CN107123835B - A kind of electrochemical method and system of lead-acid accumulator desulfurization - Google Patents
A kind of electrochemical method and system of lead-acid accumulator desulfurization Download PDFInfo
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- CN107123835B CN107123835B CN201710365429.4A CN201710365429A CN107123835B CN 107123835 B CN107123835 B CN 107123835B CN 201710365429 A CN201710365429 A CN 201710365429A CN 107123835 B CN107123835 B CN 107123835B
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- 239000002253 acid Substances 0.000 title claims abstract description 81
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 38
- 230000023556 desulfurization Effects 0.000 title claims abstract description 38
- 238000002848 electrochemical method Methods 0.000 title claims abstract description 11
- 238000007600 charging Methods 0.000 claims abstract description 88
- 238000000034 method Methods 0.000 claims abstract description 71
- 230000008569 process Effects 0.000 claims abstract description 36
- 239000000654 additive Substances 0.000 claims abstract description 11
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 7
- 239000007832 Na2SO4 Substances 0.000 claims abstract description 3
- 239000003792 electrolyte Substances 0.000 claims description 30
- 238000007599 discharging Methods 0.000 claims description 29
- 230000008439 repair process Effects 0.000 claims description 18
- 230000003009 desulfurizing effect Effects 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 10
- 230000000284 resting effect Effects 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000004073 vulcanization Methods 0.000 abstract description 6
- 230000005518 electrochemistry Effects 0.000 abstract 1
- 238000004891 communication Methods 0.000 description 13
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- 238000010586 diagram Methods 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 238000010277 constant-current charging Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000010280 constant potential charging Methods 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical class [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000002169 hydrotherapy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000010278 pulse charging Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
- H01M10/446—Initial charging measures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of electrochemical methods of lead-acid accumulator desulfurization, and the method includes at least one charge and discharge cycles, before carrying out the charge and discharge cycles for the first time, are added in lead-acid accumulator and contain Na2SO4Additive solution, and allow lead-acid accumulator stand a period of time；Wherein, charging process includes: constant-current phase, constant-voltage phase, standing stage and pulse current stage.The present invention discloses a kind of systems of lead-acid accumulator Electrochemistry Desulfurization.The present invention can will be repaired because of the lead-acid accumulator that capacity declines caused by vulcanization, restore capacity of lead acid battery to 90% or more of its rated capacity.
Description
Technical Field
The invention relates to a storage battery repair technology, in particular to an electrochemical method and system for lead-acid storage battery desulfurization.
Background
With the development of lead-acid storage batteries in recent years, large-sized valve-controlled sealed lead-acid storage batteries become the first choice of large-capacity fixed batteries due to the remarkable advantages of closed structures, small maintenance pressure, no pollution to the surrounding environment, low price, good charge and discharge performance, safe use and the like, and are widely applied to various fields, such as the fields of electric traction, energy storage and the like. However, there are still many problems in management and maintenance, and the vulcanization phenomenon is one of them. Lead-acid batteries have a positive plate (lead dioxide) and a negative plate (lead). The charging process of the storage battery is realized by the chemical reaction of active substances on the polar plate and the dilute sulfuric acid of the electrolyte, and the chemical energy of the active substances is converted into electric energy. Lead-acid batteries, however, form lead sulfate crystals during discharge, which can be reduced relatively easily during charging, and if properly maintained, lead sulfate does not adhere to the plates, or if a small amount of lead sulfate adheres, it participates in the electrochemical reaction during charging, and is eliminated. However, during long-term use, or due to poor maintenance and management during use, such as insufficient charging, long-term standing after partial discharge, etc., lead sulfate cannot be normally eliminated through the charging process, and thus, the lead sulfate gradually accumulates on the electrode plate to form a stable amorphous crystal attached to the surface of the battery electrode plate. This lead sulphate crystals are difficult to eliminate by conventional charging, a process known as sulphation, often referred to simply as "sulphidation". With further placement, these amorphous crystals will further transform into crystalline aggregates, which deposit on the negative plate. Such crystalline aggregates are coarse and hard and are more difficult to eliminate.
The sulfuration not only causes large crystallization resistance and poor conductivity on the surface of the electrode plate, but also reduces the active materials of the battery, thereby causing the gradual reduction of the battery capacity and seriously affecting the charge and discharge performance and the service life of the lead-acid storage battery.
In fact, about 80% of lead-acid batteries that are scrapped suffer from the above-mentioned problems of vulcanization. Therefore, if the lead-acid storage battery subjected to vulcanization can be repaired, the energy can be greatly saved, the pollution of the discarded battery to the environment is reduced, and positive economic and social benefits are achieved.
At present, the method for repairing the lead-acid storage battery at home and abroad after the early capacity of vulcanization is reduced mainly comprises the following steps: the method comprises the steps of high-current charging, hydrotherapy, pulse repair and the like, but the repairing effect of the methods on the vulcanized lead-acid storage battery is not obvious.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method and system for repairing a lead-acid battery whose capacity has decreased due to vulcanization.
In order to achieve the above objects, one aspect of the present invention provides an electrochemical process for the desulfurization of lead acid batteries, said process comprising at least one charge-discharge cycle, the addition of Na-containing compounds to the lead acid battery being carried out before the first said charge-discharge cycle2SO4And allowing the lead-acid storage battery to stand for a period of time; wherein, the charging process includes: a constant current stage, a constant voltage stage, a standing stage and a pulse current stage.
Preferably, wherein the additive solution contains Na2SO4Is 1 to 5 wt% based on the rated capacity of the storage battery, and the addition amount thereof is 1.1 to 1.5mL/Ah, preferably, the standing is performed for a period of timeThe duration of time is 8 to 15 hours, more preferably 10 to 13 hours.
Preferably, in the constant current stage, the constant current of 0.1-0.2A/Ah is continuously applied for 4-7 hours according to the rated capacity of the battery.
Preferably, a constant voltage of 2.4-2.7V is continuously applied for 4-6 hours in the constant voltage stage.
Preferably, when the temperature of the battery electrolyte in the constant current stage or the constant voltage stage rises to a predetermined first temperature value, the predetermined first temperature value is 50-55 ℃, preferably 55 ℃, the application of the corresponding constant current or the constant voltage is suspended, and when the temperature of the battery electrolyte is lower than a predetermined second temperature value, the predetermined second temperature value is 35-40 ℃, preferably 40 ℃, the application of the corresponding constant current or the constant voltage is resumed.
Preferably, the standing stage lasts for 1-2 hours, and in the standing stage, when the temperature of the electrolyte is lower than a predetermined third temperature, a constant voltage of 2.25-2.35V is applied to the battery, and when the temperature of the electrolyte is higher than the predetermined third temperature, the application of the constant voltage is stopped, preferably, the predetermined third temperature is 50-58 ℃, preferably 50-56 ℃, and most preferably 55 ℃.
Preferably, a pulse current is continuously applied for 2-4 hours in the pulse current stage, the pulse current value is 30-70%, preferably 40-60% of the current applied in the constant current stage, the period of the pulse current is preferably 120-360 ms, preferably 180-300 ms, and the duty ratio is 1/2.
Preferably, the method further comprises: after adding Na-containing2SO4Before the additive solution of (2), the lead-acid battery is charged to 100% of the actual capacity.
Preferably, the charge and discharge cycle is performed until the capacity of the lead-acid storage battery is restored to the desired capacity, for example, the charge and discharge cycle is performed 2 to 10 times, preferably, the charge and discharge cycle is performed 4 to 6 times, such as 4, 5, 6 times.
Another aspect of the invention provides a system for electrochemical desulfurization of lead-acid batteries according to the method of any one of claims 1 to 9, the system comprising: a battery discharge device, a programmable battery charging device; wherein,
the battery discharging device is used for setting a repair expected value and standing time in the charging and discharging cycle process; and for connecting or disconnecting the electrical connection between the constant current load and the battery; and for connecting or disconnecting the electrical connection between the programmable battery charging apparatus and the battery; and for reading various electrochemical parameters of the cell with the sensor;
the programmable battery charging device is used for programming and setting parameters of current, voltage, preset temperature and time applied during battery charging, and the current, voltage, preset temperature and time parameters can be set during charging so as to realize the constant current stage, the constant voltage stage, the standing stage and the pulse current stage of any method in the invention.
When the lead-acid storage battery is repaired, the scheme of the invention applies specific current and voltage to the lead-acid storage battery, namely: the constant current application, the constant voltage pause application and the pulse current application, and the addition of the additive during the charging process can eliminate lead sulfate crystals deposited on the polar plate, and even coarse hard crystal aggregates which are formed can be effectively removed. Especially the preferred scheme, has reached better effect. Therefore, the invention has the following beneficial effects:
1. the method and the system effectively promote the disintegration of the lead sulfate crystals deposited on the electrode plate and the re-dissolution of the lead sulfate crystals into the electrolyte. The average capacity of a lead-acid battery desulfurized by the method of the invention can be increased to more than 90%, for example more than 92%, preferably more than 97%, even 99% to 100% of the rated capacity. The capacity of the lead-acid battery is restored to near its rated capacity.
2. Effectively relieves the pollution to the environment caused by the early scrapping of the lead-acid storage battery, saves resources and can bring great economic and social benefits.
3. The method is easy to operate and popularize, and the system can automatically execute the desulfurization operation and is convenient and simple to use.
Drawings
FIG. 1 is a schematic diagram illustrating the process of applying current and voltage to charge a battery according to an embodiment of the present invention;
FIG. 2 is a schematic flow diagram of an electrochemical process for desulfurizing a lead acid battery, according to one embodiment of the invention;
FIG. 3 is a schematic diagram of the composition of a lead acid battery desulfurization system in accordance with the method of the present invention;
FIG. 4 is a schematic diagram of a system of the present invention for de-sulfurizing a lead-acid battery, according to one embodiment of the present invention;
FIG. 5 is a schematic diagram of a system of the present invention for de-sulfurizing charging a lead-acid battery, according to one embodiment of the present invention;
FIG. 6 is a schematic diagram of waveforms of voltage and current applied when charging a battery, according to one embodiment of the present invention;
fig. 7 is a graph showing the change in the actual capacity of the battery pack during the repair process according to embodiment 2 of the present invention;
FIG. 8 is a graph showing the change in the average voltage values of the unit cells at the end of the charge of the secondary battery pack in the repair process according to example 2 of the present invention;
FIG. 9 is a graph showing the change in the average density value of unit cells at the end of discharge of a battery pack during a repair process according to example 2 of the present invention;
fig. 10 is a graph showing the variation in the maximum voltage difference between unit cells at the end of discharge of a battery pack during a repair process according to embodiment 2 of the present invention;
FIG. 11 is a graph showing the change in the charge capacity value before the battery pack is charged to 2.4V during the repair process according to embodiment 2 of the present invention;
fig. 12 is a graph showing the change in the average density value of the unit cells at the end of the charge of the battery pack during the repair process according to example 1 of the present invention.
Detailed Description
The invention provides an electrochemical method and system for lead-acid battery desulphurization, aiming at the problem of capacity reduction of a lead-acid battery caused by lead sulfate crystallization on an electrode plate. The method and system of the present invention will now be described in detail with reference to a preferred embodiment thereof. Further advantages and improvements of the present invention will become apparent from the following description.
It should be understood by those skilled in the art that the following embodiments are only for illustrating the present invention so that those skilled in the art can easily understand the present invention, and are not intended to limit the scope of the present invention.
FIG. 2 shows a schematic flow diagram of an electrochemical method for desulfurizing a lead acid battery, according to one embodiment of the invention. Referring to FIG. 2, the method of the present invention may include steps 201-206.
In step 201, according to a preferred embodiment of the present invention, the battery is initially charged to 100% of the actual capacity before the charge-discharge cycle for repairing the battery is started, and the temperature of the battery is raised by charging to 100% of the actual capacity, so as to promote the additive to infiltrate into the battery and the substance to be dissolved. Of course, if the battery has been charged to 100% of actual capacity, it may be discharged first and then recharged to 100% of actual capacity. The additive is then added to the battery and allowed to stand for a period of time. The additive contains sodium sulfate salt capable of forming a competitive electrochemical reaction with lead. The sodium sulphate added is added in the form of an aqueous solution with a concentration between 1% and 5% by weight, preferably between 2% and 4% by weight. The amount of the additive is determined according to the rated capacity of the storage battery, and is about 1.1-1.5 mL/Ah, for example. The standing time of the storage battery can be determined according to the factAs the case may be. The time is usually 8 to 15 hours, for example, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, and the like. The additive can be fully infiltrated into the storage battery through standing, and PbSO on the electrode plate is partially decomposed through a series of reactions4And (4) crystals.
And then carrying out desulfurization treatment on the lead-acid storage battery by using the desulfurization system for the lead-acid storage battery.
The desulfurization system of the present invention includes a battery discharge device and a programmable battery charging device. Referring to FIG. 3, the desulfurization system of the present invention is schematically illustrated.
The battery discharge device 31 may set a repair expected value and a standing time (including a standing time after discharge and a standing time after charge) in the charge/discharge cycle. On the one hand, for discharging the battery and on the other hand, also as a controller for the desulfurization process. Control for connecting or disconnecting the electrical connection between the constant current load and the battery; controls for also connecting or disconnecting the electrical connection between the programmable battery charging apparatus 32 and the battery; and also for reading various electrochemical parameters of the cell using sensors.
The programmable battery charging device 32 is used for programming and setting parameters such as current, voltage, preset temperature (including preset first temperature, preset second temperature and preset third temperature), time and the like applied when the battery is charged through the programmable charging device, and after the programmable battery charging device is connected to the battery to be repaired, the current, voltage, preset temperature and time can be set in the charging process to realize a constant current stage, a constant voltage stage, a standing stage and a pulse current stage which are detailed below and are used for charging the lead-acid storage battery.
The relevant parameters are set by the battery discharging device and the programmable battery charging device.
According to the embodiment shown in fig. 2, the process then proceeds to step 202, where the discharge process of the battery is started. Referring to fig. 4, when discharging is performed, the battery discharging device 41 keeps the programmable battery charging device 42 off from the lead-acid battery to be repaired, while the battery discharging device performs the discharging process of the battery by turning the battery to be repaired on a constant current load.
After the discharge is completed, step 203 is executed to suspend the discharge. After the discharge is completed, the battery discharge device stops working and cuts off the electric connection with the battery to be processed, and the discharge is suspended for a period of time, so that the temperature of the battery is reduced to below 40 ℃ to the ambient temperature. The pause discharge duration is generally related to battery capacity, ambient temperature, and the like. For example, may last for about 3 hours. During disconnection, the battery discharge device performs a reading operation of the electrochemical parameters of the battery using the sensors, reading data including the battery voltage, the battery electrolyte density, the battery capacity, etc.
Then, step 204 is executed to start the charging process. Referring to fig. 5, when charging is performed, the battery discharging device 51 connects the battery to be repaired to the programmable battery charging device 52, as shown in fig. 5. The programmable battery charging device 52 executes a program to begin the charging process of the battery.
An exemplary charging process according to the present invention is illustrated in fig. 1 and 6. Fig. 1 is a schematic flow chart of applying current and voltage when charging a battery according to the method of the present invention. Fig. 6 is a schematic diagram of waveforms of voltage and current applied when charging a battery according to an embodiment of the present invention.
The first stage is as follows: i.e. step 101, a constant current charging phase. The battery charging device is programmed to charge the battery with a constant current during this phase. Different initial constant currents are adopted according to different rated capacities, and the current is determined according to the rated capacity of the battery and according to 0.1-0.2A/Ah. In the constant current charging stage, the lead sulfate just generated is not aggregated and crystallized but dissolved in the electrolyte, and meanwhile, the voltage and the internal resistance of the battery reach the highest value, and the battery panel starts to generate heat. This process usually lasts 4 to 7 hours (T1).
The second phase, step 102, is a constant voltage charging phase. The programmable battery charging device maintains a constant voltage in the range of 2.4-2.7V during this stage. This phase continues for a sufficiently long period of time (T2) until the overcharge factor is sufficiently large for the actual capacity. At this stage, the plates heat up vigorously, expand and allow a portion of the crystals to start dissolving autonomously. This phase may last for 4 to 6 hours.
In the first stage and the second stage, if the temperature of the battery electrolyte rises to a predetermined first temperature value, which is 50-55 ℃, such as 51 ℃, 52 ℃, 55 ℃ and the like, preferably 55 ℃, the application of the corresponding constant current or the corresponding constant voltage is suspended, if necessary, the battery is subjected to heat dissipation by an electric fan until the temperature is lower than a predetermined second temperature value, which is 35-40 ℃, such as 36 ℃, 38 ℃ and the like, preferably 40 ℃, and the application of the corresponding constant current or the corresponding constant voltage is immediately resumed. This prevents the lead paste on the battery electrode plate from being damaged by the combined action of the relatively high temperature and the electricity during the charging process.
The third stage, step 103, is the resting stage. This phase continues for a period of time (T3) with the battery in a relatively stationary state. When the temperature of the battery electrolyte is higher than a preset third temperature value, no treatment is carried out; applying a constant low voltage, for example 2.25V to 2.35V, for preventing electrolyte stratification and maintaining the temperature of the electrolyte only when the temperature is below the predetermined third temperature value; the application of the voltage is stopped as soon as the temperature rises to a predetermined third temperature value. The predetermined third temperature value is usually 50 to 70 ℃, for example, 55 ℃, 58 ℃, 60 ℃, 65 ℃, etc., preferably 55 ℃. Therefore, the electrolyte is kept at a certain temperature all the time, the electrolyte continues to do minimum vertical movement to prevent layering, and the layering can last for 1-2 hours in the stage.
The fourth phase, step 104, is a pulsed current charging phase. At this stage, the programmable battery charging apparatus holds the current pulse for a period of time. These pulsed currents cause a local temperature increase on the electrode plates, which increases the solubility of lead sulfate and causes further expansion of the deposited lead sulfate, resulting in crystal disintegration. This phase (T4) lasts 2 to 4 hours. The pulse current is 30-70% of the current in the constant current applying stage. The pulse period is 120-360 ms, preferably 180-300 ms, and the duty ratio is 1/2.
After the above four stages of charging, the battery discharging device cuts off the electrical connection between the programmable battery charging device and the lead-acid battery, and the process proceeds to step 205.
Step 205 performs charge suspension. During the charge pause, the battery discharge device performs a reading operation using a sensor, the reading data including: battery voltage, battery electrolyte density, battery capacity, etc. Through this stage, the temperature of the battery gradually drops to ambient temperature. The duration of this phase varies depending on the battery capacity and environmental conditions, and is approximately 3 hours.
After the above steps 202-205, a charge-discharge cycle is completed. In step 206, the battery discharge device determines whether the average capacity of the storage battery to be repaired has reached a desired value, for example, has been restored to 90% or more, for example, 92% or more, and preferably 97% or more of the rated capacity, based on the battery capacity parameter read in step 205. If the average capacity of the repaired storage battery reaches or exceeds the expected value, ending the desulfurization treatment; if the expected value has not been reached, steps 202 to 205 are repeated until the battery capacity is restored to the expected value, and the repair is completed.
One embodiment of the present invention has been described above by way of example only, and it should be understood by those skilled in the art that the present invention is not limited to the above embodiment.
According to a preferred embodiment, the method of the invention enables the capacity of the lead accumulator to be restored to more than 92% of the rated capacity, even up to close to the rated capacity. Generally, in the case of a battery whose service life is 5 to 10 years and whose actual capacity has decreased to 50 to 70% of the rated capacity, the capacity can be recovered to 92% or more of the rated capacity by repeating the above charge and discharge cycles 3 to 7 times, preferably 4 to 6 times.
The effect of the present invention is further illustrated by the following 4 specific examples.
Example 1:
as a general example, a set of GFM-500 lead acid batteries used for communication was desulfated for repair and tested using the method and system of the present invention. The lead-acid storage battery for communication is a GFM-500 type, one group comprises 24 unit batteries, the rated voltage and the rated capacity are 2V/500Ah, the average service life is 9 years, the average actual capacity is 53 percent of the rated capacity, the storage battery is not charged to 100 percent of the actual capacity, the appearance of the storage battery is normal, no physical damage exists, and the storage battery is subjected to desulfurization treatment by using the system and the method.
The lead-acid battery is initially charged to 100% of the actual capacity, and a 6 wt% sodium sulfate aqueous solution is added to the electrolyte in an amount of 0.5mL/Ah, and the battery is allowed to stand for 7 hours. And parameters such as current, voltage, preset temperature (including preset first temperature, preset second temperature and preset third temperature), time and the like applied during battery charging are programmed and set through a programmable charging device, and standing time parameters in the charging and discharging suspension process are set through a battery discharging device (in embodiments 1 to 3, the expected repairing value is not set so as to comprehensively reflect the technical effect condition of repairing through the methods of the embodiments).
The lead-acid battery is then connected to the inventive desulfurization system to begin the charge-discharge cycle.
First, the discharging device of the desulfurization system discharges by turning on the battery with a constant current load, and keeps the programmable battery charging device and the battery in an off state during the discharging period. The discharge current was 50A.
After the completion of the discharge, the discharge device of the desulfurization system was electrically disconnected from the battery and left for about 3 hours. During this time, the cell voltage, cell electrolyte density, and cell capacity were measured.
When the temperature of the battery is reduced to 35 ℃, charging is started. The discharging device of the desulfurization system connects the battery with the programmable battery charging device. The programmable battery charging device starts to charge the lead-acid storage battery according to the set program.
According to the charging procedure of the present invention, first, a first stage of constant current charging is started, and the battery is charged with a constant current of 34A (current level is 1/15 of rated capacity, which is a common parameter in constant current charging of such a storage battery in the prior art) for 5 hours, and the battery voltage reaches 2.6V. Then, the second stage of constant voltage charging is started, and charging is performed for 6 hours at a constant voltage of 2.5V (the voltage is 2.5V, which is a common parameter in constant voltage charging of such a secondary battery in the prior art). In the first and second stages, if the temperature of the electrolyte of the battery rises above 55 ℃, the constant current and constant voltage are suspended, the battery is cooled as necessary by means of an electric fan or the like until the temperature is below 40 ℃, and the constant current and constant voltage are immediately resumed. And after the constant voltage stage is finished, starting a third stage of standing for 1 hour without applying current and voltage, applying 2.15V voltage if the temperature is lower than 55 ℃, immediately stopping applying the current and voltage when the temperature is higher than 55 ℃, and returning the battery to the standing state. Finally, the third stage of pulse current charging is started, pulse current with the pulse loading period of 100ms, the duty ratio of 1/2 and the size of 40.8A (which is a common parameter in pulse charging of the storage battery in the prior art) is subjected to pulse current charging for 3 hours, and the voltage of the pulse current stage is kept at 2.3V.
The discharge device of the desulfurization system then cuts off the electrical connection between the programmable battery charging device and the battery and stands for 3 hours to reduce the temperature of the battery to between 35 ℃ and the ambient temperature. During this time, the battery discharge device measures the battery voltage, the battery electrolyte density, the battery capacity, and the like.
The above charge-discharge cycles were repeated for a total of 6 times, and the battery capacities after each cycle were: 60%, 69%, 80%, 89%, 93%.
After repair, the lead-acid storage battery pack has obviously improved performance. After the battery pack repaired by the method and the system is tested, the performances of the battery pack are shown in the following table 1 (according to the national standard YD/T799-2010 valve-controlled sealed lead storage battery for communication and the requirements of the storage battery test specification): table 1:
the various detections on the group of repaired storage batteries meet the requirements of national standard YD/T799-2010 valve-controlled sealed lead storage battery for communication and storage battery test specifications.
Example 2:
as a preferred embodiment, another set of GFM-500 lead-acid batteries used for communication was also devulcanized for repair and testing using the method and system of the present invention. The lead-acid storage battery for communication is a GFM-500 type, one group comprises 24 unit batteries, the rated voltage and the rated capacity are 2V/500Ah, the average service life is 7 years, the average actual capacity is 57 percent of the rated capacity, the storage battery is not charged to 100 percent of the actual capacity, the appearance of the storage battery is normal, no physical damage exists, and the storage battery is subjected to desulfurization treatment by using the system and the method.
The lead-acid battery is initially charged to 100% of the actual capacity, a 2 wt% sodium sulfate aqueous solution is added to the electrolyte in an amount of 1.2mL/Ah, and the battery is allowed to stand for 10 hours. The programmable charging device is used for programming parameters such as current, voltage, preset temperature (including preset first temperature, preset second temperature and preset third temperature), time and the like applied during charging of the battery, and the battery discharging device is used for setting parameters of standing time in the charging and discharging suspension process.
The lead-acid battery is then connected to the inventive desulfurization system to begin the charge-discharge cycle.
First, the discharging device of the desulfurization system discharges by turning on the battery with a constant current load, and keeps the programmable battery charging device and the battery in an off state during the discharging period. The discharge current was 50A.
After the completion of the discharge, the discharge device of the desulfurization system was electrically disconnected from the battery and left for about 3 hours. During which the discharge device measures parameters such as battery voltage, battery electrolyte density, battery capacity, etc.
When the temperature of the battery is reduced to 35 ℃, charging is started. The discharging device of the desulfurization system connects the battery with the programmable battery charging device. The programmable battery charging device starts to charge the lead-acid storage battery according to the set program.
According to the charging procedure of the present invention, first, the first stage of constant current charging was started, and the battery was charged with a constant current of 77A (applied at 0.154A/Ah) for 5 hours, and the battery voltage reached 2.6V. Then, the second stage of constant voltage charging was started, and charging was performed at a constant voltage of 2.6V for 6 hours. In the first stage and the second stage, if the temperature of the electrolyte of the battery rises to above 55 ℃, the constant current and the constant voltage are temporarily applied, the battery is radiated by an electric fan if necessary until the temperature is lower than 40 ℃, and the constant current and the constant voltage are immediately applied again. And after the constant voltage stage is finished, starting a third stage of standing for 1 hour without applying current and voltage, applying 2.25V voltage if the temperature is lower than 55 ℃, immediately stopping applying the current and voltage when the temperature is higher than 55 ℃, and returning the battery to the standing state. Finally, the third phase of pulse current charging is started, pulse current charging is carried out for 3 hours by pulse current with the pulse loading period of 360ms, the duty ratio of 1/2 and the size of 39A, and the voltage is kept at 2.3V in the pulse current phase.
The discharge device of the desulfurization system then cuts off the electrical connection between the programmable battery charging device and the battery and stands for 3 hours to reduce the temperature of the battery to between 35 ℃ and the ambient temperature. During this time, the battery discharge device measures the battery voltage, the battery electrolyte density, the battery capacity, and the like.
The above charge and discharge cycles are repeated for 5 times, and the performance of the battery after each cycle is shown in fig. 7-12 (determined according to various requirements of the national standard YD/T799-2010 valve-regulated sealed lead storage battery for communication and the storage battery test specification). The actual battery capacity respectively reaches the rated battery capacity: 62%, 73%, 88%, 92%, 98% (see fig. 7).
After repair, the lead-acid storage battery pack has obviously improved performance. The measured properties of the battery pack repaired by the method and the system of the invention are shown in the following table 2 (measured according to the requirements of the national standard YD/T799-2010 valve-regulated sealed lead storage battery for communication and the storage battery test specification): table 2:
the various detections on the group of repaired storage batteries meet the requirements of national standard YD/T799-2010 valve-controlled sealed lead storage battery for communication and storage battery test specifications.
Example 3:
as a comparative example, another set of GFM500 lead-acid batteries for communications was devulcanized repaired and tested using the method and system of the present invention, but without the addition of a sodium sulfate solution, in contrast to example 1. The lead-acid storage battery for communication is a GFM500 type, one group comprises 24 unit batteries, the rated voltage and the rated capacity are 2V/500Ah, the average service life is 7 years, the average actual capacity is 57% of the rated capacity, the storage battery is not charged to 100% of the actual capacity, the appearance of the storage battery is normal, and the storage battery is not physically damaged and is subjected to desulfurization treatment by using the system and the method.
Parameters such as current, voltage, preset temperature (including a preset first temperature, a preset second temperature and a preset third temperature), time and the like applied when the battery is charged are programmed and set through the programmable charging device, and parameters of standing time in the charging and discharging suspension process are set through the battery discharging device.
The lead-acid battery is then connected to the inventive desulfurization system to begin the charge-discharge cycle.
First, the discharging device of the desulfurization system discharges by turning on the constant current load to the battery. The programmable battery charging device is kept disconnected from the battery during the discharging. The discharge current was 50A.
After the completion of the discharge, the discharge device of the desulfurization system was electrically disconnected from the battery and left for about 3 hours. During this time, the cell voltage, cell electrolyte density, and cell capacity were measured.
When the temperature of the battery is reduced to 35 ℃, charging is started. The discharging device of the desulfurization system connects the battery with the programmable battery charging device. The programmable battery charging device starts to charge the lead-acid storage battery according to the set program.
According to the charging procedure of the present invention, first, the first stage of constant current charging was started, and the battery was charged at a constant current of 77A for 5 hours, and the battery voltage reached 2.6V. Then, the second stage of constant voltage charging was started, and charging was performed at a constant voltage of 2.6V for 6 hours. In the first stage and the second stage, if the temperature of the electrolyte of the battery rises to above 55 ℃, the constant current and the constant voltage are temporarily applied, the battery is radiated by an electric fan if necessary until the temperature is lower than 40 ℃, and the constant current and the constant voltage are immediately applied again. And after the constant voltage stage is finished, starting a third stage of standing for 1 hour without applying current and voltage, applying 2.25V voltage if the temperature is lower than 55 ℃, immediately stopping applying the current and voltage when the temperature is higher than 55 ℃, and returning the battery to the standing state. Finally, the third phase of pulse current charging is started, pulse current charging is carried out for 3 hours by pulse current with the pulse loading period of 360ms, the duty ratio of 1/2 and the size of 39A, and the voltage is kept at 2.3V in the pulse current phase.
The discharge device of the desulfurization system then cuts off the electrical connection between the programmable battery charging device and the battery and stands for 3 hours to reduce the temperature of the battery to between 35 ℃ and the ambient temperature. During this period, the battery voltage, the battery electrolyte density, the internal resistance, and the battery capacity were measured.
The charge and discharge cycles were performed 6 times in total, and the battery capacity after each cycle was: 57%, 75%, 82%, 85%, 86%.
The following properties were measured as shown in table 3 below: TABLE 3
Example 4
As a comparative example, another set of GFM500 lead-acid batteries used for communication was devulcanized repaired and tested using one of the pulse repair methods of the prior art to demonstrate the advantages of the present invention. The lead-acid storage battery for communication is a GFM500 type, one group comprises 24 unit batteries, the rated voltage and the rated capacity are 2V/500Ah, the average service life is 7 years, the average capacity is 57% of the rated capacity, and the lead-acid storage batteries are not charged to 100% of the actual capacity. The storage battery pack has normal appearance and no physical damage.
Repairing the lead-acid storage battery by using a desulfurization high-frequency pulse activation instrument (the specification is 15 Ah-1000 Ah), wherein the repairing time is 2 hours, supplementing deionized water into the lead-acid storage battery after the repairing, and then standing the storage battery for 1 hour.
And step two, connecting the storage battery into a standard discharge detector for discharging, and then supplementing and charging for 6 hours according to a constant voltage 53.5V current limiting method.
And step three, connecting the storage battery into the standard discharge detector again for discharging, and then supplementing and charging for 8 hours according to a constant voltage 53.5V current limiting method.
And step four, repeating the step two and the step three until the actual charging capacity is not changed any more.
After the repair, the final battery capacity is repaired to 85% of the rated capacity.
The repairing effect of the prior art is far lower than the corresponding repairing effect of the method and the system, and the contribution of the method and the system to the prior art is further explained.
The above embodiments describe the electrochemical method and system for desulfurizing lead-acid storage battery in detail, and the description of the above embodiments is only used to help understand the method and idea of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.
Claims (13)
1. An electrochemical process for the desulfurization of lead acid batteries, said process comprising at least one charge-discharge cycle, the addition of Na containing compounds to the lead acid battery being carried out prior to the first said charge-discharge cycle2SO4And allowing the lead-acid storage battery to stand for a period of time; wherein, the charging process includes in proper order: a constant current stage, a constant voltage stage, a standing stage and a pulse current stage; wherein the lead-acid battery is charged to 100% of actual capacity prior to addition of the additive solution; wherein the additive solution contains Na2SO4The concentration of (A) is 1 to 5 wt%, and the addition amount thereof is 1.1 to 1.5mL/Ah based on the rated capacity of the storage battery.
2. The electrochemical process for desulfurizing a lead-acid battery according to claim 1, wherein said resting period of time is 8 to 15 hours.
3. The electrochemical method for desulfurizing a lead-acid storage battery according to claim 1, wherein in the constant current stage, a constant current of 0.1-0.2A/Ah is continuously applied for 4-7 hours according to the rated capacity of the battery.
4. An electrochemical process for the desulfurization of lead acid batteries according to claim 1, wherein a constant voltage of 2.4 to 2.7V is continuously applied for 4 to 6 hours in the constant voltage phase.
5. An electrochemical method for desulfurizing a lead-acid battery according to any one of claims 1 to 4, wherein in the constant current stage and the constant voltage stage, when the temperature of the battery electrolyte rises to a first temperature value, the application of the corresponding constant current or constant voltage is suspended, and when the temperature of the battery electrolyte is lower than a second temperature value, the application of the corresponding constant current or constant voltage is resumed, wherein the first temperature value is 50 to 55 ℃ and the second temperature value is 35 to 40 ℃.
6. The electrochemical process for desulfurizing a lead-acid battery of claim 5, the first temperature value being 55 ℃ and the second temperature value being 40 ℃.
7. The electrochemical process for desulfurizing a lead-acid battery according to claim 1, wherein the resting stage lasts for 1 to 2 hours and in which a constant voltage of 2.25 to 2.35V is applied to the battery when the temperature of the electrolyte is lower than a third temperature value, and the application of said voltage is stopped when the temperature of the electrolyte is higher than said third temperature value, wherein said third temperature value is 50 to 58 ℃.
8. The electrochemical process for desulfurizing a lead-acid battery of claim 7, the third temperature value being 55 ℃.
9. The electrochemical method for desulfurizing a lead-acid storage battery according to claim 1, wherein a pulse current is continuously applied for 2-4 hours in the pulse current stage, and the pulse current value is 30-70% of the current applied in the constant current stage.
10. The electrochemical method for desulfurizing a lead-acid storage battery of claim 9, wherein the pulse current has a period of 120-360 ms and a duty cycle of 1/2.
11. The electrochemical process of desulfurizing a lead-acid battery of claim 1, wherein the charge and discharge cycles are performed until the capacity of the lead-acid battery is restored to a desired capacity.
12. An electrochemical process for the desulfurization of lead acid batteries according to claim 11, wherein said charge-discharge cycle is carried out 4 to 6 times.
13. An electrochemical desulfurization system for a lead acid battery, the system comprising: a battery discharge device, a programmable battery charging device; wherein,
the battery discharging device is used for setting a repair expected value and standing time in the charging and discharging cycle process; and for connecting or disconnecting the electrical connection between the constant current load and the battery; and for connecting or disconnecting the electrical connection between the programmable battery charging apparatus and the battery; and for reading various electrochemical parameters of the cell with the sensor;
a programmable battery charging device, which is used for programming and setting parameters of current, voltage, preset temperature and time applied when the battery is charged by the programmable battery charging device, so that the current, voltage, preset temperature and time parameters can be set during charging to realize the constant current stage, the constant voltage stage, the standing stage and the pulse current stage of any one of the methods in claims 1-12.
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| CN101093905A (en) * | 2007-07-16 | 2007-12-26 | 陈玉涛 | Sulfuration restoration agent for lead acid battery |
| CN105098269A (en) * | 2014-05-23 | 2015-11-25 | 王惠民 | Repair and maintenance type charging method of lead-acid storage battery |
| CN105958592A (en) * | 2016-06-14 | 2016-09-21 | 深圳智慧能源技术开发有限公司 | Control device for charge and discharge machine, charge and discharge machine and control method |
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| CN101752615B (en) * | 2008-12-12 | 2014-04-02 | 成都鑫元帝科技有限公司 | Desulphurized high-frequency pulse activating instrument for battery recovery, activating agent and recovery process |
| CN101599559A (en) * | 2009-06-08 | 2009-12-09 | 陕西科技大学 | Desulphurization recovery technology for battery |
| CN102013534B (en) * | 2010-11-05 | 2013-05-08 | 江西省电力科学研究院 | Cathode protection-based valve control type lead-acid battery capacity activation solution |
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| CN101093905A (en) * | 2007-07-16 | 2007-12-26 | 陈玉涛 | Sulfuration restoration agent for lead acid battery |
| CN105098269A (en) * | 2014-05-23 | 2015-11-25 | 王惠民 | Repair and maintenance type charging method of lead-acid storage battery |
| CN105958592A (en) * | 2016-06-14 | 2016-09-21 | 深圳智慧能源技术开发有限公司 | Control device for charge and discharge machine, charge and discharge machine and control method |
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