CN104064816B - A kind of electrolysis additive of lead-acid accumulator suppression liberation of hydrogen and preparation method thereof - Google Patents
A kind of electrolysis additive of lead-acid accumulator suppression liberation of hydrogen and preparation method thereof Download PDFInfo
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- CN104064816B CN104064816B CN201410201672.9A CN201410201672A CN104064816B CN 104064816 B CN104064816 B CN 104064816B CN 201410201672 A CN201410201672 A CN 201410201672A CN 104064816 B CN104064816 B CN 104064816B
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- acid
- sulfate
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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
Abstract
The present invention relates to the electrolysis additive of a kind of lead-acid accumulator suppression liberation of hydrogen, described additive is made up of poly-aspartic-acid, sulfate, succinic acid, disodiumedetate, every liter of lead-acid accumulator electrolyte contains: poly-aspartic-acid 1500 2000mg/L, sulfate 1,000 1200 mg/L, succinic acid 1,500 2000 mg/L, disodiumedetate 3,000 6000 mg/L, and remaining is sulfuric acid solution.The present invention uses succinic acid to mix by a certain percentage as sulphuric acid electrolyte solution additive with poly-aspartic-acid；By the adsorption of succinic 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 service life.
Description
Technical field
The present invention relates to lead-acid accumulator electrolyte, particularly relate to a kind of raising and bear acid accumulator negative pole overpotential of hydrogen evolution,
Improve battery performance improve circulating battery service life lead-acid accumulator suppression liberation of hydrogen electrolysis additive and
Preparation method.
Background technology
Lead-acid accumulator since coming out for 1859, and people are exploring always and adding certain solid or liquid in the electrolytic solution
Additive, improves accumulator capacity and prolonging service life of battery.Although the effect to these additives is not affirmative, but seeks
The effort asking electrolysis additive to improve accumulator property is being carried out always.
Lead-acid accumulator is widely applied to every field, especially field of telecommunications, stand-by power supply, accumulation power supply always
With power applications etc., but traditional lead-acid accumulator there is also premature capacity loss, service life short wait series of problems, its disease
Shape is positive plate grid corrosion, lead plaster softening and shedding, negative pole sulfation etc..
When circuit discharging connected by lead-acid accumulator, electronics is discharged by anode (negative plate), the Pb of formation2+Ion immediately with
SO42-Ionic reaction, is deposited into insoluble lead sulfate at the electrode surface.At negative electrode (positive plate), from the electronics of external circuit
By PbO2It is reduced to water and Pb2+Ion, Pb2+Ion reacts with sulfate ion the most immediately, by PbS04It is deposited on electrode.Electric power storage
Time electric discharge completely in pond, negative electrode (positive plate) and anode (negative plate) are transformed substantially into PbSO4(Gu).The additional reverse electricity of accumulator
, there is reversible electrochemical reaction, i.e. accumulator charging in pressure.During overcharge, positive plate generates thick titanium dioxide lead layer and release oxygen
Gas, negative plate forms biscuit lead layer and release hydrogen.
For the purpose of eliminating lead-acid accumulator sulfation, and then improve accumulator capacity and prolonging service life of battery, just
Normal accumulator after discharge, the active material on positive/negative plate, become the little crystallization of soft lead sulfate, be evenly distributed in pole plate
In, it being easy to recover original Lead oxide brown and spongy lead when charging, 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 sulphuric acid on pole plate
Lead crystallizes, and can block the micropore of pole plate and dividing plate, hinders the osmosis of electrolyte, adds resistance, is difficult to extensive when charging
Becoming spongy lead again, make the active material participating in electrochemical reaction in pole plate reduce, 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 typically uses lead-antimony alloy as grid, but the existence of antimony and migration reduce lead-acid storage battery negative
Pole overpotential of hydrogen evolution, increases negative pole hydrogen-separating quantity.For improving lead-acid battery negative pole active substance conduction and charge acceptance
Etc. performance, negative plate often adds acetylene black, activated carbon etc. and reduces the material of overpotential of hydrogen evolution.
Traditional formula of lead-acid storage battery negative pole diachylon is Hydrocerussitum (Ceruse), sulphuric acid, water and lignin, humic acid, barium sulfate, acetylene
Black extender such as grade mixes in certain proportion.The lead carbon battery of new development in recent years simultaneously and superbattery are by by different content
Carbon doping in cathode lead plaster, improve its electric conductivity, to improve the capacity of battery, extend service life of lead accumulator, reach high
There is under multiplying power the purpose of good circulation performance.But the overpotential of hydrogen evolution that the doping of carbon will make lead negative pole is shuffled, overcharging
Likely separate out substantial amounts of hydrogen when electricity and large current charge, increase water consumption, increase the possibility that the unsafe incidents such as blast occur.
Chinese patent Authorization Notice No. CN1172396C, announces October 20 2004 time, and entitled one is compound
Electrolyte additive for lead-acid accumulator, including carbon element, sodium sulfate, magnesium sulfate, sodium acetate, cobalt acetate, 2,6-di-t-butyl is to family
Phenol, PLP and distilled water, this additive can effectively reduce the internal resistance of cell, improves the battery acceptance to big electric current
Ability.It is disadvantageous in that, the cycle life of lead-acid accumulator using this additive to prepare is low.
Summary of the invention
It is an object of the invention to solve in the lifting to cycle life of the existing electrolyte additive for lead-acid accumulator
Poor defect and a kind of adsorption by succinic acid and the effect of poly-aspartic-acid refinement crystal are provided, improve negative
Acid accumulator negative pole overpotential of hydrogen evolution, improves battery performance and improves the lead-acid accumulator suppression in circulating battery service life
Liberation of hydrogen electrolysis additive.
It is a further object to provide the preparation method of a kind of lead-acid accumulator suppression liberation of hydrogen electrolysis additive.
To achieve these goals, the present invention is by the following technical solutions:
A kind of lead-acid accumulator suppression liberation of hydrogen electrolysis additive, described additive by poly-aspartic-acid, sulfate,
Succinic acid, disodiumedetate form, and every liter of lead-acid accumulator electrolyte contains: poly-aspartic-acid 1500-2000mg/
L, sulfate 1000-1200 mg/L, succinic acid 1500-2000 mg/L, disodiumedetate 3000-6000 mg/L, its
Remaining is sulfuric acid solution.
In the technical program, the poly-aspartic-acid of addition is yellow powder, and content >=93% is soluble in water, chemical
Matter is stable.
Poly-aspartic-acid is the water-soluble high-molecular substance of a kind of synthetic, for amphiphilic adsorbent, has lead sulfate
Good dispersion refining effect.When lead acid storage battery tank discharge, the active substance on positive/negative plate is converted into lead sulfate crystallization, newborn
Become and constantly can grow on the preferential nucleus generated in lead sulfate crystallization.Add poly-aspartic-acid can on lead sulfate crystal shape
Become absorption, stop lead sulfate crystal to be grown up, along with new lead sulfate nucleus is continuously generated, form tiny lead sulfate crystal, have
It is beneficial to the diffusion in sulfuric acid electrolyte active substance, makes the active matter quality of participation electrochemical reaction increase, thus improve battery
Capacity, improves charge acceptance, improves circulating battery service life.
Succinic acid is white crystalline powder, is dissolved in dilute sulfuric acid.The addition of succinic acid, at the lead that charge and discharge process can adsorb
Electrode surface, hydrogen from be not readily available electronics and generate neutrality hydrogen molecule, be equivalent to improve hydrogen deposition potential, can subtract
The precipitation of few hydrogen.Under the conditions of bigger multiplying power discharging, its effect in the electrolytic solution has been to speed up mass transfer in liquid phase process, effectively
Improve the conductive capability of the final ion of electric discharge, beneficially active substance further with the increase with battery capacity；Improve negative
Acid accumulator negative pole overpotential of hydrogen evolution, improves battery performance and improves circulating battery service life.
As preferably, described sulfate is aluminum sulfate, copper sulfate, magnesium sulfate, chromic sulfate, cobaltous sulfate, nickel sulfate, sulphuric acid
One in barium, potassium sulfate, sodium sulfate.
As preferably, the density of described sulfuric acid solution is 1.03-1.3g/cm3。
The preparation method of the electrolysis additive of a kind of lead-acid accumulator suppression liberation of hydrogen, adds pure water in concentrated sulfuric acid by close
Degree regulates to 1.03-1.3g/cm3, it is prepared as dilute sulfuric acid, takes 1L dilute sulfuric acid and be heated to 40-45 DEG C, addition poly-aspartic-acid,
Sulfate, disodiumedetate, add succinic acid the most while stirring, 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, succinic acid 1500-2000 mg/L, disodiumedetate 3000-6000 mg/L, remaining is sulphuric acid
Solution.
As preferably, ultrasonic frequency is 45-55Hz.
The invention has the beneficial effects as follows that the present invention uses succinic acid to mix by a certain percentage as sulfur with poly-aspartic-acid
Acid electrolyte additive；By adsorption and the effect of poly-aspartic-acid refinement crystal of succinic acid, improve negative acid and store
Battery cathode overpotential of hydrogen evolution, improves battery performance and improves circulating battery service 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.
Detailed description of the invention
In order to further appreciate that the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but
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
Restriction.
Embodiment 1
The preparation method of the electrolysis additive of a kind of lead-acid accumulator suppression liberation of hydrogen, adds pure water in concentrated sulfuric acid by close
Degree regulates to 1.03g/cm3, be prepared as dilute sulfuric acid, take 1L dilute sulfuric acid and be heated to 40 DEG C, add poly-aspartic-acid, sodium sulfate,
Disodiumedetate, adds succinic acid the most while stirring, and uses sonic oscillation 40min, be cooled to room temperature.
Wherein, every liter of lead-acid accumulator electrolyte contains: poly-aspartic-acid 1500mg/L, sodium sulfate 1000mg/L, amber
Amber acid 1500mg/L, disodiumedetate 3000mg/L, remaining is sulfuric acid solution；Ultrasonic frequency is 45Hz.
Embodiment 2
The preparation method of the electrolysis additive of a kind of lead-acid accumulator suppression liberation of hydrogen, adds pure water in concentrated sulfuric acid by close
Degree regulates to 1.26g/cm3, be prepared as dilute sulfuric acid, take 1L dilute sulfuric acid and be heated to 42 DEG C, add poly-aspartic-acid, sodium sulfate,
Disodiumedetate, adds succinic acid the most while stirring, and uses sonic oscillation 45min, be cooled to room temperature.
Wherein, every liter of lead-acid accumulator electrolyte contains: poly-aspartic-acid 1800mg/L, sodium sulfate 1100mg/L, amber
Amber acid 1800mg/L, disodiumedetate 4000mg/L, remaining is sulfuric acid solution；Ultrasonic frequency is 50Hz.
Embodiment 3
The preparation method of the electrolysis additive of a kind of lead-acid accumulator suppression liberation of hydrogen, adds pure water in concentrated sulfuric acid by close
Degree regulates to 1.3g/cm3, it is prepared as dilute sulfuric acid, takes 1L dilute sulfuric acid and be heated to 45 DEG C, add poly-aspartic-acid, potassium sulfate, second
Edetate disodium, adds succinic acid the most while stirring, and uses 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, amber
Amber acid 2000mg/L, disodiumedetate 6000mg/L, remaining is sulfuric acid solution；Ultrasonic frequency is 55Hz.
By laggard for battery that the lead-acid accumulator electrolyte that embodiment 1-3 and comparative example 1 prepare is fabricated to 12V12Ah
Row test.The battery capacity that embodiment 1 is prepared with comparative example 1 and comparative example 1 are shown in Fig. 1, it is seen that prepared by the electrolyte of the present invention
Battery capacity is higher than battery capacity prepared by comparative example 1 electrolyte.
Charge acceptance: by GB/T22199-2010 standard testing, the battery charge acceptance 2.4 of comparative example 1, reality
The battery charge acceptance executing example 1-3 is all higher than 3.5, specially the battery ability to accept 3.65 of embodiment 1, embodiment 2
Battery charge acceptance 3.78, the battery charge acceptance 3.82 of embodiment 3.
By 100%DOD deep discharge, use the charging of common user charger, be circulated life test, the electricity of embodiment 1
The correction data of the battery of pond and comparative example 1 is shown in Fig. 2.
From Figure 2 it can be seen that what cycle life prepared by the electrolyte of the present invention was significantly larger than prepared than the electrolyte of comparative example 1
Battery.
Have it can thus be seen that the present invention prepares the initial capacity of battery, charge acceptance and service life cycle
Bigger lifting.
Claims (3)
1. the electrolysis additive of a lead-acid accumulator suppression liberation of hydrogen, it is characterised in that described additive is by poly-aspartic
Acid, sulfate, succinic acid, disodiumedetate composition, every liter of lead-acid accumulator electrolyte contains: poly-aspartic-acid
1800mg, sulfate 1100 mg, succinic acid 1800 mg, disodiumedetate 4000 mg, remaining is sulfuric acid solution, sulfur
The density of acid solution is 1.03-1.26g/cm3；Preparation method is: add pure water in concentrated sulfuric acid by Auto-regulating System of Density of Heavy Medium to 1.03-
1.26g/cm3, it is prepared as dilute sulfuric acid, takes 1L dilute sulfuric acid and be heated to 40-45 DEG C, add poly-aspartic-acid, sulfate, ethylenediamine
Tetraacethyl disodium, adds succinic acid the most while stirring, and uses sonic oscillation 40-50min, be cooled to room temperature.
The electrolysis additive of a kind of lead-acid accumulator the most according to claim 1 suppression liberation of hydrogen, it is characterised in that described
Sulfate is in aluminum sulfate, copper sulfate, magnesium sulfate, chromic sulfate, cobaltous sulfate, nickel sulfate, barium sulfate, potassium sulfate, sodium sulfate
Kind.
The electrolysis additive of a kind of lead-acid accumulator the most according to claim 1 suppression liberation of hydrogen, it is characterised in that ultrasonic
Frequency be 45-55Hz.
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| Application Number | Priority Date | Filing Date | Title |
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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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| CN104064816B true CN104064816B (en) | 2016-10-05 |
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| 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 |
| CN110380137B (en) * | 2019-06-10 | 2021-06-15 | 吉林大学 | Lead-acid storage battery electrolyte additive and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1636297A (en) * | 2000-08-11 | 2005-07-06 | 约翰·C·菲特 | Electrochemical cells and an interchangeable electrolyte therefore |
| CN1886860A (en) * | 2003-10-28 | 2006-12-27 | 株式会社杰士汤浅 | Lead acid storage battery and method for producing same |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5310827A (en) * | 1976-07-19 | 1978-01-31 | Raika Kk | Method of regenerating lead battery with organic acid |
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2014
- 2014-05-14 CN CN201410201672.9A patent/CN104064816B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1636297A (en) * | 2000-08-11 | 2005-07-06 | 约翰·C·菲特 | Electrochemical cells and an interchangeable electrolyte therefore |
| CN1886860A (en) * | 2003-10-28 | 2006-12-27 | 株式会社杰士汤浅 | Lead acid storage battery and method for producing same |
| 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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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. |
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