CN104064816A - Electrolyte additive for hydrogen evolution suppression of lead-acid storage battery and preparation method for electrolyte additive - Google Patents
Electrolyte additive for hydrogen evolution suppression of lead-acid storage battery and preparation method for electrolyte additive Download PDFInfo
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- CN104064816A CN104064816A CN201410201672.9A CN201410201672A CN104064816A CN 104064816 A CN104064816 A CN 104064816A CN 201410201672 A CN201410201672 A CN 201410201672A CN 104064816 A CN104064816 A CN 104064816A
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- acid
- lead
- sulfate
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- liberation
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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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- 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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- Secondary Cells (AREA)
Abstract
The invention relates to an electrolyte additive for hydrogen evolution suppression of a lead-acid storage battery. The additive contains polyaspartic acid, sulfate, succinic acid and ethylenediamine tetraacetic acid disodium; each liter of electrolyte of the lead-acid storage battery contains 1,500-2,000mg/L of polyaspartic acid, 1,000-1,200mg/L of sulfate, 1,500-2,000mg/L of succinic acid, 3,000-6,000mg/L of ethylenediamine tetraacetic acid disodium and the rest of a sulfuric acid. The succinic acid and the polyaspartic acid are mixed according to a certain ratio to form a sulfuric acid electrolyte additive; under the adsorption action of the succinic acid and the crystal refining action of the polyaspartic acid, the negative electrode hydrogen evolution overpotential of the lead-acid storage battery is increased, the electrochemical performance of the battery is improved, and the cycle service life of the battery is prolonged.
Description
Technical field
The present invention relates to lead-acid accumulator electrolyte, relate in particular to the negative acid accumulator negative pole overpotential of hydrogen evolution of a kind of raising, improve the lead acid accumulator that battery performance improves circulating battery useful life and suppress electrolysis additive of liberation of hydrogen and preparation method thereof.
Background technology
Lead acid accumulator is since 1859 come out, and people are exploring always and in electrolyte, adding certain solid or liquid additive, improve battery capacity and prolonging service life of battery.Although be not sure to the effect of these additives, seek the effort of electrolysis additive improvement accumulator property and carrying out always.
Lead acid accumulator is widely applied to every field always, especially field of telecommunications, stand-by power supply, accumulation power supply and power purposes etc., but also there is premature capacity loss in traditional lead acid accumulator, useful life the short series of problems that waits, its symptom is positive plate grid corrosion, lead plaster softening and shedding, negative pole sulfation etc.
When lead acid accumulator is connected circuit discharging, electronics is discharged by anode (negative plate), the Pb of formation
2+ion immediately with SO4
2-ionic reaction is deposited as insoluble lead sulfate on electrode surface.At negative electrode (positive plate), from the electronics of external circuit by PbO
2be reduced to water and Pb
2+ion, Pb
2+ion reacts with sulfate ion again immediately, by PbS0
4be deposited on electrode.When storage battery discharges completely, negative electrode (positive plate) and anode (negative plate) change PbSO substantially into
4(Gu)., there is reversible electrochemical reaction, i.e. charge in batteries in the additional reverse voltage of storage battery.While overcharging, positive plate generates thick titanium dioxide lead layer and releasing oxygen, and negative plate forms biscuit lead layer and release hydrogen.
The elimination lead acid accumulator sulfation of take is object, and then raising battery capacity and prolonging service life of battery, normal storage battery is after electric discharge, active material on positive/negative plate, become the little crystallization of soft lead sulfate, be evenly distributed in pole plate, in when charging, be easy to the brown lead oxide and the spongy lead that recover original, this is a kind of normal sulfation.Due to battery Slurry pump, all can cause pole plate irreversible (can not recharge) sulfation.Owing to forming thick lead sulfate crystallization on pole plate, can stop up the micropore of pole plate and dividing plate, hinder the osmosis of electrolyte, increased resistance, when charging, be difficult for being restored to spongy lead, the active material of participating in electrochemical reaction in pole plate is reduced, therefore capacity seriously reduces, the lost of life.Polar plate sulfation is the one of the main reasons of waste lead-acid accumulators.
Lead acid accumulator generally adopts lead-antimony alloy as grid, but the existence of antimony and migration have reduced acid accumulator negative pole lead overpotential of hydrogen evolution, has strengthened negative pole hydrogen-separating quantity.For improving the performances such as lead-acid battery negative pole active substance conduction and charge acceptance, in negative plate, often add the material that acetylene black, active carbon etc. reduce overpotential of hydrogen evolution.
Traditional lead-acid accumulator negative pole lead paste formula is that the swelling agents such as lead powder, sulfuric acid, water and lignin, humic acid, barium sulfate, acetylene black mix in certain proportion.Lead carbon battery and the superbattery of new development in recent years simultaneously improve its conductivity by the carbon of different content being doped in cathode lead plaster, to improve the capacity of battery, extend service life of lead accumulator, reach the object under high magnification with good circulation performance.Yet the doping of carbon will make the overpotential of hydrogen evolution of plumbous negative pole shuffle, when overcharging with large current charge, likely separate out a large amount of hydrogen, increase water consumption, increase the possibility that blast waits unsafe incidents generation.
Chinese patent Granted publication CN1172396C, October 20 2004 bulletin time, name is called a kind of compound electrolyte additive for lead-acid accumulator, comprise carbon element, sodium sulphate, magnesium sulfate, sodium acetate, cobalt acetate, 2,6-di-t-butyl is to family's phenol, PLP and distilled water, this additive can effectively reduce the internal resistance of cell, improves the ability to accept of battery to large electric current.Its weak point is, uses the cycle life of the lead acid accumulator that this additive makes low.
Summary of the invention
The object of the invention is to provides a kind of by the suction-operated of butanedioic acid and the effect of poly-aspartic-acid refinement crystal in order to solve existing electrolyte additive for lead-acid accumulator to defect poor in the lifting of cycle life, improve negative acid accumulator negative pole overpotential of hydrogen evolution, improve battery performance and improve the circulating battery lead acid accumulator inhibition liberation of hydrogen electrolysis additive in useful life.
Another object of the present invention is to provide the preparation method that a kind of lead acid accumulator suppresses liberation of hydrogen electrolysis additive.
To achieve these goals, the present invention is by the following technical solutions:
A kind of lead acid accumulator suppresses the electrolysis additive of liberation of hydrogen, described additive is comprised of poly-aspartic-acid, sulfate, butanedioic acid, disodium ethylene diamine tetraacetate, every liter of lead-acid accumulator electrolyte contains: poly-aspartic-acid 1500-2000mg/L, sulfate 1000-1200 mg/L, butanedioic acid 1500-2000 mg/L, disodium ethylene diamine tetraacetate 3000-6000 mg/L, all the other are sulfuric acid solution.
In the technical program, the poly-aspartic-acid adding is yellow powder, and content >=93% is soluble in water, stable chemical nature.
Poly-aspartic-acid is a kind of artificial synthetic water-soluble high-molecular substance, is amphiphilic adsorbent, and lead sulfate is had to good dispersing and disintegrating effect.When lead acid storage battery tank discharge, the active material on positive/negative plate is converted into lead sulfate crystallization, newly-generated in lead sulfate crystallization meeting constantly growth on the preferential nucleus generating.Add poly-aspartic-acid can on lead sulfate crystal, form absorption, stop lead sulfate crystal to be grown up, along with new lead sulfate nucleus constantly generates, form tiny lead sulfate crystal, be conducive to the diffusion in sulfuric acid electrolyte active material, the active matter quality of participating in electrochemical reaction is increased, thereby improve battery capacity, improve charge acceptance, improve circulating battery useful life.
Butanedioic acid is white crystalline powder, is dissolved in dilute sulfuric acid.Adding of butanedioic acid, the lead electrode that can adsorb at charge and discharge process surface, hydrogen, from generate neutral hydrogen molecule in being not easy electron gain, is equivalent to improve the deposition potential of hydrogen, can reduce separating out of hydrogen.Under larger multiplying power discharging condition, its effect in electrolyte is to have accelerated mass transfer in liquid phase process, effectively improves the conductive capability of the final ion of electric discharge, is conducive to the further utilization of active material and the increase of battery capacity; Improve negative acid accumulator negative pole overpotential of hydrogen evolution, improve battery performance and improve circulating battery useful life.
As preferably, described sulfate is a kind of in aluminum sulfate, copper sulphate, magnesium sulfate, chromium sulfate, cobaltous sulfate, nickelous sulfate, barium sulfate, potassium sulfate, sodium sulphate.
As preferably, the density of described sulfuric acid solution is 1.03-1.3g/cm
3.
Lead acid accumulator suppresses a preparation method for the electrolysis additive of liberation of hydrogen, in the concentrated sulfuric acid, add pure water by Auto-regulating System of Density of Heavy Medium to 1.03-1.3g/cm
3, be prepared into dilute sulfuric acid, get 1L dilute sulfuric acid and be heated to 40-45 ℃, add poly-aspartic-acid, sulfate, disodium ethylene diamine tetraacetate, then add while stirring butanedioic acid, and use sonic oscillation 40-50min, be cooled to room temperature.
As preferably, every liter of lead-acid accumulator electrolyte contains: poly-aspartic-acid 1500-2000mg/L, sulfate 1000-1200 mg/L, butanedioic acid 1500-2000 mg/L, disodium ethylene diamine tetraacetate 3000-6000 mg/L, all the other are sulfuric acid solution.
As preferably, ultrasonic frequency is 45-55Hz.
The invention has the beneficial effects as follows that the present invention adopts butanedioic acid and poly-aspartic-acid to mix by a certain percentage as sulfuric acid electrolyte additive; By the suction-operated of butanedioic acid and the effect of poly-aspartic-acid refinement crystal, improve negative acid accumulator negative pole overpotential of hydrogen evolution, improve battery performance and improve circulating battery useful life.
Accompanying drawing explanation
Fig. 1 is the electric discharge figure of the embodiment of the present invention 1 and comparative example 1.
Fig. 2 is the loop test figure of the embodiment of the present invention 1 and comparative example 2.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is in order to further illustrate the features and advantages of the present invention, rather than limiting to the claimed invention.
Embodiment 1
Lead acid accumulator suppresses a preparation method for the electrolysis additive of liberation of hydrogen, in the concentrated sulfuric acid, add pure water by Auto-regulating System of Density of Heavy Medium to 1.03g/cm
3, be prepared into dilute sulfuric acid, get 1L dilute sulfuric acid and be heated to 40 ℃, add poly-aspartic-acid, sodium sulphate, disodium ethylene diamine tetraacetate, then add while stirring butanedioic acid, and use sonic oscillation 40min, be cooled to room temperature.
Wherein, every liter of lead-acid accumulator electrolyte contains: poly-aspartic-acid 1500mg/L, sodium sulphate 1000mg/L, butanedioic acid 1500mg/L, disodium ethylene diamine tetraacetate 3000mg/L, and all the other are sulfuric acid solution; Ultrasonic frequency is 45Hz.
Embodiment 2
Lead acid accumulator suppresses a preparation method for the electrolysis additive of liberation of hydrogen, in the concentrated sulfuric acid, add pure water by Auto-regulating System of Density of Heavy Medium to 1.26g/cm
3, be prepared into dilute sulfuric acid, get 1L dilute sulfuric acid and be heated to 42 ℃, add poly-aspartic-acid, sodium sulphate, disodium ethylene diamine tetraacetate, then add while stirring butanedioic acid, and use sonic oscillation 45min, be cooled to room temperature.
Wherein, every liter of lead-acid accumulator electrolyte contains: poly-aspartic-acid 1800mg/L, sodium sulphate 1100mg/L, butanedioic acid 1800mg/L, disodium ethylene diamine tetraacetate 4000mg/L, and all the other are sulfuric acid solution; Ultrasonic frequency is 50Hz.
Embodiment 3
Lead acid accumulator suppresses a preparation method for the electrolysis additive of liberation of hydrogen, in the concentrated sulfuric acid, add pure water by Auto-regulating System of Density of Heavy Medium to 1.3g/cm
3, be prepared into dilute sulfuric acid, get 1L dilute sulfuric acid and be heated to 45 ℃, add poly-aspartic-acid, potassium sulfate, disodium ethylene diamine tetraacetate, then add while stirring butanedioic acid, and use sonic oscillation 50min, be cooled to room temperature.
Wherein, every liter of lead-acid accumulator electrolyte contains: poly-aspartic-acid 2000mg/L, potassium sulfate 1200mg/L, butanedioic acid 2000mg/L, disodium ethylene diamine tetraacetate 6000mg/L, and all the other are sulfuric acid solution; Ultrasonic frequency is 55Hz.
The lead-acid accumulator electrolyte that embodiment 1-3 and comparative example 1 are prepared is tested after being made into the battery of 12V12Ah.Embodiment 1 is shown in Fig. 1 with battery capacity and the comparative example 1 of comparative example 1 preparation, and the battery capacity that battery capacity prepared by visible electrolyte of the present invention is prepared than comparative example 1 electrolyte is high.
Charge acceptance: press GB/T22199-2010 standard testing, the battery charge acceptance 2.4 of comparative example 1, the battery charge acceptance of embodiment 1-3 is all greater than 3.5, be specially the battery ability to accept 3.65 of embodiment 1, the battery charge acceptance 3.78 of embodiment 2, the battery charge acceptance 3.82 of embodiment 3.
Press 100%DOD deep discharge, adopt conventional user's charger charging, carry out cycle life test, the correction data of the battery of the battery of embodiment 1 and comparative example 1 is shown in Fig. 2.
As seen from Figure 2, the cycle life that prepared by electrolyte of the present invention is far away higher than the battery of preparing than the electrolyte of comparative example 1.
This shows, initial capacity, charge acceptance and service life cycle that the present invention prepares battery have had larger lifting.
Claims (6)
1. a lead acid accumulator suppresses the electrolysis additive of liberation of hydrogen, it is characterized in that, described additive is comprised of poly-aspartic-acid, sulfate, butanedioic acid, disodium ethylene diamine tetraacetate, every liter of lead-acid accumulator electrolyte contains: poly-aspartic-acid 1500-2000mg/L, sulfate 1000-1200 mg/L, butanedioic acid 1500-2000 mg/L, disodium ethylene diamine tetraacetate 3000-6000 mg/L, all the other are sulfuric acid solution.
2. a kind of lead acid accumulator according to claim 1 suppresses the electrolysis additive of liberation of hydrogen, it is characterized in that, described sulfate is a kind of in aluminum sulfate, copper sulphate, magnesium sulfate, chromium sulfate, cobaltous sulfate, nickelous sulfate, barium sulfate, potassium sulfate, sodium sulphate.
3. a kind of lead acid accumulator according to claim 1 and 2 suppresses the electrolysis additive of liberation of hydrogen, it is characterized in that, the density of described sulfuric acid solution is 1.03-1.3g/cm
3.
4. lead acid accumulator as claimed in claim 1 suppresses a preparation method for the electrolysis additive of liberation of hydrogen, it is characterized in that, in the concentrated sulfuric acid, add pure water by Auto-regulating System of Density of Heavy Medium to 1.03-1.3g/cm
3, be prepared into dilute sulfuric acid, get 1L dilute sulfuric acid and be heated to 40-45 ℃, add poly-aspartic-acid, sulfate, disodium ethylene diamine tetraacetate, then add while stirring butanedioic acid, and use sonic oscillation 40-50min, be cooled to room temperature.
5. a kind of lead acid accumulator according to claim 4 suppresses the preparation method of the electrolysis additive of liberation of hydrogen, it is characterized in that, every liter of lead-acid accumulator electrolyte contains: poly-aspartic-acid 1500-2000mg/L, sulfate 1000-1200 mg/L, butanedioic acid 1500-2000 mg/L, disodium ethylene diamine tetraacetate 3000-6000 mg/L, all the other are sulfuric acid solution.
6. according to a kind of lead acid accumulator described in claim 4 or 5, suppress the preparation method of the electrolysis additive of liberation of hydrogen, it is characterized in that, ultrasonic frequency is 45-55Hz.
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| CN201410201672.9A CN104064816B (en) | 2014-05-14 | 2014-05-14 | A kind of electrolysis additive of lead-acid accumulator suppression liberation of hydrogen and preparation method thereof |
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|---|---|---|---|
| CN201410201672.9A CN104064816B (en) | 2014-05-14 | 2014-05-14 | A kind of electrolysis additive of lead-acid accumulator suppression liberation of hydrogen and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107154519A (en) * | 2017-06-06 | 2017-09-12 | 明光市裕阳农业有限公司 | A kind of battery liquid additive and preparation method thereof |
| CN110380137A (en) * | 2019-06-10 | 2019-10-25 | 吉林大学 | A kind of lead-acid battery electrolysis additive and preparation method thereof |
| CN115445553A (en) * | 2022-09-08 | 2022-12-09 | 洛阳大生新能源开发有限公司 | Electrolyte additive preparation device and preparation method |
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| CN103050738A (en) * | 2012-12-25 | 2013-04-17 | 深圳市佰特瑞储能系统有限公司 | Lead acid storage battery electrolyte additive and preparation method thereof |
| CN103531850A (en) * | 2013-09-23 | 2014-01-22 | 超威电源有限公司 | Electrolyte of lead-acid storage battery |
| CN103682468A (en) * | 2013-12-04 | 2014-03-26 | 河南超威电源有限公司 | Electromobile lead acid storage battery electrolyte |
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2014
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5310827A (en) * | 1976-07-19 | 1978-01-31 | Raika Kk | Method of regenerating lead battery with organic acid |
| US5780183A (en) * | 1994-01-28 | 1998-07-14 | Kyowa Hakko Kogyo Co., Ltd. | Agent for maintaining and recovering the function of lead storage battery and electrolyte for lead storage battery using the same |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107154519A (en) * | 2017-06-06 | 2017-09-12 | 明光市裕阳农业有限公司 | A kind of battery liquid additive and preparation method thereof |
| CN110380137A (en) * | 2019-06-10 | 2019-10-25 | 吉林大学 | A kind of lead-acid battery electrolysis additive and preparation method thereof |
| CN110380137B (en) * | 2019-06-10 | 2021-06-15 | 吉林大学 | A kind of lead-acid battery electrolyte additive and preparation method thereof |
| CN115445553A (en) * | 2022-09-08 | 2022-12-09 | 洛阳大生新能源开发有限公司 | Electrolyte additive preparation device and preparation method |
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| CN104064816B (en) | 2016-10-05 |
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Address after: 313100 Zhejiang city of Huzhou province Changxing County pheasant emerging urban industrial park Patentee after: Chaowei Power Group Co.,Ltd. Address before: 313100 Zhejiang city of Huzhou province Changxing County pheasant emerging urban industrial park Patentee before: CHILWEE POWER Co.,Ltd. |
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Effective date of registration: 20191220 Address after: 246000 Huaining County Industrial Park, Anhui, Anqing Patentee after: ANHUI YONGHENG POWER CELL Co.,Ltd. Address before: 313100 Zhejiang city of Huzhou province Changxing County pheasant emerging urban industrial park Patentee before: Chaowei Power Group Co.,Ltd. |