 中航锂电（洛阳）有限公司 A kind of charging method of electrokinetic cell
CN110797585A (en) * 2018-08-02 2020-02-14 肇庆理士电源技术有限公司 Container formation method for lead-acid storage battery

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