CN107123835A - The electrochemical method and system of a kind of lead-acid accumulator desulfurization - Google Patents
The electrochemical method and system of a kind of lead-acid accumulator desulfurization Download PDFInfo
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- CN107123835A CN107123835A CN201710365429.4A CN201710365429A CN107123835A CN 107123835 A CN107123835 A CN 107123835A CN 201710365429 A CN201710365429 A CN 201710365429A CN 107123835 A CN107123835 A CN 107123835A
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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
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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
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
- H01M10/44—Methods for charging or discharging
- H01M10/446—Initial charging measures
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- 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
Abstract
The invention discloses a kind of electrochemical method of lead-acid accumulator desulfurization, methods described includes at least one charge and discharge cycles, before the charge and discharge cycles first are carried out, and is added in lead-acid accumulator and contains 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 system of lead-acid accumulator Electrochemistry Desulfurization.The present invention can be repaired the lead-acid accumulator that capacity declines caused by vulcanization, capacity of lead acid battery is recovered to more than the 90% of its rated capacity.
Description
Technical field
The present invention relates to a kind of battery recovery technique, more particularly to a kind of lead-acid accumulator desulfurization electrochemical method and
System.
Background technology
With the development of lead-acid accumulator in recent years, large-scale valve-regulated sealed lead-acid batteries with its closed construction, safeguard
Pressure is small, do not pollute surrounding environment, cheap, charge-discharge performance is good and uses the significant advantages such as safety, as Large Copacity
The first choice of self-contained battery, is widely used in each field, such as the field such as electric traction, energy stores.But in management and maintenance side
Face still has many problems, and sulfation is exactly wherein than more prominent one.Lead-acid accumulator has positive plate (titanium dioxide
Lead) and negative plate (lead).The charging process of battery is that the active material on pole plate chemically reacts with electrolyte dilute sulfuric acid
Come what is realized, its chemical energy is switched into electric energy.And lead-acid accumulator can form lead sulfate crystallization in electric discharge, it can compare during charging
Easily reduce, if maintenance is proper, lead sulfate will not be attached on pole plate, even if or have a small amount of attachment, in charging process
In, it can participate in electrochemical reaction, and be eliminated.But during long-term use, or because of maintenance management in use
It is not good at, such as long-term placement etc., causes lead sulfate normally to be disappeared by charging process after insufficient, partial discharge of charging
Remove, thus will build up on battery lead plate to form a kind of amorphous of stabilization and be attached to battery pole plates surface.It is this
It is difficult to eliminate that sulfuric acid leading crystal conventional method, which charges, and this process is exactly sulfation, often referred to simply as " is vulcanized ".With entering
The placement of one step, these amorphous can be further transformed to crystal aggregates, be deposited on negative plate.Such crystal gathers
Collective is thick hard, is more difficult to eliminate.
Vulcanization does not only result in that electrode plate surface crystallization resistance is big, electric conductivity is deteriorated, also results in the active material of battery
Reduce, so as to cause gradually decreasing for battery capacity, have a strong impact on the charge-discharge performance and service life of lead-acid accumulator.
In fact, the problem of all there is above-mentioned vulcanization in about 80% lead-acid accumulator scrapped.If it is possible to repair
The lead-acid accumulator vulcanized, will greatly save the energy and reduces pollution of the waste battery to environment, there is positive economy
And social benefit.
At present, to produce the method repaired after the capacity reduction of vulcanization early stage during use main for domestic and international lead-acid accumulator
Have：Large current charge method, hydrotherapy, pulse repair etc., but these methods to vulcanized lead-acid accumulator repairing effect simultaneously
It is unobvious.
The content of the invention
In order to solve the above problems, the present invention provides the lead-acid accumulator that a kind of capacity repaired caused by vulcanization declines
Method and system.
In order to achieve the above object, it is an aspect of the invention to provide a kind of electrochemistry side of lead-acid accumulator desulfurization
Method, methods described includes at least one charge and discharge cycles, before the charge and discharge cycles first are carried out, in lead-acid accumulator
Add and contain Na2SO4Additive solution, and allow lead-acid accumulator stand a period of time；Wherein, charging process includes：Constant current rank
Section, constant-voltage phase, standing stage and pulse current stage.
Preferably, wherein, the additive solution contain Na2SO4Concentration be 1wt%~5wt%, the volume based on battery
Constant volume, its addition be 1.1~1.5mL/Ah, it is preferable that described standing a period of time when a length of 8~15 hours, it is more excellent
Elect as 10-13 hours.
Preferably, in the constant-current phase, it is continuously applied 4~7 hours 0.1~0.2A/Ah's according to battery rated capacity
Constant current.
Preferably, 4~6 hours 2.4~2.7V constant voltage is continuously applied in the constant-voltage phase.
Preferably, when the temperature of the constant-current phase or the constant-voltage phase battery electrolyte rises to predetermined first temperature
During value, predetermined first temperature value is 50~55 DEG C, and preferably 55 DEG C, then pause applies the corresponding constant current or described
Constant voltage, and when battery electrolyte temperature is less than predetermined second temperature value, the predetermined second temperature value is 35 DEG C~40
DEG C, preferably 40 DEG C, recover to apply the corresponding constant current or the constant voltage.
Preferably, the standing stage continues 1~2 hour, and in the standing stage, when electrolyte temperature is less than predetermined
During three temperature, apply 2.25~2.35V constant voltage to battery, and when electrolyte temperature is higher than predetermined 3rd temperature
When, stop applying the constant voltage, it is preferable that the 3rd temperature that makes a reservation for is 50~58 DEG C, preferably 50~56 DEG C, most preferably
For 55 DEG C.
Preferably, the pulse current of 2~4 hours is continuously applied in the pulse current stage, the pulse current value is
The constant-current phase applies the 30%~70% of electric current, preferably 40%~60%, it is preferable that the cycle of the pulse current is
120~360ms, preferably 180~300ms, dutycycle is 1/2.
Preferably, methods described also includes：Contain Na adding2SO4Additive solution before, first lead-acid accumulator is filled
Electricity is to the 100% of actual capacity.
Preferably, the charge and discharge cycles are carried out until the capacity restoration of the lead-acid accumulator is to expection capacity, for example,
The charge and discharge cycles are carried out 2~10 times, it is preferable that the charge and discharge cycles are carried out 4~6 times, such as 4,5,6 times.
Another aspect of the present invention is to provide a kind of with according to the corresponding lead acid storage battery of any one of claim 1~9 method
The system of pond Electrochemistry Desulfurization, the system includes：Discharging device, programmable battery charger；Wherein,
Discharging device, for being configured to the time of repose during reparation desired value and charge and discharge cycles；With
For connecting or cutting off the electrical connection between Constant Current Load and battery；With for connecting or cutting off programmable battery charger
Electrical connection between battery；With the various electrochemical parameters for reading battery using sensor；
Programmable battery charger, the electric current applied when being charged by programmable charging device to battery, voltage,
Predetermined temperature, time parameter are programmed setting, for setting electric current in charging process, voltage, predetermined temperature, time parameter
Constant-current phase, constant-voltage phase, standing stage and the pulse current stage described in any one of present invention method can be realized by putting.
The present invention program is when repairing lead-acid accumulator, by applying specific electric current, voltage to lead-acid accumulator, i.e.,：
Constant current application, constant pressure apply, constant pressure pause applies and pulse current applies, and add additive in charging process, can disappear
The sulfuric acid leading crystal on pole plate is deposited on except those, even having formed thick hard crystal aggregates can also be effectively clear
Remove.Particularly preferably scheme, has reached more preferable effect.Therefore, the present invention has the advantages that：
1st, effectively facilitated using the inventive method and system be deposited on battery lead plate sulfuric acid leading crystal disintegration and again
It is dissolved into electrolyte.Average size of the lead-acid accumulator after the method desulfurization of the present invention can increase to the 90% of rated capacity
More than, such as more than 92%, preferably more than 97%, or even 99% to 100%.Make the capacity restoration of lead-acid accumulator to close to its
Rated capacity.
2nd, effectively alleviate and the pollution brought to environment is scrapped due to lead-acid accumulator in advance, saved resource, can
Bring huge economic benefit and social benefit.
3rd, method of the invention is easily operated and promotes, system of the invention can automated execution desulfurization operations, use
It is convenient and simple.
Brief description of the drawings
Fig. 1 is the flow signal for applying electric current, voltage when being charged according to one embodiment of the present invention to battery
Figure；
Fig. 2 is according to one embodiment of the present invention, the schematic flow sheet of the electrochemical method of lead-acid accumulator desulfurization；
Fig. 3 is the method according to the present invention, the schematic diagram of the composition structure of lead-acid accumulator desulphurization system；
Fig. 4 is, according to one embodiment of the present invention, to carry out desulfurization to lead-acid accumulator using the system of the present invention and put
The schematic diagram of electricity；
Fig. 5 is, according to one embodiment of the present invention, to carry out desulfurization to lead-acid accumulator using the system of the present invention and fill
The schematic diagram of electricity；
Fig. 6 is that the waveform of the voltage and current applied when being charged to battery shows according to one embodiment of the present invention
It is intended to；
Fig. 7 is the numerical value change figure of batteries actual capacity in repair process according to the embodiment of the present invention 2；
Fig. 8 be according to the embodiment of the present invention 2, in repair process at the end of battery charging element cell average voltage
Numerical value change figure；
Fig. 9 be according to the embodiment of the present invention 2, in repair process at the end of batteries electric discharge element cell averag density
Numerical value change figure；
Figure 10 is the maximum in repair process at the end of batteries electric discharge between element cell according to the embodiment of the present invention 2
Voltage difference numerical value change figure；
Figure 11 is that according to the embodiment of the present invention 2, battery charging reaches the charging capacity before 2.4V in repair process
Numerical value change figure；
Figure 12 be according to the embodiment of the present invention 1, in repair process at the end of battery charging element cell it is average close
Number of degrees value changes figure.
Embodiment
For causing the problem of capacity of lead acid battery declines because lead sulfate is crystallized on battery lead plate, the invention provides
The electrochemical method and system of a kind of lead-acid accumulator desulfurization.A kind of below according to the present invention preferred embodiment comes specific
Illustrate the method and system of the present invention.By following explanation, further advantages and improvements of the invention will become clearer.
It will be understood by those skilled in the art that implementation below is merely to illustrate the present invention so that those skilled in the art are easy
In understanding, rather than for limiting the scope of the present invention.
Fig. 2 shows that, according to one embodiment of the present invention, the flow of the electrochemical method of lead-acid accumulator desulfurization is shown
It is intended to.Referring to Fig. 2, method of the invention may include step 201~206.
In step 201, according to the preferred embodiment of the present invention, can proceed by repair battery charge and discharge cycles it
It is preceding by the 100% of battery initial charge to actual capacity, charge to actual capacity 100% can make battery heat up, and promote to add
Plus the dissolving of agent infiltration internal storage battery and material.Certainly, can be first if battery has charged to the 100% of actual capacity
The 100% of actual capacity is recharged to after electric discharge.Additive is then added in battery, and stands a period of time.It is described to add
Plus agent contain can with lead formation competition electrochemical reaction sodium sulfate salt.The sodium sulphate added is with concentration in 1wt%~5wt%
Between, the aqueous solution form addition preferably between 2wt~4wt%.Its addition can be according to the rated capacity of battery come really
It is fixed, e.g., about 1.1~1.5mL/Ah.Battery time of repose can be determined according to actual conditions.Generally at 8~15 hours,
For example, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours etc..By standing additive can be allowed fully to infiltrate
Internal storage battery, and pass through the PbSO on series reaction decomposed battery lead plate4Crystal.
Then desulfurization process is carried out to lead-acid accumulator with the lead-acid accumulator desulphurization system of the present invention.
The desulphurization system of the present invention includes discharging device and programmable battery charger.Referring to Fig. 3, wherein showing
Meaning property shows the desulphurization system of the present invention.
Discharging device 31, can be to repairing time of repose (including the electric discharge during desired value and charge and discharge cycles
Afterwards time of repose, charging after time of repose) be configured.On the one hand it is used for the electric discharge of battery, on the other hand also serves as at desulfurization
The controller of reason.Control specifically for connecting or cutting off the electrical connection between Constant Current Load and battery；It is additionally operable to connect or cuts
The control of electrical connection between disconnected programmable battery charger 32 and battery；It is additionally operable to read each of battery using sensor
Plant electrochemical parameter.
Programmable battery charger 32, the electric current applied when being charged by programmable charging device to battery, electricity
The parameters such as pressure, predetermined temperature (including predetermined first temperature, predetermined second temperature, predetermined 3rd temperature), time, which are programmed, to be set
Put, after programmable battery charger is connected to battery to be repaired, make electric current in charging process, voltage, predetermined temperature, when
Between setting can realize constant-current phase described below, constant-voltage phase, standing stage and pulse current stage, for plumbic acid store
The charging of battery.
Above-mentioned relevant parameter is set by discharging device and programmable battery charger.
Embodiment according to Fig. 2, then carries out step 202, starts the discharge process of battery.Referring to Fig. 4, when
When performing electric discharge, discharging device 41 makes to keep between programmable battery charger 42 and lead-acid accumulator to be repaired
Disconnect, while discharging device carries out the discharge process of battery by allowing battery to be repaired to connect constant current load.
After electric discharge terminates, step 203, electric discharge pause are performed.Complete after electric discharge, discharging device is stopped and cut off
Electrical connection pause electric discharge a period of time with pending battery, to make battery temperature drop to less than 40 DEG C to environment temperature.
Suspend the discharge period generally related to battery capacity, environment temperature etc..For example it may last about 3 hours.During disconnecting,
Discharging device performs the reading operation of battery electrochemical parameter using sensor, and reading includes cell voltage, battery electrolysis
The data of liquid-tight degree, battery capacity etc..
Then step 204 is performed, process is started to charge up.Referring to Fig. 5, when performing charging, discharging device 51 will be treated
Repair battery and be connected to programmable battery charger 52, as shown in Figure 5.The configuration processor of programmable battery charger 52
Start the charging process of battery.
According to a kind of exemplary electrostatic electric process of the present invention as shown in figures 1 to 6.Fig. 1 is the method pair according to the present invention
Apply electric current, the schematic flow sheet of voltage when battery is charged.Fig. 6 is, according to one embodiment of the present invention, battery to be entered
The waveform diagram of the voltage and current applied during row charging.
First stage：That is step 101, constant-current charging phase.Programmable battery charger is with constant in this stage
Electric current charges the battery.Different starting constant currents is used for different rated capacities, electric current is according to battery rated capacity
Determined according to 0.1~0.2A/Ah.In the constant-current charging phase, the also no accumulative crystallization of the lead sulfate just generated, but it is molten
Solution in the electrolytic solution, meanwhile, cell voltage and internal resistance reach highest, and cell panel starts heating.This process typically lasts for 4~7
Hour (T1).
Second stage, i.e. step 102, constant voltage charging phase.Programmable battery charger keeps one in this stage
Individual constant voltage, the number range of voltage is 2.4~2.7V.This stage continues sufficiently long a period of time (T2), until
Overcharge factor is sufficiently large for actual capacity.In this stage, the violent heating of pole plate, expansion simultaneously cause crystal
A part independently starts dissolving.Sustainable 4~6 hours of this stage.
In the first stage and the second stage, if the temperature of battery electrolyte rises to predetermined first temperature
Value, it is 50~55 DEG C to make a reservation for the first temperature value, such as 51 DEG C, 52 DEG C, 55 DEG C, preferably 55 DEG C, then pause applies corresponding institute
Constant current or the constant voltage are stated, battery is radiated with electric fan if necessary, until temperature is less than predetermined second temperature
Angle value, predetermined second temperature value is 35 DEG C~40 DEG C, such as 36 DEG C, 38 DEG C, preferably 40 DEG C, recovers to apply corresponding institute immediately
State constant current or the constant voltage.It can so prevent the lead plaster on battery electrode plate in charging process due to relatively high
The comprehensive function of gentle electricity is destroyed.
Phase III, i.e. step 103, stand the stage.In lasting a period of time (T3) in the stage, battery is in relatively quiet
Configuration state.When battery electrolyte temperature is higher than predetermined three temperature value, without any processing；Only when temperature is pre- less than this
During fixed three temperature value, just one such as 2.25V~2.35V of application constant low-voltage, for prevent electrolyte stratification and
Keep the temperature of electrolyte；Just stop the application of voltage when temperature rises to predetermined three temperature value.Predetermined 3rd temperature
Value is usually 50~70 DEG C, such as 55 DEG C, 58 DEG C, preferably 60 DEG C, 65 DEG C etc., 55 DEG C.So electrolyte is allowed to remain one
Constant temperature degree, makes electrolyte continue to do minimum vertical motion to prevent to be layered, sustainable 1~2 hour of this stage.
Fourth stage, i.e. step 104, pulse current charge stage.In the stage, programmable battery charger is kept
The current impulse of a period of time.These pulse currents make it that local temperature is raised on battery lead plate, and the place of this high temperature can increase
The solubility of lead sulfate, and the lead sulfate of deposition is produced further expansion, cause crystal to be disintegrated.This stage (T4) continues
2~4 hours.Pulse current size is that constant current applies the 30%~70% of stage current size.Pulse period is 120~360ms,
Preferably 180~300ms, dutycycle is 1/2.
After charging through above four-stage, discharging device cut-out programmable battery charger stores with plumbic acid
Electrical connection between battery, into step 205.
Step 205 performs charging pause.During the charging pause, discharging device performs reading behaviour using sensor
Make, the data of reading include：The parameters such as cell voltage, battery electrolyte density, battery capacity.Through the stage, the temperature of battery
Gradually decrease to environment temperature.The duration in the stage is influenceed and different by battery capacity, ambient conditions, and about 3 is small
When.
By above step 202~205, then a charge and discharge cycles are completed.In step 206, discharging device
According to the battery capacity parameters read in step 205, judge whether the average size of battery to be repaired has reached expection
Value, for example, returned to more than the 90% of rated capacity, such as more than 92%, preferably more than 97%.If the electric power storage being repaired
The average size in pond has met or exceeded desired value, then terminates desulfurization process；If being also not reaching to desired value, repeat
Step 202 is to step 205, until capacity resuming to desired value, then completes to repair.
Only illustrate one embodiment of the present invention in an illustrative manner above, and those skilled in the art are, it should be understood that originally
Invention is not limited to above-mentioned embodiment.
According to preferred embodiment, method of the invention can make the capacity reparation of lead accumulator arrive rated capacity
More than 92%, even up to close to rated capacity.Typically, for service life in 5 to 10 years, actual capacity has declined
To for the 50~70% of rated capacity battery, by repeating 3~7 times, preferably 4~6 times above-mentioned charge and discharge cycles, so that it may make
Capacity restoration to rated capacity more than 92%.
The effect of the present invention is further illustrated below by 4 specific embodiments.
Embodiment 1：
As general embodiments, it is used for the GFM-500 lead-acid accumulators of communication to one group with the method and system of the present invention
Desulfurization reparation and test are carried out.Communication lead-acid accumulator, model GFM-500, one group includes 24 element cells, specified
Voltage and nominal capacity are 2V/500Ah, and average life is 9 years, and average actual capacity is the 53% of rated capacity, not
The 100% of actual capacity is charged to, the batteries outward appearance is normal, no physical damage, with the system and method for the present invention to it
Carry out desulfurization process.
In advance by above-mentioned lead-acid batteries initial charge to the 100% of actual capacity, in its electrolyte according to
0.5mL/Ah amount adds the aqueous sodium persulfate solution that concentration is 6wt%, allows battery standing 7 hours.And charged by programmable
Electric current that device applies when being charged to battery, voltage, predetermined temperature (including predetermined first temperature, predetermined second temperature, predetermined the
Three temperature), the parameter such as time be programmed setting, the time of repose during charge and discharge electronic pause is joined by discharging device
Number is configured (not to be configured, to reflect that each embodiment method is repaired comprehensively in embodiment 1~3 to repairing desired value
Technique effect situation).
Then the desulphurization system for the lead-acid batteries being connected into the present invention proceeds by charge and discharge cycles.
First, the electric discharge device of desulphurization system is discharged by making battery connect Constant Current Load, is kept during electric discharge
Programmable battery charger is off with battery.Discharge current is 50A.
After electric discharge terminates, the electric discharge device cut-out and the electrical connection of battery of desulphurization system are placed about 3 hours.During this period
Determine cell voltage, battery electrolyte density, battery capacity.
When battery temperature drops to 35 DEG C, start to charge up.The electric discharge device of desulphurization system is electric by battery and programmable
Pond charging device is connected.Programmable battery charger starts to charge to lead-acid accumulator according to the program set.
According to the charging procedure of the present invention, first, start the first stage of constant-current charge, with 34A constant current (electric current
Size is the 1/15 of rated capacity, is the Common Parameters in the prior art in such battery constant-current charge) charge the battery it is 5 small
When, cell voltage reaches 2.6V.Then start the second stage of constant-voltage charge, using 2.5V constant voltage (voltage swing as
2.5V, is the Common Parameters in the prior art in such battery constant-voltage charge) charging 6 hours.In above-mentioned first stage and
Two-stage, if the electrolyte temperature of battery rises to more than 55 DEG C, pause applies the constant current and constant voltage, necessary
When battery is radiated with the mode of such as electric fan etc, until temperature be less than 40 DEG C, immediately recover apply it is described constant
Electric current and constant voltage.After constant-voltage phase terminates, start to stand the phase III, do not apply Current Voltage and stand 1 hour, in this phase
Between, if temperature is less than 55 DEG C, apply 2.15V voltages, treat that temperature is higher than 55 DEG C, stop Current Voltage immediately and apply, allow electricity
Pond returns to static condition.Finally, the phase III of execution pulse current charge is started, pulse loading cycle is 100ms, dutycycle
The pulse current for being 40.8A for 1/2, size (being the Common Parameters in such battery impulse charging in the prior art) carries out arteries and veins
Rush electric current to charge 3 hours, this pulse current stage voltage keeps 2.3V.
Then the electrical connection between the electric discharge device cut-out programmable battery charger and battery of desulphurization system, stands 3
Hour, so that battery temperature is reduced to 35 DEG C between environment temperature.During this period, discharging device determine cell voltage,
Battery electrolyte density, battery capacity etc..
Repeat above charge and discharge cycles to carry out altogether 6 times, the battery capacity after each circulation is respectively：60%th, 69%,
80%th, 89%, 93%, 93%.
Repaired, the performance of the lead-acid batteries is obviously improved.The group after being repaired using the inventive method and system
After measured, properties are as shown in table 1 below (according to national standard YD/T799-2010 for battery《Communication is stored with valve controlling sealed lead
Battery》And the requirements of accumulator testing specification are determined)：Table 1：
Every detection is carried out to this group storage battery after reparation, meets national standard YD/T799-2010《Communication valve
Control formula sealed lead accumulator》And the requirements of accumulator testing specification.
Embodiment 2：
As the presently preferred embodiments, also another group of GFM-500 plumbic acid for being used to communicate is stored with the method and system of the present invention
Battery has carried out desulfurization reparation and test.Communication lead-acid accumulator, model GFM-500, one group includes 24 element cells,
Rated voltage and nominal capacity are 2V/500Ah, and average life is 7 years, and average actual capacity is the 57% of rated capacity,
Uncharged to the 100% of actual capacity, the batteries outward appearance is normal, no physical damage, with the system and method for the present invention
Desulfurization process is carried out to it.
In advance by above-mentioned lead-acid batteries initial charge to the 100% of actual capacity, in its electrolyte according to
1.2mL/Ah amount adds the aqueous sodium persulfate solution that concentration is 2wt%, allows battery standing 10 hours.And charged by programmable
Electric current that device applies when being charged to battery, voltage, predetermined temperature (including predetermined first temperature, predetermined second temperature, predetermined the
Three temperature), the parameter such as time be programmed setting, the time of repose during charge and discharge electronic pause is joined by discharging device
Number is configured.
Then the desulphurization system for the lead-acid batteries being connected into the present invention proceeds by charge and discharge cycles.
First, the electric discharge device of desulphurization system is discharged by making battery connect Constant Current Load, is kept during electric discharge
Programmable battery charger is off with battery.Discharge current is 50A.
After electric discharge terminates, the electric discharge device cut-out and the electrical connection of battery of desulphurization system are placed about 3 hours.During this period
Electric discharge device determines the parameters such as cell voltage, battery electrolyte density, battery capacity.
When battery temperature drops to 35 DEG C, start to charge up.The electric discharge device of desulphurization system is electric by battery and programmable
Pond charging device is connected.Programmable battery charger starts to charge to lead-acid accumulator according to the program set.
According to the charging procedure of the present invention, first, start the first stage of constant-current charge, (pressed with 77A constant current
0.154A/Ah applies) charge the battery 5 hours, cell voltage reaches 2.6V.Then the second stage of constant-voltage charge is started, with
2.6V constant-potential charge 6 hours.In above-mentioned first stage and second stage, if the electrolyte temperature of battery rises to 55 DEG C
More than, then pause applies the constant current and constant voltage, battery is radiated with electric fan if necessary, until temperature is low
In 40 DEG C, recover to apply the constant current and constant voltage immediately.After constant-voltage phase terminates, start to stand the phase III, no
Apply Current Voltage and stand 1 hour, during this period, if temperature is less than 55 DEG C, apply 2.25V voltages, treat that temperature is higher than 55
DEG C, stop Current Voltage immediately and apply, allow battery to return to static condition.Finally, the 3rd rank of execution pulse current charge is started
Section, pulse loading cycle is that 360ms, dutycycle are that the pulse current that 1/2, size is 39A carries out pulse current charge 3 hours,
This pulse current stage voltage keeps 2.3V.
Then the electrical connection between the electric discharge device cut-out programmable battery charger and battery of desulphurization system, stands 3
Hour, so that battery temperature is reduced to 35 DEG C between environment temperature.During this period, discharging device determine cell voltage,
Battery electrolyte density, battery capacity etc..
Repeat above charge and discharge cycles to carry out altogether 5 times, the battery performance after each circulation refers to Fig. 7~12 (according to state
Family standard YD/T799-2010《Valve controlling sealed lead accumulator is used in communication》And the requirements of accumulator testing specification are determined).
Its actual battery capacity respectively reaches rated cell capacity：62%th, 73%, 88%, 92%, 98% (referring to Fig. 7).
Repaired, the performance of the lead-acid batteries is obviously improved.The group after being repaired using the inventive method and system
Properties are as shown in table 2 below (according to national standard YD/T799-2010 after measured for battery《Communicate with valve controlling sealed lead electric power storage
Pond》And the requirements of accumulator testing specification are determined)：Table 2：
Every detection is carried out to this group storage battery after reparation, meets national standard YD/T799-2010《Communication valve
Control formula sealed lead accumulator》And the requirements of accumulator testing specification.
Embodiment 3：
As a comparison case, another group of GFM500 lead-acid accumulator for being used to communicate is carried out with the method and system of the present invention
Desulfurization reparation and test, but do not add metabisulfite solution, it is contrasted with embodiment 1.Communication lead-acid accumulator, type
Number it is GFM500, one group includes 24 element cells, and rated voltage and nominal capacity are 2V/500Ah, and average life is 7
Year, average actual capacity is the 57% of rated capacity, and uncharged to the 100% of actual capacity, the batteries outward appearance is normal,
Without physical damage, desulfurization process is carried out to it with the system and method for the present invention.
The electric current that applies when being charged by programmable charging device to battery, voltage, predetermined temperature (including predetermined first
Temperature, predetermined second temperature, predetermined 3rd temperature), the parameter such as time be programmed setting, and by discharging device to filling
Time of repose parameter during electric discharge pause is configured.
Then the desulphurization system for the lead-acid batteries being connected into the present invention proceeds by charge and discharge cycles.
First, the electric discharge device of desulphurization system is discharged by making battery connect Constant Current Load.Kept during electric discharge
Programmable battery charger is off with battery.Discharge current is 50A.
After electric discharge terminates, the electric discharge device cut-out and the electrical connection of battery of desulphurization system are placed about 3 hours.During this period
Determine cell voltage, battery electrolyte density, battery capacity.
When battery temperature drops to 35 DEG C, start to charge up.The electric discharge device of desulphurization system is electric by battery and programmable
Pond charging device is connected.Programmable battery charger starts to charge to lead-acid accumulator according to the program set.
According to the charging procedure of the present invention, first, start the first stage of constant-current charge, with 77A constant current to electricity
Pond is charged 5 hours, and cell voltage reaches 2.6V.Then the second stage of constant-voltage charge is started, with 2.6V constant-potential charge 6
Hour.In above-mentioned first stage and second stage, if the electrolyte temperature of battery rises to more than 55 DEG C, pause applies described
Constant current and constant voltage, are radiated with electric fan to battery if necessary, until temperature is less than 40 DEG C, recover to apply immediately
The constant current and constant voltage.After constant-voltage phase terminates, start to stand the phase III, do not apply Current Voltage standing 1 small
When, during this period, if temperature is less than 55 DEG C, apply 2.25V voltages, treat that temperature is higher than 55 DEG C, stop Current Voltage immediately
Apply, allow battery to return to static condition.Finally, the phase III of execution pulse current charge is started, pulse loading cycle is
360ms, dutycycle are that the pulse current that 1/2, size is 39A carries out pulse current charge 3 hours, this pulse current stage electricity
Pressure keeps 2.3V.
Then the electrical connection between the electric discharge device cut-out programmable battery charger and battery of desulphurization system, stands 3
Hour, so that battery temperature is reduced to 35 DEG C between environment temperature.During this period, cell voltage, battery electrolyte are determined close
Degree, internal resistance, battery capacity.
Above charge and discharge cycles are carried out 6 times altogether, and the battery capacity after each circulation is respectively：57%th, 75%, 82%,
85%th, 86%, 86%.
After measured, properties are as shown in table 3 below：Table 3
Embodiment 4
As a comparison case, it is used for the GFM500 plumbic acids of communication to another group with a kind of pulse restorative procedure of the prior art
Battery has carried out desulfurization reparation and test, to illustrate advantages of the present invention.Communication lead-acid accumulator, model GFM500,
One group includes 24 element cells, and rated voltage and nominal capacity are 2V/500Ah, and average life is 7 years, average size
It is uncharged to the 100% of actual capacity for the 57% of rated capacity.The batteries outward appearance is normal, no physical damage.
Step one, lead-acid accumulator is repaiied using desulphurized high-frequency pulse activating instrument (specification is 15Ah~1000Ah)
Multiple, repair time is 2 hours, after above-mentioned reparation, deionized water is supplemented in lead-acid accumulator, then allows battery to stand
1 hour.
Step 2, battery access standard discharge detector is discharged, then supplemented by constant pressure 53.5V current-limiting methods
Charging 6 hours.
Step 3, is again discharged battery access standard discharge detector, then by constant pressure 53.5V current-limiting methods
Boost charge 8 hours.
Step 4, repeat step two and three, until charging actual capacity no longer changes.
It is repaired, final battery capacity reparation to the 85% of rated capacity.
The repairing effect of prior art is far below repairs corresponding effect using the inventive method and system, further illustrates
Present contribution to the art.
Above example is carried out to the electrochemical method and system of a kind of lead-acid accumulator desulfurization provided by the present invention
It is discussed in detail, the explanation of above example is only intended to the method and its thought for helping to understand the present invention；Simultaneously for this area
Those skilled in the art, according to the present invention thought, will change in specific embodiments and applications, to sum up
Described, this specification content should not be construed as limiting the invention.
Claims (10)
1. a kind of electrochemical method of lead-acid accumulator desulfurization, methods described includes at least one charge and discharge cycles, head is being carried out
Before the secondary charge and discharge cycles, added in lead-acid accumulator and contain Na2SO4Additive solution, and allow lead-acid accumulator to stand
For a period of time；Wherein, charging process includes：Constant-current phase, constant-voltage phase, standing stage and pulse current stage.
2. the electrochemical method of lead-acid accumulator desulfurization according to claim 1, wherein, the additive solution contains
Na2SO4Concentration be 1wt%~5wt%, the rated capacity based on battery, its addition be 1.1~1.5mL/Ah, preferably
Ground, described standing a period of time when a length of 8~15 hours.
3. the electrochemical method of lead-acid accumulator desulfurization according to claim 1, wherein, in the constant-current phase, according to
Battery rated capacity is continuously applied 4~7 hours 0.1~0.2A/Ah constant current.
4. the electrochemical method of lead-acid accumulator desulfurization according to claim 1, wherein, persistently applied in the constant-voltage phase
Plus 4~6 hours 2.4~2.7V constant voltage.
5. the electrochemical method of the lead-acid accumulator desulfurization according to any one of Claims 1 to 4, wherein, in the constant current
Stage and the constant-voltage phase, when the temperature of battery electrolyte rises to the first temperature value, then pause applies corresponding described
Constant current or the constant voltage, and when battery electrolyte temperature is less than second temperature value, recover to apply corresponding described
Constant current or the constant voltage, wherein, first temperature value is 50~55 DEG C, preferably 55 DEG C, the second temperature value
For 35 DEG C~40 DEG C, preferably 40 DEG C.
6. the electrochemical method of lead-acid accumulator desulfurization according to claim 1, wherein, the standing stage continues 1~2
Hour, and in the standing stage, when electrolyte temperature is less than three temperature values, apply 2.25~2.35V perseverance to battery
Determine voltage, and when electrolyte temperature is higher than three temperature value, stop applying the voltage, wherein, the 3rd temperature
It is worth for 50~58 DEG C, preferably 55 DEG C.
7. the electrochemical method of lead-acid accumulator desulfurization according to claim 1, wherein, held in the pulse current stage
The continuous pulse current for applying 2~4 hours, the pulse current value is applied the 30%~70% of electric current by the constant-current phase,
Preferably, the cycle of the pulse current is 120~360ms, and dutycycle is 1/2.
8. the electrochemical method of lead-acid accumulator desulfurization according to claim 1, wherein, methods described also includes：Adding
Before entering the additive solution, first by the 100% of lead acid battery charge to actual capacity.
9. the electrochemical method of lead-acid accumulator desulfurization according to claim 1, wherein, carry out the charge and discharge cycles straight
Capacity restoration to the lead-acid accumulator arrives expected capacity, it is preferable that the charge and discharge cycles progress 4~6 times.
10. a kind of Electrochemistry Desulfurization system for lead-acid accumulator, the system includes：Discharging device, programmable
Battery charger；Wherein,
Discharging device, for being configured to the time of repose during reparation desired value and charge and discharge cycles；With for
Electrical connection between connection or cut-out Constant Current Load and battery；With for connect or cut off programmable battery charger with electricity
Electrical connection between pond；With the various electrochemical parameters for reading battery using sensor；
Programmable battery charger, it is the electric current applied when being charged by programmable charging device to battery, voltage, predetermined
Temperature, time parameter are programmed setting, the setting for enabling electric current in charging process, voltage, predetermined temperature, time parameter
Enough realize constant-current phase, constant-voltage phase, standing stage and the pulse current stage described in any one of claim 1-9 method.
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