CN104505538B - A kind of lead-acid accumulator suppresses the electrolysis additive of negative plate liberation of hydrogen - Google Patents
A kind of lead-acid accumulator suppresses the electrolysis additive of negative plate liberation of hydrogen Download PDFInfo
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- CN104505538B CN104505538B CN201410812827.2A CN201410812827A CN104505538B CN 104505538 B CN104505538 B CN 104505538B CN 201410812827 A CN201410812827 A CN 201410812827A CN 104505538 B CN104505538 B CN 104505538B
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- lead
- hydrogen
- liberation
- negative plate
- acid
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/12—Construction or manufacture
- H01M10/121—Valve regulated lead acid batteries [VRLA]
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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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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of lead-acid accumulator suppresses electrolysis additive and its using method and the application of negative plate liberation of hydrogen, additive is one of rare earth compound, fluoropolymer or two kinds, and addition is the 0.01 ~ 0.1% of sulfuric acid solution quality.The present invention can effectively improve the liberation of hydrogen overpotential of the negative plate of different carbonaceous materials, reduces liberation of hydrogen speed, reduces the fluid loss of battery, thus improving performances of the lead-acid battery and then extending battery life.Additive is applied to including the analysing valve control type lead-acid accumulator battery producing containing a large amount of Carbon anode plates and pregnant solution type lead acid accumulator.
Description
Technical field
The invention belongs to battery electrolyte additive technology field is and in particular to a kind of lead-acid accumulator suppression negative plate is analysed
The electrolysis additive of hydrogen and its using method and application.
Background technology
Lead-acid accumulator is during hybrid electric vehicle traveling often under high magnification partial state of charge (HRPSoC)
Circulation, is easily caused negative plate sulfation, in order to suppress this phenomenon, needs to add a large amount of carbonaceous additives in negative plate,
The addition of material with carbon element can make lead sulfate be uniformly distributed in pole plate.The carbon of high-specific surface area can not only reduce charge and discharge
When electric current density, conductive network can also be internally formed in pole plate, be conducive to the transmission of electronics, improve charge efficiency.But by
Liberation of hydrogen overpotential in carbons material is corrected than Pb electrode potential, therefore accelerates charging process negative plate liberation of hydrogen.
A small amount of metal impurities are inevitably brought into, the liberation of hydrogen overpotential of these impurity is relative to Pb in negative plate production process
Electrode potential is corrected, and exacerbates negative plate liberation of hydrogen, thus leading to battery charging later stage charge efficiency more and more lower.
In Battery formation, the acceleration of negative plate liberation of hydrogen can pollute ring along with taking the acid mist in a large number with severe corrosive out of
Border；During circulating battery, the aggravation of negative plate liberation of hydrogen can lead to oxygen combined efficiency to reduce, and battery dehydration is accelerated, and is easily caused battery
Thermal runaway or sulfation and then impact battery life.
Additive is added to slow down negative pole liberation of hydrogen method in cathode lead plaster：Typically add some mistakes in cathode lead plaster
Cross metal ion, to improve analysis in sulfuric acid electrolyte for the carbon containing negative plate as dissolvable oxides, hydroxide, sulfate etc.
Hydrogen over potential, such as（US20070104981A1）；Also have and add modified material with carbon element, will by ball-milling method or solvent precipitation
In2O3、Ga2O3、Bi2O3And its hydroxide loads on activated carbon so that the liberation of hydrogen overpotential of modified activated carbon and Pb
Electrode potential near reducing liberation of hydrogen speed, such as（Authorization Notice No. CN102306784A）.Because the additive adding is in lead plaster
In, therefore be difficult to be uniformly distributed, lead to additive not to be apparent to the inhibitory action of negative pole liberation of hydrogen.
Additive is added to slow down negative pole liberation of hydrogen method in the electrolytic solution：It is to add a certain amount of phosphoric acid can prevent grid table
The reduction further of face Lead oxide brown, reduces self discharge；Add 0.12% copperon, can be with Sb, the Fe in electrolyte and other gold
Belong to ion forming complex, the self-discharge of battery reducing the micro presence of Sb, Fe etc. and causing, extend the life-span of battery；Add
Ionic liquid, such as triethyl group Ammonium hydrogen sulfate, dibutyl Ammonium hydrogen sulfate, benzyl Ammonium hydrogen sulfate, 1- butyl -3- Methylimidazole. sulphuric acid
Hydrogen amine, can improve the evolution or deposition potential of hydrogen.Although this kind of additive adds simply, additive is mostly Organic substance in lead
Unstable in electrolyte of lead-acid accumulator, and dissolubility in the solution is limited, its effect is mainly the liberation of hydrogen suppressing metal impurities
Speed and then the self discharge of minimizing battery, lead to additive to be not apparent to the inhibitory action of negative pole liberation of hydrogen.
Content of the invention
It is an object of the invention to provide a kind of lead-acid accumulator suppresses the electrolysis additive of negative plate liberation of hydrogen and its makes
With methods and applications, the liberation of hydrogen overpotential of the negative plate of different carbonaceous materials can be effectively improved, reduce liberation of hydrogen speed, reduce electricity
The fluid loss in pond, thus improving performances of the lead-acid battery and then extending battery life.
For achieving the above object, the present invention adopts the following technical scheme that：
It is rare earth compound that a kind of lead-acid accumulator suppresses the electrolysis additive of negative plate liberation of hydrogen, and addition is that sulphuric acid is molten
The 0.01 ~ 0.1% of liquid quality.
It is fluoropolymer that a kind of lead-acid accumulator suppresses the electrolysis additive of negative plate liberation of hydrogen, and addition is that sulphuric acid is molten
The 0.01 ~ 0.1% of liquid quality.
It is rare earth compound and fluoropolymer that a kind of lead-acid accumulator suppresses the electrolysis additive of negative plate liberation of hydrogen
Mixture, addition is respectively the 0.01 ~ 0.1% of sulfuric acid solution quality.
Described rare earth compound is rare earth oxide, rare-earth hydroxide, rare earth sulfate, in rare earth carbonate one
Plant or several mixture, rare earth element is one or more of lanthanum, samarium, gadolinium, neodymium, dysprosium；Fluoropolymer is solid or
The emulsion of fixed solid content, including politef, perfluoro caprylic acid, perfluorooctanoic acid salt, perfluoro octyl sulfonic acid, perfluoro capryl sulphur
One or more of hydrochlorate.
Using method：Rare earth compound is added directly in lead-acid accumulator electrolyte and uses；Fluoropolymer is added to
Use after needing before lead-acid accumulator electrolyte to carry out ultrasonic disperse, ultrasound condition is：Ultrasonic power 100W, ultrasonic time：
30min.
Additive is applied to including the analysing valve control type lead-acid accumulator battery producing containing a large amount of Carbon anode plates and pregnant solution type lead acid storage
Battery.
The remarkable advantage of the present invention is：
（1）Hybrid electrically automobile-used analysing valve control type lead-acid accumulator battery negative plate needs to add different material with carbon elements in a large number at present, this
Bright additive can effectively solving due in material with carbon element impurity reduce liberation of hydrogen overpotential and cause water consume increase problem.
（2）Additive used in the present invention is stable in lead-acid accumulator, will not be oxidized and ineffective.
（3）Add a small amount of additive just can greatly improve the liberation of hydrogen overpotential of different carbonaceous material negative plates, reduce
Liberation of hydrogen speed, reduces the fluid loss of battery.
（4）The wide material sources of additive, low price, nontoxic pollution-free.
（5）Additive can be added directly in lead-acid accumulator electrolyte, is uniformly dispersed, simple to operation.
（6）Additive is applied to the lead-acid accumulator of the carbon containing negative plate including analysing valve control type lead-acid accumulator battery, will not
Battery is had a negative impact.
Brief description
Fig. 1 is the Tafel curve containing different carbon material negative pole plates evolving hydrogen reaction in different sulfuric acid solutions.Negative plate：1、
0.5% activated carbon negative electrode plate, 2,1.5% expanded graphite negative plate, 3,2.0% crystalline flake graphite negative plate, 4,0.5% acetylene black negative pole
Plate；Electrolyte：A, sulfuric acid solution, b, contain 0.025% Dy2O3Sulfuric acid solution with 0.025%PTFE.
Fig. 2 is the circulation dehydration curve of the analysing valve control type lead-acid accumulator battery adding different additive.1st, blank battery, 2,
Experimental cell.
Specific embodiment
It is rare earth compound that a kind of lead-acid accumulator suppresses the electrolysis additive of negative plate liberation of hydrogen, and addition is that sulphuric acid is molten
The 0.01 ~ 0.1% of liquid quality.As added 0.025%Dy in sulfuric acid electrolyte2O3, according to material with carbon element impurities amount in negative plate
Difference, liberation of hydrogen overpotential can improve 20-171mV.
It is fluoropolymer that a kind of lead-acid accumulator suppresses the electrolysis additive of negative plate liberation of hydrogen, and addition is that sulphuric acid is molten
The 0.01 ~ 0.1% of liquid quality.As added 0.025%PTFE in sulfuric acid electrolyte, miscellaneous according to contained by material with carbon elements various in negative plate
Quality is different, and liberation of hydrogen overpotential can improve 20-222mV.
It is rare earth compound and fluoropolymer that a kind of lead-acid accumulator suppresses the electrolysis additive of negative plate liberation of hydrogen
Mixture, addition is respectively the 0.01 ~ 0.1% of sulfuric acid solution quality.As added 0.025%Dy in sulfuric acid electrolyte2O3With
The mixture of 0.025%PTFE,（Add order be：It is initially charged Dy2O3, add PTFE).According to contained by material with carbon element in negative plate
Impurity level is different, and liberation of hydrogen overpotential can improve 20-192mV.
Described rare earth compound is rare earth oxide, rare-earth hydroxide, rare earth sulfate, in rare earth carbonate one
Plant or multiple mixture, rare earth element is one or more of lanthanum, samarium, gadolinium, neodymium, dysprosium；Fluoropolymer for solid or
The emulsion of certain solids content, including politef, perfluoro caprylic acid, perfluorooctanoic acid salt, perfluoro octyl sulfonic acid, perfluoro capryl
One or more of sulfonate.
Using method：Rare earth compound is added directly in lead-acid accumulator electrolyte and uses；Fluoropolymer is added to
Use after needing before lead-acid accumulator electrolyte to carry out ultrasonic disperse, ultrasound condition is：Ultrasonic power 100W, ultrasonic time：
30min.
Additive is applied to including the analysing valve control type lead-acid accumulator battery producing containing a large amount of Carbon anode plates and pregnant solution type lead acid storage
Battery.
Embodiment 1：
The negative plate containing 0.5% activated carbon for the preparation, puts it into 1.28g/cm after chemical conversion3Sulfuric acid solution in soak 24h.
Then with negative plate as working electrode, the positive plate taking plant produced is to electrode, Hg/Hg2SO4Electrode is reference electrode,
1.28g/cm3Sulfuric acid solution be electrolyte composition three-electrode system.Adopt constant current polarization method to working electrode with the moon of 10mA
Electrode current polarization 16h, makes the active substance in negative plate be fully converted to lead, and produces gas removal negative plate by overcharge
The oxygen of dissolving in surrounding medium, then respectively with the electric current constant current polarization 2h of 8mA, 7mA, 6mA, 5mA, 3mA, 2mA, polarization electricity
After gesture φ is stable, gassing rate is measured using foam effusion meter, calculates liberation of hydrogen electric current I, repeatedly measurement is averaged, then with Log (I) ~
φ does Tafel curve.Then electrolyte is changed to 1.28g/cm3Sulfuric acid solution, and be separately added into 0.025%Gd2O3、
0.025%Sm2O3、0.025%Nd2O3、0.025%Dy2O3, repeat above-mentioned test operation.
Result shows：After adding additive in electrolyte, the liberation of hydrogen overpotential of negative plate significantly improves, and wherein adds and contains
Amount is 0.025% Gd2O3、Sm2O3、Nd2O3、Dy2O3, 10 are respectively increased to the negative plate liberation of hydrogen overpotential containing 0.5% activated carbon
~ 14mV, 12 ~ 19 mV, 13 ~ 18 mV, 19 ~ 24 mV.Therefore in the lead-acid accumulator electrolyte containing 0.5% activated carbon negative electrode plate
Add a certain proportion of Rare-earth oxide additives and can significantly improve liberation of hydrogen overpotential, reduce liberation of hydrogen speed.
Embodiment 2：
First prepare the negative plate containing different material with carbon elements, after chemical conversion, put it into 1.28g/cm3Sulfuric acid solution in soak
24h.Then with negative plate as working electrode, the positive plate taking plant produced is to electrode, Hg/Hg2SO4Electrode is reference electrode,
1.28g/cm3Sulfuric acid solution be electrolyte composition three-electrode system.Adopt constant current polarization method to working electrode with the moon of 10mA
Electrode current polarization 16h, makes the active substance in negative plate be fully converted to lead, and produces gas removal negative plate by overcharge
The oxygen of dissolving in surrounding medium, is then respectively polarized 2h with the electric current constant current of 8mA, 7mA, 6mA, 5mA, 3mA, 2mA respectively, polarization
After potential φ is stable, gassing rate is measured using foam effusion meter, calculate liberation of hydrogen electric current I, repeatedly measurement is averaged, then with Log
(I) ~ φ does Tafel curve.Then electrolyte is changed to 1.28g/cm3Sulfuric acid solution and sequentially add 0.025%
Dy2O3, 0.025% PTFE, additive pass through ultrasonic disperse in sulfuric acid solution.Repeat aforesaid operations, result is as shown in Figure 1.
Result shows：After adding additive in electrolyte, the liberation of hydrogen overpotential of negative plate significantly improves, and wherein contains 0.5%
The negative plate liberation of hydrogen overpotential of activated carbon improves 14 ~ 23mV；Negative plate liberation of hydrogen overpotential containing 0.5% acetylene black improves 50 ~ 77
mV；Negative plate liberation of hydrogen overpotential containing 1.5% expanded graphite improves 34 ~ 43 mV；Negative plate liberation of hydrogen mistake containing 2.0% crystalline flake graphite
Potential improves 13 ~ 33 mV.Add Dy therefore in the lead-acid accumulator electrolyte of different carbon containing negative plates2O3Rare earth oxide with
And politef（PTFE）Additive package significantly improves liberation of hydrogen overpotential, reduces liberation of hydrogen speed.
Embodiment 3：
Additive application of the present invention carries out the impact to water consumption for the Life Cycle in actual battery：Two are taken not to be melted into first
12V12Ah analysing valve control type lead-acid accumulator battery (material with carbon element being added in negative plate be acetylene black), be respectively labeled as No. 1 (blank
Control cell), No. 2 (experimental cell).No. 1 battery adds conventional lead-acid accumulator electrolyte, and No. 2 battery electrolytes are 1
0.025% Dy is sequentially added on the basis of number battery electrolyte2O3With 0.025% PTFE, after electrolyte ultrasonic disperse, add electricity
Chi Zhong.Then two batteries are internalized into by identical program.Weigh after being melted into and record battery original weight, then by identical
Program circulation carries out dehydration experiment.At set intervals battery is weighed and calculated fluid loss, as shown in Fig. 2 experiment table
The fluid loss of bright No. 2 batteries reduces by more than 20%.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modify, all should belong to the covering scope of the present invention.
Claims (3)
1. a kind of lead-acid accumulator suppress negative plate liberation of hydrogen electrolysis additive it is characterised in that：Additive is rare earth chemical combination
Thing and the mixture of fluorochemical, addition is respectively the 0.01 ~ 0.1% of sulfuric acid solution quality；Described rare earth compound is
The mixture of one or more of rare earth oxide, rare-earth hydroxide, rare earth sulfate, rare earth carbonate, rare earth element
For one or more of lanthanum, samarium, gadolinium, neodymium, dysprosium；Fluorochemical is politef, perfluoro caprylic acid, in perfluorooctanoic acid salt
One or more.
2. a kind of lead-acid accumulator as claimed in claim 1 suppresses the using method of the electrolysis additive of negative plate liberation of hydrogen,
It is characterized in that：Rare earth compound is added directly in lead-acid accumulator electrolyte and uses；Fluorochemical is added to plumbic acid and stores
Use after needing before battery electrolyte to carry out ultrasonic disperse, ultrasound condition is：Ultrasonic power 100W, ultrasonic time：30min.
3. a kind of lead-acid accumulator as claimed in claim 1 suppresses the application of the electrolysis additive of negative plate liberation of hydrogen, and it is special
Levy and be：Additive is applied to including the analysing valve control type lead-acid accumulator battery producing containing a large amount of Carbon anode plates and pregnant solution type lead acid electric power storage
Pond.
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| CN201410812827.2A CN104505538B (en) | 2014-12-24 | 2014-12-24 | A kind of lead-acid accumulator suppresses the electrolysis additive of negative plate liberation of hydrogen |
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| CN106785080A (en) * | 2015-11-25 | 2017-05-31 | 衡阳瑞达电源有限公司 | Additive using in electrolyte of lead accumulator, preparation method, electrolyte and lead accumulator |
| CN108899591B (en) * | 2018-05-23 | 2020-12-29 | 淄博火炬能源有限责任公司 | Power type valve-controlled lead-acid storage battery electrolyte and preparation method thereof |
| CN110336038B (en) * | 2019-04-12 | 2020-07-24 | 淄博火炬能源有限责任公司 | Bipolar battery plate and preparation method thereof |
| CN113224312B (en) * | 2021-04-15 | 2022-07-29 | 淄博火炬能源有限责任公司 | Titanium/copper-based long-life high-power lead-acid storage battery and preparation method thereof |
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| CN1227762C (en) * | 2003-03-24 | 2005-11-16 | 谯凤华 | Rare-earth containing collidal electrolyte solution for accumulator and its preparing method |
| CN102945981B (en) * | 2012-10-30 | 2015-05-20 | 中南大学 | Electrolyte for super lead acid battery |
| CN103531791B (en) * | 2013-10-29 | 2016-02-17 | 上饶市云龙实业有限公司 | A kind of super-capacitor lead carbon battery and preparation method |
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