CN109037819A - A kind of battery refresh liquid, regeneration method and application - Google Patents
A kind of battery refresh liquid, regeneration method and application Download PDFInfo
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- CN109037819A CN109037819A CN201810817496.XA CN201810817496A CN109037819A CN 109037819 A CN109037819 A CN 109037819A CN 201810817496 A CN201810817496 A CN 201810817496A CN 109037819 A CN109037819 A CN 109037819A
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- acid
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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
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The application provides a kind of battery refresh liquid, regeneration method and application.Battery refresh liquid provided by the present application includes organic acid stannous.Organic acid stannous in acid condition can be with the PbSO of inactivation4Complex reaction occurs, so that the PbSO of inactivation4Activity recovery, and then it is dissociated into Pb2+And SO4 2‑, charging process is completed, realizes the regeneration of lead-acid accumulator.Pass through the battery refresh liquid and regeneration method provided by the present application comprising organic acid stannous, the capacity resuming of the lead-acid accumulator of premature capacity loss is enabled to the 93.2-96% of nominal capacity, reaches the requirement that battery capacity is nominal capacity 80%.The regeneration of lead-acid accumulator improves the utilization rate of lead plaster, while also improving economic benefit, social benefit and environmental benefit.
Description
Technical field
The present invention relates to battery technology field more particularly to a kind of battery refresh liquid, regeneration method and application.
Background technique
Lead-acid accumulator is a kind of common battery, and electrode is made of lead and its oxide, and electrolyte is by sulfuric acid solution
Composition.Lead-acid accumulator with high security, good reliability, wide at low cost and working range the features such as, therefore, lead acid storage battery
Pond is a kind of important secondary power supply.
In use for some time, battery capacity decays lead-acid accumulator, causes it that design is not achieved using the time
The half in service life.Simultaneously as the difference of manufacture craft, the actual battery capacity of each lead-acid accumulator is different, and battery holds
The attenuation degree of amount is different.After the battery capacity of lead-acid accumulator decays to a certain degree, the lesser lead-acid accumulator of capacity
The requirement of user cannot be reached.At this point, the lesser lead-acid accumulator of capacity forms many refuse batteries, cause greatly to provide
Source waste.
In order to extend the service life of lead-acid accumulator, the lead-acid accumulator of premature capacity loss can be regenerated,
To achieve the purpose that restore battery capacity.Currently, most commonly seen lead-acid accumulator regeneration method is that low current high potential fills deeply
Circulation.Through practical proof, this method enables to the capacity restoration rate of lead-acid accumulator to reach 15-25%.But this is only to reality
Battery capacity is that the lead-acid accumulator of 70% or more design capacity works, and therefore, still has most lead-acid accumulator can not
Regeneration.
Summary of the invention
The present invention provides a kind of battery refresh liquid, regeneration method and application, to solve existing battery refresh method
The lower problem of capacity restoration rate.
Currently, lead-acid accumulator is usually by the brown lead oxide (PbO of anode2), the lead (Pb) and the dilute sulphur of electrolyte of cathode
Acid solution (H2SO4) composition.The reaction equation of the normal charge and discharge of lead-acid accumulator are as follows:
Charging: 2PbSO4+2H2O=PbO2+Pb+2H2SO4；
Electric discharge: PbO2+Pb+2H2SO4=2PbSO4+2H2O。
Lead-acid accumulator is in prolonged charge and discharge process, the PbSO of generation4Inactivation, i.e., PbSO in the charge state4No
Regenerate PbO2+Pb+2H2SO4.A large amount of inactivation PbSO4Generation cause the battery capacity of lead-acid accumulator to reduce, and then formed
Refuse battery.
For the service life for extending lead-acid accumulator, i.e., the battery capacity of the lead-acid accumulator of capacity attenuation is carried out extensive
Multiple, the application restores the battery capacity of the lead-acid accumulator of capacity attenuation by organic acid stannous.When organic acid stannous is added to
In the lead-acid accumulator of capacity attenuation, in the charge state, organic acid stannous enables to the PbSO of inactivation4Activity recovery, into
And realize PbSO4Dissociation, realize charging reaction.Organic acid stannous activates PbSO4Principle are as follows: organic acid stannous is in acid item
It can be with the PbSO of inactivation under part4Complex reaction occurs, so that the PbSO of inactivation4Activity recovery, and it is dissociated into Pb2+With
SO4 2-.As the PbSO of inactivation4Pb is dissociated under the action of organic acid stannous2+And SO4 2-Afterwards, Pb2+、SO4 2-And H2O is in charging shape
PbO is generated under state2, Pb and H2SO4, and then complete charging process.
The application passes through experimental verification and enables to early stage capacity to decline it is found that adding organic acid stannous in lead-acid accumulator
For the capacity resuming of the lead-acid accumulator subtracted to the 93.2-96% of nominal capacity, it is nominal hold that this, which complies fully with battery capacity,
The requirement of amount 80%.
It is used to restore the application of the battery capacity of the lead-acid accumulator of capacity attenuation corresponding to organic acid stannous, the application mentions
For a kind of battery refresh liquid, which includes organic acid stannous.In this application, organic acid stannous is organic acid
The substance constituted with stannous ion, such as carboxylic acid stannous, sulfonic acid stannous, sulfinic acid stannous, thionothiolic acid stannous, stannous sulfate, nitric acid
Stannous, phosphoric acid stannous chloride, chloric acid stannous or silicic acid stannous etc..
Since lead-acid accumulator is continuously generated the PbSO of inactivation during battery capacity reduces4, therefore, former plumbic acid stores
The electrolysis liquid hold-up of battery is constantly reduced.Since organic acid stannous in acid condition could be with the PbSO of inactivation4It is complexed
Reaction, therefore, for the generation for ensuring complex reaction, battery refresh liquid further includes dilution heat of sulfuric acid and water.
In the battery refresh liquid being made of organic acid stannous, dilution heat of sulfuric acid and water, organic acid stannous is in battery
Mass ratio in regenerated liquid is 0.2-1%.Mass ratio is that the organic acid stannous of 0.2-1% enables to the battery of lead-acid accumulator
Capacity restoration degree reaches higher level.
Further, according to the additional amount of organic acid stannous and water, to make the pH value and former plumbic acid storage in battery refresh liquid
The pH value of the electrolyte of battery is similar, and mass ratio of the dilution heat of sulfuric acid in battery refresh liquid is 0.8-1.5%.
To improve degree of the capacity resuming of lead-acid accumulator to nominal capacity, the application by battery refresh liquid
A kind of regeneration method of battery refresh liquid is also provided, this method comprises:
Battery refresh liquid comprising organic acid stannous is added in the lead-acid accumulator of capacity attenuation；
The lead-acid accumulator of the battery refresh liquid will be added in pulse width 5 seconds, pulse current 0.08C10A、
Stop trickle charge 48h under conditions of filling width 3 seconds；Wherein, 0.08C10A refers to that bulk charge stream is the 0.8/10 of battery capacity, i.e.,
80A electric current；
The lead-acid accumulator for charging electricity is continued in pulse current 0.01C10It charges, while extracting out more under conditions of A
The remaining battery refresh liquid；
After the extra battery refresh liquid exhausts, stop charging, stands 2h.
The plumbic acid of premature capacity loss is enabled to store by battery refresh liquid provided by the present application and regeneration method
The capacity resuming of battery, it is highest to restore to the 93.2-96% of nominal capacity.
The technical solution that the embodiment of the present invention provides can include the following benefits:
The application provides a kind of battery refresh liquid, regeneration method and application.Battery refresh liquid packet provided by the present application
Stannous containing organic acid.Organic acid stannous in acid condition can be with the PbSO of inactivation4Complex reaction occurs, so that inactivation
PbSO4Activity recovery, and then it is dissociated into Pb2+And SO4 2-, charging process is completed, realizes the regeneration of lead-acid accumulator.Pass through this
The battery refresh liquid and regeneration method comprising organic acid stannous provided is provided, the plumbic acid of premature capacity loss is enabled to
The capacity resuming of battery reaches the use that battery capacity is nominal capacity 80% and wants to the 93.2-96% of nominal capacity
It asks.The regeneration of lead-acid accumulator improves the utilization rate of lead plaster, while also improving economic benefit, social benefit and environmental protection effect
Benefit.
It should be understood that above general description and following detailed description be only it is exemplary and explanatory, not
It can the limitation present invention.
Detailed description of the invention
In order to illustrate more clearly of the technical solution of the application, letter will be made to attached drawing needed in the embodiment below
Singly introduce, it should be apparent that, for those of ordinary skills, without any creative labor,
It is also possible to obtain other drawings based on these drawings.
Fig. 1 is the flow diagram of the regeneration method of battery refresh liquid provided in an embodiment of the present invention.
Specific embodiment
Attached drawing 1 is please referred to, attached drawing 1 shows the process of the regeneration method of battery refresh liquid provided in an embodiment of the present invention
Schematic diagram.The description of following specific embodiments is based on attached drawing 1.
Embodiment 1
The embodiment of the present application provides a kind of battery refresh liquid, which includes organic acid stannous.Wherein, machine
Sour stannous be selected from carboxylic acid stannous, sulfonic acid stannous, sulfinic acid stannous, thionothiolic acid stannous, stannous sulfate, nitric acid stannous, phosphoric acid stannous chloride,
One of chloric acid stannous and silicic acid stannous.
Battery refresh liquid provided by the embodiments of the present application is used to restore the battery of the lead-acid accumulator of premature capacity loss
Capacity.
The embodiment of the present application also provides a kind of regeneration method of battery refresh liquid, and this method specifically includes:
S01: the battery refresh liquid comprising organic acid stannous is added in the lead-acid accumulator of capacity attenuation；
S02: the lead-acid accumulator of battery refresh liquid will be added in pulse width 5 seconds, pulse current 0.08C10A, stop to fill
Trickle charge 48h under conditions of width 3 seconds；
S03: the lead-acid accumulator for charging electricity is continued in pulse current 0.01C10It charges, while extracting out more under conditions of A
Remaining battery refresh liquid；
S04: after extra battery refresh liquid exhausts, stop charging, stand 2h.
Embodiment 2
The embodiment of the present application provides a kind of battery refresh liquid, which includes organic acid stannous, dilute sulfuric acid
Solution and water.Wherein, mass ratio of the organic acid stannous in battery refresh liquid is 0.2%.The selection of organic acid stannous refers to
Embodiment 1, but it is different from embodiment 1.
Battery refresh liquid provided by the embodiments of the present application is used to restore the battery of the lead-acid accumulator of premature capacity loss
Capacity.
The embodiment of the present application also provides a kind of regeneration method of battery refresh liquid, and this method please refers to embodiment 1.
Embodiment 3
The embodiment of the present application provides a kind of battery refresh liquid, which includes organic acid stannous, dilute sulfuric acid
Solution and water.Wherein, mass ratio of the organic acid stannous in battery refresh liquid is 1%；Bright sulfur acid in dilution heat of sulfuric acid exists
Mass ratio in battery refresh liquid is 0.8%.The selection reference implementation example 1 of organic acid stannous, but it is different from embodiment 1-2.
Battery refresh liquid provided by the embodiments of the present application is used to restore the battery of the lead-acid accumulator of premature capacity loss
Capacity.
The embodiment of the present application also provides a kind of regeneration method of battery refresh liquid, and this method please refers to embodiment 1.
Embodiment 4
The embodiment of the present application provides a kind of battery refresh liquid, which includes organic acid stannous, dilute sulfuric acid
Solution and water.Wherein, mass ratio of the organic acid stannous in battery refresh liquid is 0.5%；Bright sulfur acid in dilution heat of sulfuric acid
Mass ratio in battery refresh liquid is 1.5%.The selection reference implementation example 1 of organic acid stannous, but it is different from embodiment 1-
3。
Battery refresh liquid provided by the embodiments of the present application is used to restore the battery of the lead-acid accumulator of premature capacity loss
Capacity.
The embodiment of the present application also provides a kind of regeneration method of battery refresh liquid, and this method please refers to embodiment 1.
Embodiment 5
The embodiment of the present application provides a kind of battery refresh liquid, which includes organic acid stannous, dilute sulfuric acid
Solution and water.Wherein, mass ratio of the organic acid stannous in battery refresh liquid is 0.6%；Bright sulfur acid in dilution heat of sulfuric acid
Mass ratio in battery refresh liquid is 1%.The selection reference implementation example 1 of organic acid stannous, but it is different from embodiment 1-4.
Battery refresh liquid provided by the embodiments of the present application is used to restore the battery of the lead-acid accumulator of premature capacity loss
Capacity.
The embodiment of the present application also provides a kind of regeneration method of battery refresh liquid, and this method please refers to embodiment 1.
For the power of regeneration for verifying battery refresh liquid provided by the embodiments of the present application, the application use two comparative examples with
And embodiment 5 compares test.Wherein, comparative example 1 is deionized water；Comparative example 2 is that electrolyte and anhydrous sodium sulfate configure
Regenerated liquid；Test example is the battery refresh liquid that the embodiment of the present application 5 provides.Test content is specific as follows:
1, the configuration of regenerated liquid
Comparative example 1: deionized water.Take quality standard by the deionization of accumulator water professional standard JB/T10053-2010
Water.
Comparative example 2: the activating solution of electrolyte and anhydrous sodium sulfate configuration.It is pure using the reagent for meeting national standard GB4554-84
It is 1.30g/cm that the concentrated sulfuric acid, which is configured to apparent gravity,3Dilute sulfuric acid, obtain electrolyte.By configured electrolyte and anhydrous sodium sulfate
It is 99:1 mixing according to mass ratio, forms mixture.It is 1.05g/cm that mixture, which is diluted to apparent gravity with deionized water,3, obtain
To regenerated liquid.
Test example: the battery refresh liquid provided using the embodiment of the present application 5.
2, the determination of battery to be regenerated
The lead-acid accumulator of 24 capacity attenuations is chosen, and the battery capacity after decaying is relatively uniform.24 plumbic acids are stored
Battery is divided into three groups, and detects initial capacity of the every lead-acid accumulator before capacity restoration respectively.It is chosen in the application
The nominal capacity of 24 lead-acid accumulators is 500AH, and initial capacity is about 50% or so.The open circuit electricity of 24 lead-acid accumulators
Pressure, charging voltage, the data of 4h discharge voltage and 5h discharge voltage are as shown in table 1.
The open-circuit voltage of 1:24 lead-acid accumulator of table, charging voltage, the data of 4h discharge voltage and 5h discharge voltage
3, the addition of regenerated liquid
First group of lead-acid accumulator: opening emergency valve seat, with the inner cavity of flashlight irradiation lead-acid accumulator.Observe lead acid storage battery
The partition humidity in pond, humidity is with saturated aqueous best, it can be seen that the gloss of wet water.If there is the shape of water shortage in 8 lead-acid accumulators
Condition then adds the regenerated liquid that a small amount of comparative example 1 provides.It is unified that 100ml is added after observation partition water content is almost the same repeatedly
The regenerated liquid that comparative example 1 provides.At this point, interior depending on it can be seen that there is one layer of extra water to cover baffle surface.Safety valve is put on, is twisted
Tightly.Stick mark 1.~serial number 8..
Second group of lead-acid accumulator: according to the method for first group of lead-acid accumulator by 8 lead-acid accumulator moisturizings to partition
Water content is almost the same.Then 8 lead-acid accumulators are separately added into the regenerated liquid of the offer of 400ml comparative example 1.Put on pregnant solution kettle.
Stick mark (1)~(8) serial number.
Third group lead-acid accumulator: according to the method for first group of lead-acid accumulator by 8 lead-acid accumulator moisturizings to partition
Water content is almost the same.Then 8 lead-acid accumulators are separately added into the regenerated liquid of 400ml test example offer.Put on pregnant solution kettle.Patch
The serial number of upper (one)~(eight).
By three groups of lead-acid accumulators respectively connect formed three tunnels, every circuit respectively electric current be 30A, voltage 18V
Under the conditions of floating charge 2h, it is spare.
4, the activation of regenerated liquid
Second day after floating charge 2h, measure and record the open-circuit voltage of each lead-acid accumulator.Three groups of plumbic acids are stored respectively
Battery carries out charge test, and charging process is as follows:
First group of lead-acid accumulator: charge 48h under the conditions of electric current is 15A, voltage is 21.6V.Charging terminates preceding 5min
Inside measure and record the charging voltage of every lead-acid accumulator.After charging, continuation is filled under conditions of pulse current 10A
Electricity, while extracting the regenerated liquid that extra comparative example 1 provides out.After extra regenerated liquid exhausts, stop charging, stands 2h.
Second group of lead-acid accumulator: the first stage, charge 2h under conditions of electric current is 50A, voltage is 19.2V.Second
In the stage, discharge 4h under the conditions of electric current is 50A.Phase III, charge 20h under conditions of electric current is 50A, voltage is 19.2V.
Fourth stage, discharge 4h under the conditions of electric current is 50A.5th stage charged under conditions of electric current is 10A, voltage is 19.2V
18h.The charging voltage of every lead-acid accumulator is measured and recorded before the charging of 5th stage terminates in 5min.Stop charging, stands
2h。
Third group lead-acid accumulator: pulse width 5 seconds, pulse current 80A, stop and filling width 3 seconds under conditions of continuously fill
Electric 48h.After charging, continuation is charged under conditions of pulse current 10A, while extracting the electric power storage that extra test example provides out
Pond regenerated liquid.After extra battery refresh liquid exhausts, stop charging, stands 2h.
5, discharge test
Every battery in three groups of lead-acid accumulators is discharged 10h under conditions of electric current is 50A.In discharge process
In, since the 6th hour of electric discharge, the discharge voltage of every lead-acid accumulator is measured and recorded every 1h, until electric discharge knot
Beam or voltage drop to 1.8V.When the voltage of single battery of whole group lead-acid accumulator is below 1.8V, stop electric discharge.So
Afterwards, it is changed to the 12h that charges under the conditions of electric current is 10A, voltage is 19.2V.The voltage data of first group of lead-acid accumulator such as table 2,
The voltage data of second group of lead-acid accumulator such as table 3, the voltage data of third group lead-acid accumulator such as table 4.
The voltage data of 2: the first groups of lead-acid accumulators of table
The voltage data of 3: the second groups of lead-acid accumulators of table
Table 4: the voltage data of third group lead-acid accumulator
Data in analytical table 1-4 are it is found that the regenerated liquid and small electricity that first group of lead-acid accumulator is provided by adding comparative example 1
Flow depth fills overcharge after, the battery capacity of every lead-acid accumulator averagely improves 53.8AH, capacity restoration to nominal capacity
72.7%, but still it is not able to satisfy the requirement of 80% capacity.The regenerated liquid that second group of lead-acid accumulator is provided by adding comparative example 2
With three fill two put circulation after, the battery capacity of every lead-acid accumulator averagely improves 105.95AH, and capacity restoration holds to nominal
The 79.2% of amount, but still it is not able to satisfy the requirement of 80% capacity.Third group lead-acid accumulator provides again by adding test example
After raw liquid and pulse charge, the battery capacity of every lead-acid accumulator averagely improves 198.8AH, and capacity restoration has arrived nominal appearance
The 94.57% of amount, is entirely capable of using as spec battery.Thus, it is possible to illustrate, battery refresh provided by the embodiments of the present application
Liquid enables to the battery capacity of the lead-acid accumulator of capacity attenuation to be restored, and can be restored to the 93.2- of nominal capacity
96%, reach the requirement that battery capacity is nominal capacity 80%.In addition, the regeneration of lead-acid accumulator improves the benefit of lead plaster
With rate, while also improving economic benefit, social benefit and environmental benefit.
Those skilled in the art will readily occur to of the invention its after considering specification and the disclosure invented here of practice
Its embodiment.This application is intended to cover any variations, uses, or adaptations of the invention, these modifications, purposes or
Person's adaptive change follows general principle of the invention and including the undocumented common knowledge in the art of the present invention
Or conventional techniques.The description and examples are only to be considered as illustrative, and true scope and spirit of the invention are by following
Claim is pointed out.
It should be understood that the relational terms of such as " first " and " second " or the like be used merely to an entity or
Operation is distinguished with another entity or operation, and without necessarily requiring or implying between these entities or operation, there are any
This actual relationship or sequence.The present invention is not limited to the precise structure already described above and shown in the accompanying drawings,
And various modifications and changes may be made without departing from the scope thereof.The scope of the present invention is only limited by the attached claims
System.
Claims (7)
1. the battery capacity that organic acid stannous is used to restore the lead-acid accumulator of capacity attenuation.
2. application according to claim 1, which is characterized in that the 93.2- of the capacity resuming to nominal capacity
96%.
3. a kind of battery refresh liquid, which is characterized in that including organic acid stannous.
4. battery refresh liquid according to claim 3, which is characterized in that the organic acid stannous include carboxylic acid stannous,
Sulfonic acid stannous, sulfinic acid stannous, thionothiolic acid stannous, stannous sulfate, nitric acid stannous, phosphoric acid stannous chloride, chloric acid stannous or silicic acid stannous.
5. battery refresh liquid according to claim 3, which is characterized in that the battery refresh liquid further includes dilute sulfuric acid
Solution and water；Mass ratio of the organic acid stannous in the battery refresh liquid is 0.2-1%.
6. battery refresh liquid according to claim 5, which is characterized in that the bright sulfur acid in the dilution heat of sulfuric acid is in institute
Stating the mass ratio in battery refresh liquid is 0.8-1.5%.
7. a kind of regeneration method of battery refresh liquid characterized by comprising
Battery refresh liquid comprising organic acid stannous is added in the lead-acid accumulator of capacity attenuation；
The lead-acid accumulator of the battery refresh liquid will be added in pulse width 5 seconds, pulse current 0.08C10A, stop to fill
Trickle charge 48h under conditions of width 3 seconds；
The lead-acid accumulator for charging electricity is continued in pulse current 0.01C10Charge under conditions of A, at the same extract out it is extra
The battery refresh liquid；
After the extra battery refresh liquid exhausts, stop charging, stands 2h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111029664A (en) * | 2019-12-13 | 2020-04-17 | 国网山东综合能源服务有限公司 | Lead storage battery regeneration liquid and preparation method and regeneration method thereof |
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Application publication date: 20181218 |