CN105280963B - The method and its lead-acid accumulator of a kind of lead-acid accumulator anacidity tank formation - Google Patents
The method and its lead-acid accumulator of a kind of lead-acid accumulator anacidity tank formation Download PDFInfo
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- CN105280963B CN105280963B CN201510592667.XA CN201510592667A CN105280963B CN 105280963 B CN105280963 B CN 105280963B CN 201510592667 A CN201510592667 A CN 201510592667A CN 105280963 B CN105280963 B CN 105280963B
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- lead
- electrolyte
- acid
- anacidity
- acid accumulator
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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
- H01M10/06—Lead-acid accumulators
- H01M10/12—Construction or manufacture
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a kind of method of lead-acid accumulator anacidity tank formation and its lead-acid accumulator, in chemical conversion electrolyte sulfuric acid is instead of with neutral electrolyte, acid mist pollution is prevented, avoid traditional tank formation pole plate and rinse the lead waste water produced, formation efficiency, pole plate quality are better than internal formation process simultaneously, and the spent acid without internal formation process process is produced, reach not only energy-saving and emission-reduction but also improve the purpose of product quality.
Description
Technical field
The present invention relates to lead-acid accumulator, more particularly to a kind of energy-saving and emission-reduction, environmental protection, the lead acid storage battery for improving product quality
The method and its lead-acid accumulator of pond anacidity tank formation.
Background technology
Environmental is protected and the policy of labor protection is constantly put into effect（For example：《Lead-acid accumulator industry access condition》
Middle regulation, the battery manufacturers for starting for 2013 to found the factory need to use internal formation process）, it is meant that lead-acid storage battery production enterprise gives birth to
The formulation of production. art should meet environment-friendly requirement.No matter use and be internalized into or alienation during existing storage battery production
Into technique, the problem of there is open chemical conversion, battery opening chemical conversion has meant that substantial amounts of acid mist is produced, and influences environment.
, it is necessary to be swashed both positive and negative polarity material inside pole plate by certain charge and discharge system in the manufacturing process of battery
It is living, it is changed into state-of-charge, this chemical reaction process of the combination property such as the charge-discharge performance of improvement battery and self discharge, storage
Referred to as chemical synthesis technology process, container formation is, by green plate assembled batteries, after the completion of assembling, to add dilute sulfuric acid, chargingization
Into the conversion for making green plate is positive/negative plate material.
Lead-acid accumulator is widely used in national economy, and the life production with the people contacts close, indispensable, but its
Also widely disease is dirty for problem of environmental pollution present in manufacturing process, and especially traditional pole plate tank formation technique can not only be produced
A large amount of acid mists, and chemical conversion after-ripening pole plate flushing can also produce flood tide lead waste water, and therefore, the technique give stricts orders time limit by country
Terminate（The end of the year 2015）, the substitute is container formation technique.However, although internal formation process is conducive to environmental protection, but simultaneously
Do not save, relative to tank formation, formation charging amount increase by more than 50%, pole plate is melted into quality also not as good as tank formation, in fact, outside
The disabled of chemical conversion is because of environmental issue, rather than technical problem.
China Patent Publication No. CN101459258A, publication date on June 17th, 2009, entitled lead-acid accumulator is internalized into
Reverse charge chemical synthesis technology, this application case discloses a kind of internal chemical synthetic reverse charging chemical process for lead acid battery, including lead acid storage battery
The acid filling or encapsulating step and charge step in pond, after the completion of acid filling or encapsulating step and before charge step, are carried out anti-to battery
To charging.It is disadvantageous in that although internal formation process is conducive to environmental protection, but does not save, and relative to tank formation, chemical conversion is filled
Electricity increase by more than 50%, pole plate is melted into quality also not as good as tank formation.
The content of the invention
The purpose of the present invention is that traditional dilute sulfuric acid tank formation technique is substituted with anacidity tank formation technique, has prevented acid mist dirty
Dye, it is to avoid pole plate produces the lead waste water rinsed, while formation efficiency, pole plate quality are better than internal formation process, and does not have
The spent acid of internal formation process process is produced, and is reached not only energy-saving and emission-reduction but also is improved the purpose of product quality.
To achieve these goals, the present invention uses following technical scheme：
Electrolyte is neutral electrolyte, neutral electrolyte in a kind of method of lead-acid accumulator anacidity tank formation, electrolytic bath
Electrolyte be inorganic salts, solvent is deionized water, and the mass fractions of inorganic salts is also to add organic resistance in 1-50%, electrolyte
Solvent.In the technical program, anacidity pole plate tank formation is not only produced without acid mist and lead waste water, and without tradition
Tank formation or the reaction for being internalized into sulfuric acid at initial stage and lead oxide effect generation lead sulfate, therefore chemical conversion electricity only has theoretical capacity
1.1-1.5 times, less than 1.5-2 times of traditional sulfuric acid tank formation technique, also it is significantly less than 1.8-3 times of internal formation process；Traditional
It is internalized into, includes the acid filling charging of the ripe pole plate of alienation, in order to which active matter conversion is complete, all using excessive acid filling, chemical conversion terminates
Need to extract unnecessary sulfuric acid out afterwards, it is difficult accurate control to take out sour process, acid solution density is also changed, cause between battery, even
Electrolyte consumption is inconsistent between cell negative terminal, and anacidity tank formation, retains the acid amount that acid amount is exactly acid filling, acid amount, density are all
Accurate control can be accomplished, therefore, battery with two side terminals is improved；Being added to of organic resistance solvent prevents the thing in cathode lead plaster
Matter dissolving enters electrolyte.
Preferably, the inorganic salts are chlorate, sulfate or nitrate.
Preferably, chlorate is mass ratio 1:1:The mixture of 1 sodium chloride, potassium chloride and magnesium chloride, sulfate is
Mass ratio 1:1:The mixture of 1 sodium sulphate, potassium sulfate and magnesium sulfate, nitrate is mass ratio 1:1:1 sodium nitrate, potassium nitrate
With the mixture of magnesium nitrate.
Preferably, adding nucleating agent and sustained release agent in anode diachylon, the addition of nucleating agent is the 0.5- of lead powder weight
10%, the addition of sustained release agent is the 0.01-0.5% of lead powder weight.In the technical program, nucleating agent and sustained release agent are in chemical conversion
Control the crystal formation and pattern of the active matter of generation.
Preferably, the nucleating agent is surface treated brown lead oxide.
Preferably, the process of surface treatment of brown lead oxide is to obtain acetic acid so that 10-12 parts of brown lead oxide are dissolved in into acetic acid
Solution for standby, weighs 5-7 parts of stannic chloride pentahydrates, 12-15 parts of erbium nitrates, 3-4 parts of graphenes, adds 30-45 parts of absolute ethyl alcohols,
1.5-3 parts of acetamides are added, mixed alcohol solution for standby is uniformly mixing to obtain, 2.6-3.2mol/L citric acid solution is configured,
Acetic acid solution is added into citric acid solution, mixing is added at 35-45 DEG C after ultrasonic vibration 30-60min in 10-15min
Then alcoholic solution, 75-95 DEG C of ultrasonic vibration 65-80min adjust pH to neutrality, 0.1-5 μ be ground to after being dried at 220-280 DEG C
M, acetic acid solution, citric acid solution are 1 with the volume ratio for mixing alcoholic solution：2：1.In the technical program, by surface treatment
Brown lead oxide belong to rutile-type, specific surface area is big, is conducive to formation crystal, the crystal habit of formation by nucleus of brown lead oxide
It is full, activity and service life can be effectively improved.
Preferably, organic resistance solvent is paranitrobenzoic acid, addition is the 0.5-2% of electrolyte quality.At this
In technical scheme, nitro is hydrophobic group, and adding can prevent the material in cathode lead plaster from dissolving to enter electrolysis in the electrolytic solution
Liquid
A kind of lead-acid accumulator, positive plate and negative plate are obtained by the process such as cast panel and cream, coated plate, solidification；Both positive and negative polarity
Plate is spaced, and there is negative plate the both sides of every positive plate；Positive plate is in parallel and is connected with formation charging machine anode, negative plate
Parallel connection is simultaneously connected with formation charging machine negative terminal；Liquid level of electrolyte did not had pole plate in electrolytic bath, but less than lug；According to the mould of setting
Formula charges, and positive plate lead plaster is converted into active brown lead oxide, meanwhile, cathode lead plaster is converted into active sponge
Lead；Dried after positive plate convection drying, negative plate leaching boric acid, or be directly entered anaerobic kiln dried；It is melted into dried ripe
Pole plate is after burst, encapsulating combo, cast welding, entering the processes such as groove gland, quantitative acid filling；Fill gas bleeder valve, cover plate glue envelope, by 2-
After 3 charge and discharge cycles, credit rating is judged, cleaning storage, chemical synthesizing method uses the process described above.
The beneficial effects of the invention are as follows
1）Anacidity pole plate tank formation, is not only produced without acid mist and lead waste water, and without traditional tank formation or interior
Chemical conversion sulfuric acid at initial stage acts on the reaction of generation lead sulfate with lead oxide, therefore chemical conversion electricity only has 1.1-1.5 times of theoretical capacity,
Less than 1.5-2 times of traditional sulfuric acid tank formation technique, 1.8-3 times of internal formation process is also significantly less than；
2）The crystal formation and pattern of nucleating agent A and sustained release agent B active matters of control generation in chemical conversion in formula of positive lead paste,
While guaranteed capacity, be conducive to extending battery；
Tank formation pole plate is in full electric state, and the volume of its active matter is less than electric discharge state, and the cluster of tank formation pole plate composition enters
After groove, relative to battery is internalized into, cluster pressure is easier to keep, and positive electrode active material softening and shedding is delayed；
3）Traditional is internalized into, and includes the acid filling charging of the ripe pole plate of alienation, in order to which active matter conversion is complete, all used
Acid filling is measured, chemical conversion is needed to extract unnecessary sulfuric acid out after terminating, and it is difficult accurate control to take out sour process, and acid solution density is also changed, caused
Electrolyte consumption is inconsistent between battery, or even between cell negative terminal, and anacidity tank formation, retains the acid that acid amount is exactly acid filling
Amount, acid amount, density can accomplish accurate control, therefore, and battery with two side terminals is improved；
4）The consumption of all process procedure sulfuric acid is all controllable, is produced in theory without spent acid, and traditional chemical synthesis technology,
No matter it is internalized into or tank formation, there are a large amount of spent acid to need processing；
5）Energy consumption and blowdown are all compared with traditional handicraft reduction, and battery cost declines, and economic benefit is improved.
Embodiment
In order to further appreciate that the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are intended merely to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
Sustained release agent is purchased from Qingdao Zhong electricity lightning protection Science and Technology Ltd., production code member TT-HS-A.
Remaining raw material is commercially available.
Embodiment 1
Electrolyte is neutral electrolyte, neutral electrolyte in a kind of method of lead-acid accumulator anacidity tank formation, electrolytic bath
Electrolyte be inorganic salts, solvent is deionized water, and the mass fractions of inorganic salts is that also to add organic resistance in 1%, electrolyte molten
Agent, organic resistance solvent is paranitrobenzoic acid, and addition is the 0.5% of electrolyte quality.Inorganic salts are mass ratio 1:1:1 chlorine
Change the mixture of sodium, potassium chloride and magnesium chloride.
Nucleating agent and sustained release agent are added in anode diachylon, the addition of nucleating agent is the 0.5% of lead powder weight, sustained release agent
Addition is the 0.01% of lead powder weight.Nucleating agent is surface treated brown lead oxide.
The process of surface treatment of brown lead oxide is that to obtain acetic acid solution standby so that 10 parts of brown lead oxide are dissolved in into 30 parts of acetic acid,
5 parts of stannic chloride pentahydrates, 12 parts of erbium nitrates, 3 parts of graphenes are weighed, 30 parts of absolute ethyl alcohols is added, adds 1.5 parts of acetamides,
Mixed alcohol solution for standby is uniformly mixing to obtain, 2.6mol/L citric acid solution is configured, acetic acid solution is added molten to citric acid
In liquid, mixing alcoholic solution is added at 35 DEG C after ultrasonic vibration 30min in 10min, then 75 DEG C of ultrasonic vibration 65min are adjusted
PH is ground to 0.1 μm, acetic acid solution, citric acid solution and the volume ratio for mixing alcoholic solution are 1 to neutrality after being dried at 220 DEG C：
2：1.
Embodiment 2
Electrolyte is neutral electrolyte, neutral electrolyte in a kind of method of lead-acid accumulator anacidity tank formation, electrolytic bath
Electrolyte be inorganic salts, solvent is deionized water, and the mass fractions of inorganic salts is that also to add organic resistance in 20%, electrolyte molten
Agent, organic resistance solvent is paranitrobenzoic acid, and addition is the 1% of electrolyte quality.Inorganic salts are mass ratio 1:1:1 sulfuric acid
The mixture of sodium, potassium sulfate and magnesium sulfate.
Nucleating agent and sustained release agent are added in anode diachylon, the addition of nucleating agent is the 5% of lead powder weight, sustained release agent plus
It is the 0.2% of lead powder weight to enter amount.Nucleating agent is surface treated brown lead oxide.The process of surface treatment of brown lead oxide is
So that 11 parts of brown lead oxide are dissolved in into 35 parts of acetic acid, to obtain acetic acid solution standby, weigh 6 parts of stannic chloride pentahydrates, 13 parts of erbium nitrates,
3.5 parts of graphenes, add 40 parts of absolute ethyl alcohols, add 2 parts of acetamides, be uniformly mixing to obtain mixed alcohol solution for standby, configure
2.8mol/L citric acid solution, acetic acid solution is added into citric acid solution, at 40 DEG C after ultrasonic vibration 40min
Add mixing alcoholic solution in 12min, then 85 DEG C of ultrasonic vibration 70min adjust pH to neutrality, and 2 are ground to after being dried at 255 DEG C
μm, acetic acid solution, citric acid solution are 1 with the volume ratio for mixing alcoholic solution：2：1.
Embodiment 3
Electrolyte is neutral electrolyte, neutral electrolyte in a kind of method of lead-acid accumulator anacidity tank formation, electrolytic bath
Electrolyte be inorganic salts, solvent is deionized water, and the mass fractions of inorganic salts is that also to add organic resistance in 50%, electrolyte molten
Agent, organic resistance solvent is paranitrobenzoic acid, and addition is the 2% of electrolyte quality.Inorganic salts are mass ratio 1:1:1 nitric acid
The mixture of sodium, potassium nitrate and magnesium nitrate.
Nucleating agent and sustained release agent are added in anode diachylon, the addition of nucleating agent is the 10% of lead powder weight, sustained release agent plus
It is the 0.5% of lead powder weight to enter amount.Nucleating agent is surface treated brown lead oxide.The process of surface treatment of brown lead oxide is
So that 12 parts of brown lead oxide are dissolved in into 10 parts of acetic acid, to obtain acetic acid solution standby, weighs 7 parts of stannic chloride pentahydrates, 15 parts of erbium nitrates, 4
Part graphene, adds 45 parts of absolute ethyl alcohols, adds 3 parts of acetamides, be uniformly mixing to obtain mixed alcohol solution for standby, configures
3.2mol/L citric acid solution, acetic acid solution is added into citric acid solution, at 45 DEG C after ultrasonic vibration 60min
Add mixing alcoholic solution in 15min, then 95 DEG C of ultrasonic vibration 80min adjust pH to neutrality, are ground after being dried at 280 DEG C
To 5 μm, acetic acid solution, citric acid solution are 1 with the volume ratio for mixing alcoholic solution：2：1.
Dried after the positive plate convection drying that embodiment 1-3 is obtained, negative plate leaching boric acid, or be directly entered anaerobic drying
Stove is dried；Dried ripe pole plate is melted into after burst, encapsulating combo, cast welding, entering the processes such as groove gland, quantitative acid filling；Dress
Gas bleeder valve, cover plate glue envelope after 2-3 charge and discharge cycles, judges credit rating, cleaning storage.
Claims (5)
1. a kind of method of lead-acid accumulator anacidity tank formation, it is characterised in that electrolyte is neutral electrolyte in electrolytic bath, in
Property electrolyte electrolyte be inorganic salts, solvent is deionized water, and the mass fractions of inorganic salts is also to add in 1-50%, electrolyte
Added with machine resistance solvent；Nucleating agent and sustained release agent are added in anode diachylon, the addition of nucleating agent is the 0.5-10% of lead powder weight,
The addition of sustained release agent is the 0.01-0.5% of lead powder weight；Nucleating agent is surface treated brown lead oxide；Brown lead oxide
Process of surface treatment is that to obtain acetic acid solution standby so that 10-12 part brown lead oxide are dissolved in into acetic acid, weighs 5-7 parts and crystallizes four chlorinations
Tin, 12-15 part erbium nitrate, 3-4 parts of graphenes, add 30-45 parts of absolute ethyl alcohols, add 1.5-3 parts of acetamides, stir
Mixed alcohol solution for standby is obtained, 2.6-3.2mol/L citric acid solution is configured, acetic acid solution is added into citric acid solution,
Add mixing alcoholic solution, 75-95 DEG C of ultrasonic vibration 65- at 35-45 DEG C after ultrasonic vibration 30-60min in 10-15min
80min, then adjusts pH to neutrality, is ground to 0.1-5 μm after being dried at 220-280 DEG C, acetic acid solution, citric acid solution with it is mixed
The volume ratio for closing alcoholic solution is 1：2：1.
2. a kind of method of lead-acid accumulator anacidity tank formation according to claim 1, it is characterised in that the inorganic salts
For chlorate, sulfate or nitrate.
3. the method for a kind of lead-acid accumulator anacidity tank formation according to claim 2, it is characterised in that chlorate is matter
Amount compares 1:1:The mixture of 1 sodium chloride, potassium chloride and magnesium chloride, sulfate is mass ratio 1:1:1 sodium sulphate, potassium sulfate with
The mixture of magnesium sulfate, nitrate is mass ratio 1:1:The mixture of 1 sodium nitrate, potassium nitrate and magnesium nitrate.
4. a kind of method of lead-acid accumulator anacidity tank formation according to claim 1, it is characterised in that organic resistance
Solvent is paranitrobenzoic acid, and addition is the 0.5-2% of electrolyte quality.
5. a kind of lead-acid accumulator, by cast panel and cream, coated plate, solidification, chemical conversion, drying, burst, encapsulating combo, cast welding, enter
Groove gland, charge and discharge cycles, the flow manufacturing of storage, it is characterised in that chemical synthesizing method is as described in claim 1-4 any one
Method.
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| CN105826615A (en) * | 2016-03-11 | 2016-08-03 | 超威电源有限公司 | Lead-acid battery positive plate acid-free electrolyte formation method |
| CN111682273B (en) * | 2020-05-15 | 2021-09-07 | 天能电池集团股份有限公司 | Lead storage battery formation method |
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| CN1010634B (en) * | 1987-02-12 | 1990-11-28 | 国营第四八一厂 | Chemically-making method of polar plate by adding catalyzer into electrolyte |
| US6063525A (en) * | 1997-11-20 | 2000-05-16 | Bipolar Technologies Corp. | Source of electrical power for an electric vehicle and other purposes, and related methods |
| CN1170332C (en) * | 1999-02-11 | 2004-10-06 | 陆安民 | High-energy low-consumption long-life environment-protecting type lead battery and its preparation method |
| CN1201418C (en) * | 2002-12-16 | 2005-05-11 | 武汉大学 | Method for preparing lead-acid battery negative pole |
| JP2008071717A (en) * | 2006-09-15 | 2008-03-27 | Shin Kobe Electric Mach Co Ltd | Method of chemical conversion of lead-acid battery |
| CN100541900C (en) * | 2006-09-30 | 2009-09-16 | 冯艺峰 | Directly be liquefied as storage battery and the method for making thereof that changes electrolyte system into by changing into |
| CN103219547B (en) * | 2013-04-23 | 2015-05-20 | 河南省中正电源股份有限公司 | Novel electrolyte for storage battery |
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