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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- 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 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 present invention relates to the electrochemical method of a kind of battery recovery technique more particularly to a kind of lead-acid accumulator desulfurization and
System.
Background technique
With the development of lead-acid accumulator in recent years, large-scale valve-regulated sealed lead-acid batteries are with its closed construction, maintenance
Pressure is small, do not pollute ambient enviroment, is cheap, charge-discharge performance is good and using the significant advantages such as safe, becomes large capacity
The first choice of fixed battery, is widely used, such as the fields such as electric traction, energy stores in each field.But in the side of managing and maintaining
Face still has many problems, and sulfation is exactly wherein one more outstanding.Lead-acid accumulator has positive plate (titanium dioxide
Lead) and negative plate (lead).The charging process of battery is that the active material and electrolyte dilute sulfuric acid on pole plate chemically react
Come what is realized, its chemical energy is switched into electric energy.And lead-acid accumulator will form lead sulfate crystallization in electric discharge, when charging, can compare
Easily restore, if maintenance is proper, lead sulfate will not be attached on pole plate, even if having a small amount of attachment, in charging process
In, it can participate in electrochemical reaction, and be eliminated.But in the long-term use, or because of maintenance management in use
Be not good at, for example placed for a long time after insufficient, partial discharge of charging etc., cause lead sulfate that cannot normally be disappeared by charging process
It removes, thus will build up on electrode plate to form a kind of stable amorphous and be attached to battery pole plates surface.It is this
The charging of sulfuric acid leading crystal conventional method is difficult to eliminate, this process is exactly sulfation, often referred to simply as " is vulcanized ".With into
The placement of one step, these amorphous can be further transformed to crystal aggregates, be deposited on negative plate.Such crystal is poly-
Collective is coarse 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
It reduces, to cause gradually decreasing for battery capacity, seriously affects the charge-discharge performance and service life of lead-acid accumulator.
In fact, 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 be greatly energy saving and reduce pollution of the waste battery to environment, there is positive economy
And social benefit.
Currently, it is main to generate the method repaired after vulcanization early stage capacity reduction during lead-acid accumulator use both at home and abroad
Have: large current charge method, hydrotherapy, pulse reparation etc., but these methods to vulcanized lead-acid accumulator repairing effect simultaneously
It is unobvious.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of repair because of the lead-acid accumulator of capacity decline caused by vulcanizing
Method and system.
In order to achieve the above object, it is an aspect of the invention to provide a kind of electrochemistry sides of lead-acid accumulator desulfurization
Method, the method includes at least one charge and discharge cycles, before carrying out the charge and discharge cycles for the first time, in lead-acid accumulator
It is added and contains Na2SO4Additive solution, and allow lead-acid accumulator stand a period of time；Wherein, charging process includes: constant current rank
Section, stands stage and pulse current stage at constant-voltage phase.
Preferably, wherein the additive solution contains Na2SO4Concentration be 1wt%~5wt%, the volume based on battery
Constant volume, additive amount be 1.1~1.5mL/Ah, it is preferable that it is described stand a period of time when it is 8~15 hours a length of, it is more excellent
It is selected 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, the constant voltage of 4~6 hours 2.4~2.7V 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
When value, predetermined first temperature value is 50~55 DEG C, preferably 55 DEG C, then suspends and applies the corresponding constant current or described
Constant voltage, and when battery electrolyte temperature is lower than predetermined second temperature value, the predetermined second temperature value is 35 DEG C~40
DEG C, preferably 40 DEG C, restore 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 lower than predetermined
When third temperature, apply the constant voltage of 2.25~2.35V to battery, and when electrolyte temperature is higher than the predetermined third temperature
When, stopping applying the constant voltage, it is preferable that the predetermined third temperature is 50~58 DEG C, preferably 50~56 DEG C, most preferably
It is 55 DEG C.
Preferably, 2~4 hours pulse currents are continuously applied in the pulse current stage, the pulse current value is
30%~70%, preferably the 40%~60% of the applied electric current of constant-current phase, it is preferable that the period of the pulse current is
120~360ms, preferably 180~300ms, duty ratio 1/2.
Preferably, the method also includes: be added contain Na2SO4Additive solution before, first lead-acid accumulator is filled
Electricity is to the 100% of actual capacity.
Preferably, carry out the charge and discharge cycles until the lead-acid accumulator capacity restoration to expection capacity, for example,
The charge and discharge cycles carry out 2~10 times, it is preferable that and the charge and discharge cycles carry out 4~6 times, and 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 comprises: 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 being electrically connected between Constant Current Load and battery；With for connecting or cut off programmable battery charger
Being electrically connected between battery；With the various electrochemical parameters for reading battery using sensor；
Programmable battery charger, by programmable charging unit to battery charge when apply electric current, voltage,
Predetermined temperature, time parameter are programmed setting, for setting electric current in charging process, voltage, predetermined temperature, time parameter
It sets and can be realized constant-current phase described in any one of present invention method, constant-voltage phase, standing stage and pulse current stage.
The present invention program is when repairing lead-acid accumulator, by applying specific electric current, voltage to lead-acid accumulator, it may be assumed that
Constant current application, constant pressure apply, constant pressure pause applies and pulse current applies, and additive is added during the charging process, can disappear
Except those are deposited on the sulfuric acid leading crystal on pole plate, even having formed coarse hard crystal aggregates can also be effectively clear
It removes.Particularly preferably scheme has reached better effect.Therefore, the invention has the following beneficial effects:
1, effectively facilitated using the method for the present invention and system be deposited on electrode plate sulfuric acid leading crystal disintegration and again
It is dissolved into electrolyte.Average size of the lead-acid accumulator after method desulfurization of the invention can increase the 90% of rated capacity
More than, such as 92% or more, preferably 97% or more or even 99% to 100%.Make the capacity restoration of lead-acid accumulator to close to its
Rated capacity.
2, it has been effectively relieved since scrapping in advance for lead-acid accumulator is polluted to environment bring, has saved resource, it can
Bring huge economic benefit and social benefit.
3, method of the invention it is easily operated and promote, system of the invention can automated execution desulfurization operations, use
It is convenient and simple.
Detailed description of the invention
Fig. 1 is the process signal for applying electric current, voltage when charging the battery according to one embodiment of the present invention
Figure；
Fig. 2 is according to one embodiment of the present invention, the flow diagram of the electrochemical method of lead-acid accumulator desulfurization；
Fig. 3 is method according to the present invention, the schematic diagram of the composed structure of lead-acid accumulator desulphurization system；
Fig. 4 is to carry out desulfurization according to one embodiment of the present invention to lead-acid accumulator using system of the invention and put
The schematic diagram of electricity；
Fig. 5 is to carry out desulfurization according to one embodiment of the present invention to lead-acid accumulator using system of the invention and fill
The schematic diagram of electricity；
Fig. 6 is according to one embodiment of the present invention, and the waveform of the voltage and current applied when charging the battery shows
It is intended to；
Fig. 7 is the numerical value change figure of battery group 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 the electric discharge of battery group element cell averag density
Numerical value change figure；
Figure 10 is the maximum according to the embodiment of the present invention 2, in repair process at the end of the electric discharge of battery group between element cell
Voltage difference numerical value change figure；
Figure 11 is according to the embodiment of the present invention 2, and 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
Degree value variation diagram.
Specific embodiment
Due to lead sulfate on electrode plate crystallization cause capacity of lead acid battery to decline aiming at the problem that, the present invention provides
A kind of electrochemical method and system of lead-acid accumulator desulfurization.Come below according to a kind of preferred embodiment of the invention specific
Illustrate method and system of the invention.By following explanation, further advantages and improvements of the invention be will become clearer.
It will be understood by those skilled in the art that following implementation is merely to illustrate the present invention so that those skilled in the art are easy
In understanding, rather than it is used to limit the scope of the invention.
Fig. 2 shows a kind of embodiment according to the present invention, the process 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 the charge and discharge cycles for starting to carry out to repair battery it
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
Add the dissolution of agent infiltration internal storage battery and substance.It 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
Agent is added to contain the sodium sulfate salt that can form competition electrochemical reaction with lead.Added sodium sulphate is with concentration in 1wt%~5wt%
Between, the aqueous solution form addition preferably between 2wt~4wt%.Its additive amount 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 determine according to the actual situation.Usually at 8~15 hours,
For example, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours etc..Additive can be allowed sufficiently to infiltrate by standing
Internal storage battery, and pass through the PbSO on series reaction decomposed electrode plate4Crystal.
Then desulfurization process is carried out to lead-acid accumulator with lead-acid accumulator desulphurization system of the invention.
Desulphurization system of the invention includes discharging device and programmable battery charger.Referring to Fig. 3, wherein showing
Meaning property shows desulphurization system of the invention.
Discharging device 31, can time of repose (including electric discharge to repairing during desired value and charge and discharge cycles
Time of repose after time of repose, charging afterwards) it is configured.On the one hand it is used for the electric discharge of battery, is on the other hand also served as at desulfurization
The controller of reason.Specifically for connecting or cutting off the control being electrically connected between Constant Current Load and battery；It is also used to connect or cut
The control being electrically connected between disconnected programmable battery charger 32 and battery；It is also used to read each of battery using sensor
Kind electrochemical parameter.
Programmable battery charger 32, electric current, the electricity applied when being charged by programmable charging unit to battery
The parameters such as pressure, predetermined temperature (including predetermined first temperature, predetermined second temperature, predetermined third temperature), time, which are programmed, to be set
Set, after programmable battery charger is connected to battery to be repaired, make electric current in charging process, voltage, predetermined temperature, when
Between setting can be realized 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.
The embodiment shown according to fig. 2 then carries out step 202, starts the discharge process of battery.Referring to fig. 4, when
When executing electric discharge, discharging device 41 makes to keep between programmable battery charger 42 and lead-acid accumulator to be repaired
It disconnects, while discharging device carries out the discharge process of battery by allowing battery to be repaired to connect constant current load.
After electric discharge, step 203, electric discharge pause are executed.After completing electric discharge, discharging device stops working and cuts off
It discharges a period of time with the pause that is electrically connected of battery to be processed, to make battery temperature drop to 40 DEG C down toward environment temperature.
It is usually related to battery capacity, environment temperature etc. to suspend the discharge period.Such as it may last about 3 hours.During disconnection,
Discharging device executes the reading operation of battery electrochemical parameter using sensor, and reading includes cell voltage, battery electrolysis
The data of liquid density, battery capacity etc..
Then step 204 is executed, process is started to charge.Referring to Fig. 5, when executing charging, discharging device 51 will be to
It repairs battery and is connected to programmable battery charger 52, as shown in Figure 5.Programmable battery charger 52 executes program
Start the charging process of battery.
A kind of exemplary electrostatic electric process according to the present invention is as shown in figures 1 to 6.Fig. 1 is method pair according to the present invention
Apply the flow diagram of electric current, voltage when battery is charged.Fig. 6 be according to one embodiment of the present invention, to battery into
The waveform diagram of the voltage and current applied when row charging.
First stage: i.e. step 101, constant-current charging phase.Programmable battery charger is in this stage with constant
Electric current charges the battery.Different starting constant currents is used for different rated capacities, electric current is according to battery rated capacity
It is determined according to 0.1~0.2A/Ah.In the constant-current charging phase, the lead sulfate that has just generated is but molten there are no accumulative crystallization
Solution in the electrolytic solution, meanwhile, cell voltage and internal resistance reach highest, and solar panel starts to generate heat.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
A constant voltage, the numberical range of voltage are 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 expands and makes crystal
A part automatically starts to dissolve.This stage sustainable 4~6 hours.
In the first stage and the second stage, if the temperature of battery electrolyte rises to predetermined first temperature
Value, making a reservation for the first temperature value is 50~55 DEG C, such as 51 DEG C, 52 DEG C, 55 DEG C etc., preferably 55 DEG C, then suspends and applies corresponding institute
Constant current or the constant voltage are stated, is radiated when necessary with electric fan to battery, until temperature is lower than predetermined second temperature
Angle value, predetermined second temperature value are 35 DEG C~40 DEG C, such as 36 DEG C, 38 DEG C etc., preferably 40 DEG C, recover immediately and apply corresponding institute
State constant current or the constant voltage.The lead plaster on battery electrode plate can be prevented during the charging process due to relatively high in this way
The comprehensive function of mild 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
Set state.When battery electrolyte temperature is higher than predetermined third temperature value, without any processing；It is only pre- lower than this when temperature
When determining third temperature value, just apply a such as 2.25V~2.35V constant low-voltage, for prevent electrolyte stratification and
Keep the temperature of electrolyte；Just stop the application of voltage when temperature rises to predetermined third temperature value.Predetermined third temperature
Usually 50~70 DEG C of value, such as 55 DEG C, 58 DEG C, 60 DEG C, 65 DEG C etc., preferably 55 DEG C.Electrolyte is allowed to remain one in this way
Determine temperature, electrolyte is made to continue to do minimum vertical movement to prevent to be layered, this stage sustainable 1~2 hour.
Fourth stage, i.e. step 104, pulse current charge stage.At this stage, programmable battery charger is kept
The current impulse of a period of time.These pulse currents increase local temperature on electrode plate, and the place of this high temperature will increase
The solubility of lead sulfate, and the lead sulfate of deposition is made to generate further expansion, cause crystal to be disintegrated.This stage (T4) continues
2~4 hours.Pulse current magnitude is that constant current applies the 30%~70% of stage current size.Pulse period is 120~360ms,
Preferably 180~300ms, duty ratio 1/2.
After charging through the above four-stage, discharging device cuts off programmable battery charger and plumbic acid stores
Electrical connection between battery, enters step 205.
Step 205 executes charging pause.During the charging pause, discharging device executes 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 influenced 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
It is worth, such as 90% or more be restored to rated capacity, such as 92% or more, preferably 97% or more.If the electric power storage being repaired
The average size in pond has reached or has been more than desired value, then terminates desulfurization process；If desired value has not been reached yet, repeat
Step 202 is then completed to repair to step 205 until capacity resuming to desired value.
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 the above embodiment.
According to preferred embodiment, method of the invention can make the capacity reparation of lead storage battery arrive rated capacity
92% or more, even up to close to rated capacity.Typically, for service life in 5 to 10 years, actual capacity is had declined
To for the 50~70% of rated capacity battery, by repeating 3~7 times, preferably 4~6 above-mentioned charge and discharge cycles, so that it may make
Capacity restoration to rated capacity 92% or more.
Effect of the invention is further illustrated below by 4 specific embodiments.
Embodiment 1:
As general embodiments, with method and system of the invention to one group of GFM-500 lead-acid accumulator for communication
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 battery group appearance is normal, no physical damage, with system and method for the 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
The aqueous sodium persulfate solution that concentration is 6wt% is added in the amount of 0.5mL/Ah, allows battery standing 7 hours.And it is charged by programmable
Electric current that device applies when charging to battery, voltage, predetermined temperature (including predetermined first temperature, predetermined second temperature, predetermined the
Three temperature), the parameters 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 reparation desired value, to reflect that each embodiment method is repaired comprehensively in Examples 1 to 3
Technical effect situation).
Then the lead-acid batteries desulphurization system of the invention is connected to start to carry out charge and discharge cycles.
Firstly, the electric discharge device of desulphurization system is discharged by making battery connect Constant Current Load, kept during electric discharge
Programmable battery charger is in an off state with battery.Discharge current is 50A.
After electric discharge, the cutting of the electric discharge device of desulphurization system is electrically connected with battery, placement about 3 hours.During this period
Measure cell voltage, battery electrolyte density, battery capacity.
When battery temperature drops to 35 DEG C, start to charge.The electric discharge device of desulphurization system is electric by battery and programmable
Pond charging unit is connected.Programmable battery charger starts to charge to lead-acid accumulator according to the program set.
Charging procedure according to the present invention, firstly, starting the first stage of constant-current charge, with the constant current (electric current of 34A
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, (voltage swing is with the constant voltage of 2.5V
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 is suspended if the electrolyte temperature of battery rises to 55 DEG C or more and applies the constant current and constant voltage, necessary
When radiated with the mode of such as electric fan etc to battery, until temperature be lower than 40 DEG C, recover immediately apply it is described constant
Electric current and constant voltage.After constant-voltage phase, start to stand the phase III, does not apply Current Voltage and stand 1 hour, in this phase
Between, if temperature is lower than 55 DEG C, apply 2.15V voltage, be higher than 55 DEG C to temperature, stops Current Voltage immediately and apply, allow electricity
Pond returns to static condition.Finally, starting the phase III of execution pulse current charge, pulse loading cycle is 100ms, duty ratio
The pulse current (being the Common Parameters in such battery impulse charging in the prior art) for being 40.8A for 1/2, size carries out arteries and veins
It rushes electric current to charge 3 hours, this pulse current stage voltage keeps 2.3V.
Then the electric discharge device of desulphurization system cuts off programmable battery charger and being electrically connected between battery, stands 3
Hour, so that battery temperature is reduced to 35 DEG C between environment temperature.During this period, discharging device measurement cell voltage,
Battery electrolyte density, battery capacity etc..
Above charge and discharge cycles are repeated to carry out altogether 6 times, the battery capacity after recycling for each time is respectively as follows: 60%, 69%,
80%, 89%, 93%, 93%.
Repaired, the performance of the lead-acid batteries is obviously improved.The group after being repaired using the method for the present invention and system
After measured, properties are as shown in table 1 below, and (according to national standard YD/T799-2010, " the valve controlling sealed lead of communication stores battery
Battery " and accumulator testing specification requirements measurement): 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 accumulator testing specification requirements.
Embodiment 2:
As a preferred embodiment, also another group of GFM-500 plumbic acid for communication is stored with method and system of the invention
Battery has carried out desulfurization reparation and test.Communication lead-acid accumulator, model GFM-500, one group includes 24 element cells,
Voltage rating and nominal capacity are 2V/500Ah, and average life is 7 years, and average actual capacity is the 57% of rated capacity,
It is uncharged to the 100% of actual capacity, the battery group appearance is normal, no physical damage, with system and method for the 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
The aqueous sodium persulfate solution that concentration is 2wt% is added in the amount of 1.2mL/Ah, allows battery standing 10 hours.And it is charged by programmable
Electric current that device applies when charging to battery, voltage, predetermined temperature (including predetermined first temperature, predetermined second temperature, predetermined the
Three temperature), the parameters 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 lead-acid batteries desulphurization system of the invention is connected to start to carry out charge and discharge cycles.
Firstly, the electric discharge device of desulphurization system is discharged by making battery connect Constant Current Load, kept during electric discharge
Programmable battery charger is in an off state with battery.Discharge current is 50A.
After electric discharge, the cutting of the electric discharge device of desulphurization system is electrically connected with battery, placement about 3 hours.During this period
Electric discharge device measures the parameters such as cell voltage, battery electrolyte density, battery capacity.
When battery temperature drops to 35 DEG C, start to charge.The electric discharge device of desulphurization system is electric by battery and programmable
Pond charging unit is connected.Programmable battery charger starts to charge to lead-acid accumulator according to the program set.
Charging procedure according to the present invention (is pressed firstly, starting the first stage of constant-current charge with the constant current of 77A
0.154A/Ah applies) it charges the battery 5 hours, cell voltage reaches 2.6V.Then start the second stage of constant-voltage charge, with
The constant voltage charging of 2.6V 6 hours.In above-mentioned first stage and second stage, if the electrolyte temperature of battery rises to 55 DEG C
More than, then suspend and apply the constant current and constant voltage, is radiated when necessary with electric fan to battery, until temperature is low
In 40 DEG C, recovers immediately and apply the constant current and constant voltage.After constant-voltage phase, start to stand the phase III, no
Apply Current Voltage and stand 1 hour, during this period, if temperature is lower than 55 DEG C, apply 2.25V voltage, is higher than 55 to temperature
DEG C, stop Current Voltage immediately and apply, battery is allowed to return to static condition.Finally, starting the third rank of execution pulse current charge
Section, the pulse current that pulse loading cycle is 360ms, duty ratio 1/2, size are 39A carry out pulse current charge 3 hours,
This pulse current stage voltage keeps 2.3V.
Then the electric discharge device of desulphurization system cuts off programmable battery charger and being electrically connected between battery, stands 3
Hour, so that battery temperature is reduced to 35 DEG C between environment temperature.During this period, discharging device measurement cell voltage,
Battery electrolyte density, battery capacity etc..
It repeats the 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
The requirements measurement of family standard YD/T799-2010 " communicating valve controlling sealed lead storage battery " and accumulator testing specification).
Its practical battery capacity respectively reaches rated cell capacity: 62%, 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 method for the present invention and system
Properties are as shown in table 2 below (according to national standard YD/T799-2010 " the valve controlling sealed lead electric power storage of communication after measured for battery
Pond " and accumulator testing specification requirements measurement): 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 accumulator testing specification requirements.
Embodiment 3:
As a comparison case, another group of GFM500 lead-acid accumulator for communication is carried out with method and system of the invention
Desulfurization reparation and test, but without addition metabisulfite solution, be contrasted with embodiment 1.Communication lead-acid accumulator, type
It number is GFM500, one group includes 24 element cells, and voltage rating and nominal capacity are 2V/500Ah, average life 7
Year, average actual capacity is the 57% of rated capacity, and uncharged to the 100% of actual capacity, the battery group appearance is normal,
Without physical damage, desulfurization process is carried out to it with system and method for the invention.
The electric current that applies when being charged by programmable charging unit to battery, voltage, predetermined temperature (including predetermined first
Temperature, predetermined second temperature, predetermined third temperature), the parameters such as time be programmed setting, and by discharging device to filling
Time of repose parameter during electric discharge pause is configured.
Then the lead-acid batteries desulphurization system of the invention is connected to start to carry out charge and discharge cycles.
Firstly, the electric discharge device of desulphurization system is discharged by making battery connect Constant Current Load.It is kept during electric discharge
Programmable battery charger is in an off state with battery.Discharge current is 50A.
After electric discharge, the cutting of the electric discharge device of desulphurization system is electrically connected with battery, placement about 3 hours.During this period
Measure cell voltage, battery electrolyte density, battery capacity.
When battery temperature drops to 35 DEG C, start to charge.The electric discharge device of desulphurization system is electric by battery and programmable
Pond charging unit is connected.Programmable battery charger starts to charge to lead-acid accumulator according to the program set.
Charging procedure according to the present invention, firstly, starting the first stage of constant-current charge, with the constant current of 77A to electricity
Pond is charged 5 hours, and cell voltage reaches 2.6V.Then start the second stage of constant-voltage charge, with the constant voltage charging 6 of 2.6V
Hour.Suspend described in application in above-mentioned first stage and second stage if the electrolyte temperature of battery rises to 55 DEG C or more
Constant current and constant voltage when necessary radiate to battery with electric fan, until temperature be lower than 40 DEG C, recover immediately application
The constant current and constant voltage.After constant-voltage phase, start to stand the phase III, it is small not apply Current Voltage standing 1
When, during this period, if temperature is lower than 55 DEG C, apply 2.25V voltage, is higher than 55 DEG C to temperature, stops Current Voltage immediately
Apply, battery is allowed to return to static condition.Finally, starting the phase III of execution pulse current charge, pulse loading cycle is
The pulse current that 360ms, duty ratio 1/2, size are 39A carries out pulse current charge 3 hours, this pulse current stage electricity
Pressure keeps 2.3V.
Then the electric discharge device of desulphurization system cuts off programmable battery charger and being electrically connected between battery, stands 3
Hour, so that battery temperature is reduced to 35 DEG C between environment temperature.During this period, it is close that cell voltage, battery electrolyte are measured
Degree, internal resistance, battery capacity.
The above charge and discharge cycles carry out 6 times altogether, the battery capacity after each circulation is respectively as follows: 57%, 75%, 82%,
85%, 86%, 86%.
After measured, properties are as shown in table 3 below: table 3
Embodiment 4
As a comparison case, with a kind of GFM500 plumbic acid that pulse restorative procedure is used to communicate to another group in 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 voltage rating and nominal capacity are 2V/500Ah, and average life is 7 years, average size
It is the 57% of rated capacity, it is uncharged to the 100% of actual capacity.The battery group appearance is normal, no physical damage.
Step 1 repairs lead-acid accumulator 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 battery is allowed to stand
1 hour.
Battery access standard discharge detector is discharged, is then supplemented by constant pressure 53.5V current-limiting method by step 2
Charging 6 hours.
Battery access standard discharge detector is discharged again, then presses constant pressure 53.5V current-limiting method by step 3
Boost charge 8 hours.
Step 4 repeats step 2 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 the prior art, which is far below, repairs corresponding effect using the method for the present invention and system, further illustrates
Present contribution to the art.
Above embodiments carry out the electrochemical method and system of a kind of lead-acid accumulator desulfurization provided by the present invention
It is discussed in detail, method and its thought of the invention that the above embodiments are only used to help understand；Simultaneously for this field
Those skilled in the art, according to the thought of the present invention, there will be changes in the specific implementation manner and application range, to sum up
Described, the contents of this specification are not to be construed as limiting the invention.
Claims (13)
1. a kind of electrochemical method of lead-acid accumulator desulfurization, the method includes at least one charge and discharge cycles, head is being carried out
Before the secondary charge and discharge cycles, it is added in lead-acid accumulator and contains Na2SO4Additive solution, and lead-acid accumulator is allowed to stand
For a period of time；Wherein, charging process successively includes: constant-current phase, constant-voltage phase, standing stage and pulse current stage；Wherein,
Before adding the additive solution, first by the 100% of the lead acid battery charge to actual capacity；Wherein, described to add
Add agent solution containing Na2SO4Concentration be 1wt%~5wt%, the rated capacity based on battery, additive amount be 1.1~
1.5mL/Ah。
2. the electrochemical method of lead-acid accumulator desulfurization according to claim 1, it is described stand 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 the constant current of 4~7 hours 0.1~0.2A/Ah.
4. the electrochemical method of lead-acid accumulator desulfurization according to claim 1, wherein persistently applied in the constant-voltage phase
Add the constant voltage of 4~6 hours 2.4~2.7V.
5. the electrochemical method of lead-acid accumulator desulfurization according to any one of claims 1 to 4, wherein in the constant current
It is corresponding constant then to suspend application when the temperature of battery electrolyte rises to the first temperature value for stage and the constant-voltage phase
Electric current or constant voltage, and when battery electrolyte temperature is lower than second temperature value, restore to apply the corresponding constant current
Or the constant voltage, wherein first temperature value is 50~55 DEG C, and the second temperature value is 35 DEG C~40 DEG C.
6. the electrochemical method of lead-acid accumulator desulfurization according to claim 5, first temperature value is 55 DEG C, described
Second temperature value is 40 DEG C.
7. the electrochemical method of lead-acid accumulator desulfurization according to claim 1, wherein the standing stage continues 1~2
Hour, and apply the perseverance of 2.25~2.35V to battery when electrolyte temperature is lower than third temperature value in the standing stage
Constant voltage, and when electrolyte temperature is higher than the third temperature value, stop applying the voltage, wherein the third temperature
Value is 50~58 DEG C.
8. the electrochemical method of lead-acid accumulator desulfurization according to claim 7, the third temperature value is 55 DEG C.
9. 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 apply the 30%~70% of electric current by the constant-current phase.
10. the electrochemical method of lead-acid accumulator desulfurization according to claim 9, the period of the pulse current is 120
~360ms, duty ratio 1/2.
11. the electrochemical method of lead-acid accumulator desulfurization according to claim 1, wherein carry out the charge and discharge cycles
Until the lead-acid accumulator capacity restoration to expection capacity.
12. the electrochemical method of lead-acid accumulator desulfurization according to claim 11, the charge and discharge cycles carry out 4~6
It is secondary.
13. a kind of Electrochemistry Desulfurization system for lead-acid accumulator, the system comprises: 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；Be used for
Being electrically connected between connection or cutting Constant Current Load and battery；With for connect or cut off programmable battery charger and electricity
Electrical connection between pond；With the various electrochemical parameters for reading battery using sensor；
Programmable battery charger, the electric current applied when being charged by programmable charging unit to battery, make a reservation for voltage
Temperature, time parameter are programmed setting, for enabling the setting of electric current in charging process, voltage, predetermined temperature, time parameter
It enough realizes constant-current phase described in any one of claim 1-12 method, constant-voltage phase, stand stage and pulse current stage.
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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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