CN108306057A - A kind of lead-acid accumulator additive - Google Patents
A kind of lead-acid accumulator additive Download PDFInfo
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- CN108306057A CN108306057A CN201810198625.1A CN201810198625A CN108306057A CN 108306057 A CN108306057 A CN 108306057A CN 201810198625 A CN201810198625 A CN 201810198625A CN 108306057 A CN108306057 A CN 108306057A
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- lead
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- acid accumulator
- additive
- ammonium acetate
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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
- H01M10/08—Selection of materials as electrolytes
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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
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
- H01M2300/0011—Sulfuric acid-based
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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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of lead-acid accumulator additive, is related to Lead-acid Battery Technology field, the lead-acid accumulator additive includes the raw material of following parts by weight：1~3 part of ammonium acetate, 1~3 part of sodium sulphate, 1~3 part of carbon black, 0.5~1.5 part of molybdenum disulfide, 1.5~3.5 parts of alum, 0.8~2.6 part of activated carbon, 0.3~0.6 part of mercaptoethylamine hydrochloride, 2,3 0.15~0.3 part of sodium dimercaptopropane sulfonate, 0.05~0.15 part of corrosion inhibiter, 0.5~1.5 part of anion surfactant, 70~92 parts of water.Electrolysis additive proposed by the present invention; precipitation, metal ion and the micelle in electrolyte are effectively removed, purifying electrolysis liquid protects pole plate not by sour corrosion; extend the service life of lead-acid accumulator, the invention also provides a kind of methods for preparing additive easy to operate.
Description
Technical field
The present invention relates to Lead-acid Battery Technology field more particularly to a kind of lead-acid accumulator additives.
Background technology
Lead-acid accumulator had become widely used a kind of electrochmical power source in the world by development and perfection in over one hundred year, had
Have the advantages that good invertibity, voltage characteristic are steady, service life is long, applied widely, abundant raw materials and cheap.
It is mainly used in each neck of the national economy such as communications and transportation, communication, electric power, railway, mine, harbour, national defence, computer, scientific research
Indispensable product in domain, social production business activities and human lives.
Electrolyte is one of essential component part in lead-acid accumulator, and the quality of quality is to lead-acid accumulator
Service life and capacity it is of great impact.The initial electrolyte of common lead-acid accumulator be by a certain proportion of sulfuric acid and
The sulfuric acid solution that water is configured to, usual density are 1.24~1.30g/cm3, proportion is 12.75~12.85g/cm3.But common
In use for some time, moisture content in electrolyte the reasons such as can lose to electrolyte because of evaporation, water electrolysis, through the wall shell of battery
Certain loss is caused, the concentration of electrolyte is caused to become larger, thus influences the service life of lead-acid accumulator.And battery makes
With that also the impurity in electrolyte can be made to increase in the process, the electric conductivity of electrolyte is influenced, these impurity include mainly that pole plate is given birth to
At lead sulfate precipitation and reaction process in the metal ion that generates, lead sulfate can influence effective contact surface of electrolyte and pole plate
Product, and then the capacity of lead-acid accumulator is influenced, and the metal ion generated can flow to lead-acid accumulator with the corrosion of sulfuric acid
Between positive and negative anodes, cause lead-acid accumulator self discharge, damages lead-acid accumulator.Based on above statement, the present invention proposes one kind
The electrolysis additive that impurity generates, extends lead-acid accumulator service life can be reduced.
Invention content
It is fast, more than impurity generation that the purpose of the present invention is to solve the moisture evaporations of electrolyte existing in the prior art
Problem, and a kind of lead-acid accumulator additive proposed.
In order to achieve the above object, the present invention is achieved by the following technical programs：
A kind of lead-acid accumulator additive, includes the raw material of following parts by weight：1~3 part of ammonium acetate, sodium sulphate 1~3
Part, 1~3 part of carbon black, 0.5~1.5 part of molybdenum disulfide, 1.5~3.5 parts of alum, 0.8~2.6 part of activated carbon, mercaptoethylmaine hydrochloric acid
0.3~0.6 part of salt, 0.15~0.3 part of Unithiol, 0.05~0.15 part of corrosion inhibiter, anion surface active
0.5~1.5 part of agent, 70~92 parts of water.
Preferably, the lead-acid accumulator additive includes the raw material of following parts by weight：1.2~2.8 parts of ammonium acetate, sulphur
1~3 part of sour sodium, 1.2~2.8 parts of carbon black, 0.8~1.2 part of molybdenum disulfide, 2~3.2 parts of alum, 1.2~2.2 parts of activated carbon, mercapto
0.3~0.6 part of base ethylamine hydrochloride, 0.15~0.3 part of Unithiol, 0.05~0.15 part of corrosion inhibiter, it is cloudy from
0.8~1.2 part of sub- surfactant, 74~88 parts of water.
Preferably, the lead-acid accumulator additive includes the raw material of following parts by weight：2 parts of ammonium acetate, sodium sulphate 2
Part, 2 parts of carbon black, 1 part of molybdenum disulfide, 2.6 parts of alum, 1.8 parts of activated carbon, 0.45 part of mercaptoethylamine hydrochloride, 2,3- dimercaptos
0.25 part of propanesulfonate, 0.1 part of corrosion inhibiter, 1 part of anion surfactant, 80 parts of water.
Preferably, the mass ratio of the ammonium acetate and sodium sulphate is 1~3：1~3, further preferably, the ammonium acetate and
The mass ratio of sodium sulphate is 1：1.
Preferably, the specific surface area of the carbon black is 850~1000m2/ kg, grain size are 10~15nm, the molybdenum disulfide
It is 11~15m for hexagonal crystal, specific surface area2/ g, grain size are 35~45nm.
Preferably, the corrosion inhibiter is methyl benzotriazazole, naphthenic base imidazoline, diisopropyl imidazoline, oleic acid base
At least one of hydroxyethyl imidazole quinoline.
Preferably, the anion surfactant is that polyacrylamide mixes or gathers with neopelex
Acrylamide is mixed with lauryl sodium sulfate, and the mass ratio of polyacrylamide and neopelex is 1：2,
Polyacrylamide and the mass ratio of lauryl sodium sulfate are 1：2.
The invention also provides a kind of preparation methods of lead-acid accumulator additive, include the following steps：
S1, each raw material is weighed according to parts by weight；
S2, ammonium acetate and sodium sulphate are added to the water, are stirred, it is to be dissolved complete, sequentially add mercaptoethylmaine hydrochloric acid
Salt, Unithiol, anion surfactant and alum continue to stir, to be dissolved complete, are then transferred to super
In sound instrument, corrosion inhibiter, carbon black, molybdenum disulfide and activated carbon are sequentially added in ultrasound, is uniformly dispersed.
The present invention provides a kind of lead-acid accumulator reinforcing activating agent, and advantage is compared with prior art：
Electrolysis additive proposed by the present invention rationally compares especially suitable for Lead-acid Battery Technology field in additive
The ammonium acetate and the compounding of sodium sulphate of example can effectively inhibit the generation of lead sulfate on pole plate, and can dissolve and be generated on pole plate
Lead sulfate precipitation, and the lead sulfate on pole plate can be also transferred under the action of carbon black and molybdenum disulfide in electrolyte, and by
Ammonium acetate solution in electrolyte, the lead sulfate precipitation not dissolved in time can be also tightly held by activated carbon, to reach purifying electrolysis liquid
Effect, alum, activated carbon, mercaptoethylamine hydrochloride and being used in compounding for Unithiol can also effectively remove
Metal ion in electrolyte and micelle ensure the excellent electric conductivity of electrolyte, and the corrosion inhibiter in additive can be in carbon
It is adsorbed on pole plate under the action of black, molybdenum disulfide and anion surfactant, improves pole plate acid corrosion performance, and then improve
The service life of lead-acid accumulator；In addition to this invention also provides a kind of lead-acid accumulators for preparing easy to operate to add
The method of agent.
Specific implementation mode
The present invention is made further to explain with reference to specific embodiment.
Embodiment 1~13, according to 2 parts of carbon black, 1 part of molybdenum disulfide, 2.6 parts of alum, 1.8 parts of activated carbon, mercaptoethylmaine salt
0.45 part of hydrochlorate, 0.25 part of Unithiol, 0.1 part of corrosion inhibiter, 1 part of anion surfactant, 80 parts of water into
Row sampling, samples according still further to the corresponding parts by weight Dichlorodiphenyl Acetate ammonium of following table and sodium sulphate, and respectively according to addition proposed by the present invention
The preparation method of agent carries out the preparation of lead-acid accumulator additive, and concrete operations are as follows：S1, each original is weighed according to parts by weight
Material；S2, ammonium acetate and sodium sulphate are added to the water, are stirred, it is to be dissolved to sequentially add mercaptoethylamine hydrochloride, 2 completely,
3- sodium dimercaptopropane sulfonate, anion surfactant and alum continue to stir, to be dissolved complete, are then transferred to Ultrasound Instrument
In, corrosion inhibiter, carbon black, molybdenum disulfide and activated carbon are sequentially added in ultrasound, is uniformly dispersed, and the specific surface area of carbon black is
850~1000m2/ kg, grain size are 10~15nm, and molybdenum disulfide is hexagonal crystal, specific surface area is 11~15m2/ g, grain size
For 35~45nm, corrosion inhibiter is the compounding of methyl benzotriazazole and naphthenic base imidazoline, and anion surfactant is poly- third
Acrylamide is mixed with neopelex, and the mass ratio of polyacrylamide and neopelex is 1：2.
The lead-acid accumulator of 14 12V300AH is taken, adds prepared by embodiment 1 in the electrolyte of the 1st lead-acid accumulator
Additive, the additive that prepared by addition embodiment 2 in the electrolyte of the 2nd lead-acid accumulator, and so on, the 13rd plumbic acid stores
Additive prepared by embodiment 13 is added in the electrolyte of battery, the 14th lead-acid accumulator is comparative example 1, does not add addition
14 lead-acid accumulators are carried out performance detection, testing result by agent, and 2% that the additive amount of additive is electrolyte gross mass
It is shown in Table 1.
Table 1：
| Embodiment | Ammonium acetate | Sodium sulphate | Capacity AH | Service life | Estimate substrate attack situation |
| 1 | - | 2 | Corrosion | ||
| 2 | 2 | - | Corrosion | ||
| 3 | 1 | 1 | 299 | 732 | Slightly corrode |
| 4 | 1 | 2 | 297 | 721 | Slightly corrode |
| 5 | 1 | 3 | 296 | 711 | Slightly corrode |
| 6 | 1 | 4 | 291 | 683 | Slightly corrode |
| 7 | 2 | 1 | 296 | 719 | Slightly corrode |
| 8 | 2 | 2 | 302 | 733 | Slightly corrode |
| 9 | 2 | 3 | 298 | 724 | Slightly corrode |
| 10 | 4 | 1 | 292 | 679 | Slightly corrode |
| 11 | 3 | 1 | 296 | 711 | Slightly corrode |
| 12 | 3 | 2 | 298 | 722 | Slightly corrode |
| 13 | 3 | 3 | 300 | 731 | Slightly corrode |
The capacity of comparative example 1 is 290AH, and the service life is 659 times, and range estimation substrate attack situation is heavy corrosion.
The result of Examples 1 to 3 is shown in table 1：Ammonium acetate and sodium sulphate are added simultaneously to imitate the protection of lead-acid accumulator
Fruit will be much better than to be individually added into ammonium acetate or sodium sulphate, show that ammonium acetate and sodium sulphate have synergistic effect.
The result of embodiment 3~13 is shown in table：The mass ratio of ammonium acetate and sodium sulphate to service life of lead-acid accumulator, hold
Amount is affected, when the mass ratio of ammonium acetate and sodium sulphate is 3：1 to 1：When between 3, the capacity of lead-acid accumulator can reach
It can reach 710 times or more to 295AH or more, service life, when the mass ratio of ammonium acetate and sodium sulphate is higher than 3：1 or be less than 1：When 3,
The capacity and service life of lead-acid accumulator significantly reduce, and the mass ratio of ammonium acetate and sodium sulphate is 1：Lead-acid accumulator when 1
Capacity highest, service life longest.
In addition to this, in table embodiment 3~13 substrate attack speed be less than embodiment 1 and embodiment 2 corrosion rate,
And the substrate attack speed of embodiment 1 and embodiment 2 is less than the corrosion rate of comparison spr substrate, shows proposed by the present invention add
Add agent that can effectively delay the corrosion rate of substrate.
Embodiment 14
It is 1 that anion surfactant in embodiment 8, which is changed to mass ratio,：2 polyacrylamide and dodecyl sulphur
The mixture of sour sodium, other conditions prepare additive with embodiment 12.
Comparative example 2
Change the anion surfactant in embodiment 8 into polyacrylamide respectively, other conditions are the same as embodiment 8, system
Standby additive.
Comparative example 3
Change the anion surfactant in embodiment 8 into neopelex respectively, other conditions are the same as implementation
Example 8, prepares additive.
Comparative example 4
Change the anion surfactant in embodiment 8 into lauryl sodium sulfate, the same embodiment of other conditions respectively
8, prepare additive.
The lead-acid accumulator of 4 12V300AH is taken, adds prepared by embodiment 14 in the electrolyte of the 1st lead-acid accumulator
Additive, the additive that prepared by addition comparative example 2 in the electrolyte of the 2nd lead-acid accumulator, and so on, the 4th plumbic acid stores
Additive prepared by comparative example 4 is added in the electrolyte of battery, the additive amount of additive is the 2% of electrolyte gross mass, to 14
A lead-acid accumulator carries out performance detection, and testing result is shown in Table 2.
Table 2：
The result of embodiment 4 is suitable with embodiment 8 in table 3, and the battery capacity of comparative example 2~4 and service life are significantly lower than
Embodiment 4 shows that polyacrylamide and neopelex mix or polyacrylamide and lauryl sodium sulfate
Synergistic effect can be played by mixing, and the effect reached is than being used alone polyacrylamide, neopelex
Or the effect of lauryl sodium sulfate is good.
Embodiment 15
Corrosion inhibiter equivalent in above-described embodiment 8 is substituted for methyl benzotriazazole, naphthenic base imidazoline, diisopropyl
At least one of imidazoline, oleic acid base hydroxyethyl imidazole quinoline carry out preparing additive, and if being added to the additive of preparation
In the electrolyte of the lead-acid accumulator of dry 12V300AH, the additive amount of additive is the 2% of electrolyte gross mass, then to plumbic acid
Accumulator carry out performance detection, as a result the capacity of display in 300~304 ranges, the service life in 327~733 ranges, corrosion condition
It is slightly to corrode, shows：In additive proposed by the present invention corrosion inhibiter be methyl benzotriazazole, it is naphthenic base imidazoline, two different
The additive prepared when at least one of propyl imidazole quinoline, oleic acid base hydroxyethyl imidazole quinoline all has excellent corrosion mitigating effect.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto, and it is any to be familiar with
Those skilled in the art in the technical scope disclosed by the present invention, according to the technical scheme of the invention and its inventive conception
It is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (8)
1. a kind of lead-acid accumulator additive, which is characterized in that the lead-acid accumulator additive includes following parts by weight
Raw material：1~3 part of ammonium acetate, 1~3 part of sodium sulphate, 1~3 part of carbon black, 0.5~1.5 part of molybdenum disulfide, alum 1.5~3.5
Part, 0.8~2.6 part of activated carbon, 0.3~0.6 part of mercaptoethylamine hydrochloride, 0.15~0.3 part of Unithiol delay
Lose 0.05~0.15 part of agent, 0.5~1.5 part of anion surfactant, 70~92 parts of water.
2. lead-acid accumulator additive according to claim 1, which is characterized in that the lead-acid accumulator additive
Include the raw material of following parts by weight：1.2~2.8 parts of ammonium acetate, 1~3 part of sodium sulphate, 1.2~2.8 parts of carbon black, molybdenum disulfide 0.8
~1.2 parts, 2~3.2 parts of alum, 1.2~2.2 parts of activated carbon, 0.3~0.6 part of mercaptoethylamine hydrochloride, 2,3- the third sulphurs of dimercapto
0.15~0.3 part of sour sodium, 0.05~0.15 part of corrosion inhibiter, 0.8~1.2 part of anion surfactant, 74~88 parts of water.
3. lead-acid accumulator additive according to claim 1, which is characterized in that the lead-acid accumulator additive
Include the raw material of following parts by weight：2 parts of ammonium acetate, 2 parts of sodium sulphate, 2 parts of carbon black, 1 part of molybdenum disulfide, 2.6 parts of alum, activated carbon
1.8 parts, 0.45 part of mercaptoethylamine hydrochloride, 0.25 part of Unithiol, 0.1 part of corrosion inhibiter, anionic surface work
1 part of agent of property, 80 parts of water.
4. lead-acid accumulator additive according to claim 1, which is characterized in that the matter of the ammonium acetate and sodium sulphate
Amount is than being 1~3：1~3.
5. a kind of lead-acid accumulator additive according to claim 1, which is characterized in that the specific surface area of the carbon black
For 850~1000m2/ kg, grain size are 10~15nm, and the molybdenum disulfide is hexagonal crystal, specific surface area is 11~15m2/
G, grain size is 35~45nm.
6. a kind of lead-acid accumulator additive according to claim 1, which is characterized in that the corrosion inhibiter is methylbenzene
And at least one of triazole, naphthenic base imidazoline, diisopropyl imidazoline, oleic acid base hydroxyethyl imidazole quinoline.
7. a kind of lead-acid accumulator additive according to claim 1, which is characterized in that the anion surface active
Agent is that polyacrylamide is mixed with neopelex or polyacrylamide is mixed with lauryl sodium sulfate,
And the mass ratio of polyacrylamide and neopelex is 1：2, the quality of polyacrylamide and lauryl sodium sulfate
Than being 1：2.
8. a kind of lead-acid accumulator additive according to claim 1, which is characterized in that preparation method includes following
Step：
S1, each raw material is weighed according to parts by weight；
S2, ammonium acetate and sodium sulphate are added to the water, are stirred, it is to be dissolved to sequentially add mercaptoethylamine hydrochloride, 2 completely,
3- sodium dimercaptopropane sulfonate, anion surfactant and alum continue to stir, to be dissolved complete, are then transferred to Ultrasound Instrument
In, corrosion inhibiter, carbon black, molybdenum disulfide and activated carbon are sequentially added in ultrasound, are uniformly dispersed.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2017111141026 | 2017-11-13 | ||
| CN201711114102 | 2017-11-13 |
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| CN108306057A true CN108306057A (en) | 2018-07-20 |
| CN108306057B CN108306057B (en) | 2020-04-10 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111668557A (en) * | 2020-04-29 | 2020-09-15 | 广东英业达电子有限公司 | Colloid electrolyte of nano colloid long-life battery and preparation method thereof |
| CN112103562A (en) * | 2020-10-16 | 2020-12-18 | 江苏师范大学 | Electrolyte additive, electrolyte containing additive and lithium metal battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101022181A (en) * | 2006-02-15 | 2007-08-22 | 王一锋 | Lead-acid battery recovery active agent and lead-acid battery sulfation recovery method |
| CN101636512A (en) * | 2007-01-17 | 2010-01-27 | 米尔布鲁克铅再生科技有限公司 | From the scrap lead battery that contains electrode paste, reclaim the lead of high purity carbon lead plumbate form |
-
2018
- 2018-03-12 CN CN201810198625.1A patent/CN108306057B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101022181A (en) * | 2006-02-15 | 2007-08-22 | 王一锋 | Lead-acid battery recovery active agent and lead-acid battery sulfation recovery method |
| CN101636512A (en) * | 2007-01-17 | 2010-01-27 | 米尔布鲁克铅再生科技有限公司 | From the scrap lead battery that contains electrode paste, reclaim the lead of high purity carbon lead plumbate form |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111668557A (en) * | 2020-04-29 | 2020-09-15 | 广东英业达电子有限公司 | Colloid electrolyte of nano colloid long-life battery and preparation method thereof |
| CN112103562A (en) * | 2020-10-16 | 2020-12-18 | 江苏师范大学 | Electrolyte additive, electrolyte containing additive and lithium metal battery |
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| CN108306057B (en) | 2020-04-10 |
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