CN102945981B - Electrolyte for super lead acid battery - Google Patents
Electrolyte for super lead acid battery Download PDFInfo
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- CN102945981B CN102945981B CN201210424189.8A CN201210424189A CN102945981B CN 102945981 B CN102945981 B CN 102945981B CN 201210424189 A CN201210424189 A CN 201210424189A CN 102945981 B CN102945981 B CN 102945981B
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- acid
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- liberation
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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 invention provides an electrolyte formula for a super lead acid battery. The electrolyte for the super lead acid battery comprises sulfuric acid solution, hydrogen evolution inhibitor and additives, wherein the hydrogen evolution inhibitor is a mixture of one or more of metal salts, metal-ion complexes and organic matters which are capable of blocking hydrogen ions from discharging on the carbon negative electrode, raising the hydrogen evolution over potentiality of the carbon negative electrode surface of the super lead acid battery. The advantage of the electrolyte is that the hydrogen evolution inhibitor can block hydrogen ions from discharging on the carbon negative electrode, thus the hydrogen evolution over potentiality of the carbon negative electrode material of the super lead acid battery is raised, the problem of serious hydrogen evolution of the carbon negative electrode surface of the super lead acid battery is solved, and simultaneously the specific capacity of the carbon negative electrode is increased. The electrolyte disclosed herein is suitable for industrial application.
Description
Technical field
The invention discloses a kind of lead-acid ultra-battery electrolyte, belong to electrochemical energy storing device field.
Background technology
Electrokinetic cell is one of key technology of new-energy automobile, is had an optimistic view of by vast automobile and Automobile Parts Industry and investor.Current driving force battery mainly contains lead acid accumulator, Cd-Ni battery, MH-Ni battery, liquid lithium ionic cell, polymer Li-ion battery, Proton Exchange Membrane Fuel Cells (PEMFC), direct methanol fuel cell (DMFC), and these batteries all have on-board measurement.Lead-acid battery is as the longest battery of applicating history, widely as electronic equipment power source in orthodox car, in new-energy automobile field, it not only as the traction power source of compact car as tour bus, radio car etc., is used in the 12V power supply of EV, HEV and plug-in especially widely.
But lead-acid battery significantly limit its application due to shortcomings such as specific energy low (35-40Wh/kg), volume are large, useful life short (300-800 time), quick charge difficulties.Many lead-acid battery new technologies were developed in recent years, as new construction, corrosion-resistant lead alloy anode plate grid, Lead Foam grid, Carbon foam grid, novel cathode additive agent, lead-acid ultra-battery, lead carbon battery, bipolarity ceramic diaphragm VRLA battery etc.Wherein lead-acid ultra-battery technology receives much concern.It is by Australia Commonwealth Scientific and Industrial Research Organisation (CSIR O) in 2004 exploitation a kind of Novel super lead-acid battery (also known as superbattery, ultra battery), ultracapacitor and lead-acid battery are parallel in a monomer by it, the carbon resistance rod dominant absorption of lead-acid ultra-battery and release electric charge, play cushioning effect when vehicle launch and braking.The high-specific-power of double electric layer capacitor, long-life blend of predominance in lead-acid battery, while maintenance " also " improves power, extending battery life advantage, are simplified the circuit of battery outward, reduce total cost by it.The lead-acid ultra-battery of research and development is loaded into the life test that Honda Insight hybrid-electric car have passed 170,000 kilometers by company of Furukawa Electronic, battery is operational excellence still, and with use Ni-MH battery with compared with money vehicle, cost reduces 40%, oil consumption and CO
2discharge capacity all has and to a certain degree reduces.
But it should be noted that, because carbon surface hydrogen-evolution overpotential is more plumbous low, charcoal negative pole " inside also " must cause battery liberation of hydrogen to increase, excessive liberation of hydrogen then can make concentration of electrolyte increase, and even causes battery dehydration to lose efficacy, affects battery life.Therefore charcoal negative pole liberation of hydrogen is the key technical problem that lead-acid ultra-battery must solve.The current hydrogen modification that presses down to Carbon Materials both at home and abroad concentrates on the doping vario-property to Carbon Materials, although achieve some effects, complex process, adds battery cost.This patent proposition is a kind of directly adds the method that hydrogen inhibitor realizes the suppression of super lead-acid battery negative pole liberation of hydrogen in the electrolytic solution, the method technique is simple, and press down hydrogen Be very effective, can effectively increase charcoal cathode specific capacity while pressing down hydrogen, there is good economy and adaptability.
Summary of the invention
The object of this invention is to provide a kind of electrolyte for super lead acid battery, Carbon Materials can be made effectively for lead-acid ultra-battery operational environment, the gassing rate of battery to be greatly reduced.
The object of the invention is to realize in the following manner:
A kind of lead-acid ultra-battery electrolyte, described electrolyte is by sulfuric acid, and liberation of hydrogen inhibitor and additive form;
The molar concentration of described sulfuric acid is 5mol/L; Containing liberation of hydrogen inhibitor 0.001-20g, additive 0.001-10g in often liter of electrolyte; Described liberation of hydrogen inhibitor is at least one in metallic compound or organic substance;
Described metallic compound is at least one in the oxide of metal, salt, hydroxide or ionic complex.
Described metallic compound is selected from Pb
2+, Pb
4+, Zn
2+, Ag
+, Cd
2+, Ba
2+, Ca
2+, Al
3+, As
3+, As
5+, Sb
3+, Sb
5+, In
+, In
3+, Ga
3+, Hg
+metallic compound in the mixture of any 1-3 kind.
Described metallic compound also comprises Bi
3+or Bi
5+metallic compound.The salt of described metal is the one in sulfate, nitrate, phosphate, carbonate.
The part of the ionic complex of described metal is amino (-NH
3), at least one in cyano group (-CN) or thiocyanogen (-SCN).
The organic substance of described liberation of hydrogen inhibitor is the mixture of a kind of in 1-METHYLPYRROLIDONE, sodium carboxymethylcellulose, aniline, acid amides, rosin amine, thiocarbamide and thiourea derivative, cinnamic acid, furfural, amyl group 1,2-two (dimethyl amine)-acetone, heterocycle ketoamine, dehydrogenated rosin imidazoline, N-vinylpyridine polymer, alkyl pyridine xanthates, pyridine and pyridine derivate, quinoline, isoquinolin, isoquinilone derivatives or any two kinds.
Described additive is CdSO
4, CaSO
4, CoSO
4, ZnSO
4, Na
2sO
4, (NH
4)
2sO
4, glutamic acid, aspartic acid, phosphoric acid, citric acid, natrium citricum, at least one in nitrilotriacetic acid disodium.
The invention has the advantages that:
(1) add hydrogen inhibitor in the solution, comparatively simple by carrying out pressing down hydrogen modification to carbon cathode material itself, be conducive to the increase of practical application and minimizing cost, economy is strong;
(2) the metal ion part in hydrogen inhibitor is high overpotential of hydrogen evolution metal, and it, in cathode surface absorption or after cathodic reduction, can hinder carbon surface hydrogen ion discharge, increases overpotential of hydrogen evolution; And the organic macromolecule in hydrogen inhibitor can adsorb and is attached to charcoal negative terminal surface, form unimolecule or polymolecular rete, increase the impedance of charcoal negative terminal surface liberation of hydrogen, thus increase overpotential of hydrogen evolution.Meanwhile, metal ion forms complex compound can reduce hydrogen ion activity in electrolyte, increases overpotential of hydrogen evolution further;
(3) hydrogen inhibitor is used in combination, can the advantage of comprehensive all kinds of hydrogen inhibitor, reaches larger suppression liberation of hydrogen effect;
(4) some organic macromolecule and metal ion are when charcoal negative terminal surface is adsorbed, and can produce fake capacitance, thus can increase charcoal capacity of negative plates while suppression liberation of hydrogen.
Accompanying drawing explanation
Accompanying drawing 1 is the electrolyte of embodiment 2,3 preparation and the polarization curve of traditional electrolyte.
Accompanying drawing 2 is the electrolyte of embodiment 11,18,20,23 preparation and the polarization curve of traditional electrolyte.
In Fig. 1, curve 1 is the polarization curve of traditional electrolyte; Curve 2 is polarization curves of electrolyte prepared by embodiment 2; Curve 3 is polarization curves of electrolyte prepared by embodiment 3;
In Fig. 2, curve 1 is the polarization curve of traditional electrolyte; Curve 4 is polarization curves of electrolyte prepared by embodiment 11;
Curve 5 is polarization curves of electrolyte prepared by embodiment 18; Curve 6 is polarization curves of electrolyte prepared by embodiment 20; Curve 7 is polarization curves of electrolyte prepared by embodiment 23.
The polarization curve (LSV) that accompanying drawing 1,2 provides can reacting phase with the instantaneous liberation of hydrogen size of current of AC electrode in different electrolytes under different potentials.As can be seen from accompanying drawing 1,2, electrolyte prepared by the present invention (-0.4V ~-0.65V) under high potential does not suppress the effect of liberation of hydrogen, but under electronegative potential (-0.65V ~-0.9V), obviously can reduce electrode surface liberation of hydrogen electric current.Different formulations electrolyte liberation of hydrogen compared with traditional electrolyte reduces about 50% ~ 80%, effect highly significant.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but these embodiments must not be interpreted as limiting the scope of the invention.
Embodiment 1
100ppmPb (NO is allocated in 5M sulfuric acid
3)
2and 0.1g/L citric acid makes electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in 8:1:1 ratio, fully grind after 30min in mortar, add solvent NMP and continue grinding a period of time, then mixed slurry is applied on collector, be pressed into pole plate, dry and obtain activated carbon negative electrode.
Assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, investigates the liberation of hydrogen characteristic of activated carbon electrodes with the sweep speed of 10mV/s in-0.9 ~-0.4V scope.Compared with general electrolytic liquid superbattery, novel electrolyte super lead-acid battery negative pole liberation of hydrogen reduces 10%-20%.
Embodiment 2
100ppmPb (NO is allocated in 5M sulfuric acid
3)
2, 20g/LZnSO
4and 5g/L citric acid makes electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in 8:1:1 ratio, fully grind after 30min in mortar, add solvent NMP and continue grinding a period of time, then mixed slurry is applied on collector, be pressed into pole plate, dry and obtain activated carbon negative electrode.
Assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, investigates the liberation of hydrogen characteristic of activated carbon electrodes with the sweep speed of 10mV/s in-0.9 ~-0.4V scope.Compared with general electrolytic liquid superbattery, novel electrolyte super lead-acid battery negative pole liberation of hydrogen reduces about 20%.
Embodiment 3
100ppmBi is allocated in 5M sulfuric acid
2o
3, 100ppmPb (NO
3)
2, 1g/LZnSO
4and 5g/L citric acid makes electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in 8:1:1 ratio, fully grind after 30min in mortar, add solvent NMP and continue grinding a period of time, then mixed slurry is applied on collector, be pressed into pole plate, dry and obtain activated carbon negative electrode.
Assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, investigates the liberation of hydrogen characteristic of activated carbon electrodes with the sweep speed of 10mV/s in-0.9 ~-0.4V scope.Compared with general electrolytic liquid superbattery, novel electrolyte super lead-acid battery negative pole liberation of hydrogen reduces 50%-60%.
Embodiment 4
In 5M sulfuric acid, allocate 100ppm isoquinolin into as hydrogen inhibitor, allocate the NTA of 1g/L into, 100ppmZnSO
4, 200ppm glutamic acid is mixed with electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in 8:1:1 ratio, fully grind after 30min in mortar, add solvent NMP and continue grinding a period of time, then mixed slurry is applied on collector, be pressed into pole plate, dry and obtain activated carbon negative electrode.
Assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, investigates the liberation of hydrogen characteristic of activated carbon electrodes with the sweep speed of 10mV/s in-0.9 ~-0.4V scope.Test finds, compared with general electrolytic liquid superbattery, novel electrolyte super lead-acid battery negative pole liberation of hydrogen reduces 30%-40%.
Embodiment 5
In 5M sulfuric acid, allocate 100ppm isoquinolin into, 200ppm thiocarbamide, as hydrogen inhibitor, allocates 5g/L (NH into
4)
2sO
4make electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in 8:1:1 ratio, fully grind after 30min in mortar, add solvent NMP and continue grinding a period of time, then mixed slurry is applied on collector, be pressed into pole plate, dry and obtain activated carbon negative electrode.
Assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, investigates the liberation of hydrogen characteristic of activated carbon electrodes with the sweep speed of 10mV/s in-0.9 ~-0.4V scope.Test finds, compared with general electrolytic liquid superbattery, novel electrolyte super lead-acid battery negative pole liberation of hydrogen reduces 10%-20%.
Embodiment 6
200ppmPb (NO is allocated in 5M sulfuric acid
3)
2, 5g/L (NH
4)
2sO
4be mixed with electrolyte, a certain amount of [Pb (NH in solution, can be formed
3)
2]
2+complex.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in 8:1:1 ratio, fully grind after 30min in mortar, add solvent NMP and continue grinding a period of time, then mixed slurry is applied on collector, be pressed into pole plate, dry and obtain activated carbon negative electrode.
Assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, investigates the liberation of hydrogen characteristic of activated carbon electrodes with the sweep speed of 10mV/s in-0.9 ~-0.4V scope.Test finds, compared with general electrolytic liquid superbattery, novel electrolyte super lead-acid battery negative pole liberation of hydrogen reduces 20%-30%.
Embodiment 7
In 5M sulfuric acid, allocate 100ppm tetra-sulphur cyanogen two ammonium into close chromium, 5g/L natrium citricum is mixed with electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in 8:1:1 ratio, fully grind after 30min in mortar, add solvent NMP and continue grinding a period of time, then mixed slurry is applied on collector, be pressed into pole plate, dry and obtain activated carbon negative electrode.
Assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, investigates the liberation of hydrogen characteristic of activated carbon electrodes with the sweep speed of 10mV/s in-0.9 ~-0.4V scope.Test finds, compared with general electrolytic liquid superbattery, novel electrolyte super lead-acid battery negative pole liberation of hydrogen reduces 30%-50%.
Embodiment 8
100ppmBi is allocated in 5M sulfuric acid
2o
3, 5g/LGa (OH)
2, 5g/LZnSO
4, 10g/L (NH
4)
2sO
4be mixed with electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in 8:1:1 ratio, fully grind after 30min in mortar, add solvent NMP and continue grinding a period of time, then mixed slurry is applied on collector, be pressed into pole plate, dry and obtain activated carbon negative electrode.
Assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, investigates the liberation of hydrogen characteristic of activated carbon electrodes with the sweep speed of 10mV/s in-0.9 ~-0.4V scope.Test finds, compared with general electrolytic liquid superbattery, novel electrolyte super lead-acid battery negative pole liberation of hydrogen reduces 30%-50%.
Embodiment 9
200ppmBi is added in 5M sulfuric acid
2o
3, 200pm isoquinolin, the NTA that 200ppm tetra-sulphur cyanogen two ammonium closes chromium and 1g/L is mixed with electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in 8:1:1 ratio, fully grind after 30min in mortar, add solvent NMP and continue grinding a period of time, then mixed slurry is applied on collector, be pressed into pole plate, dry and obtain activated carbon negative electrode.
Assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, investigates the liberation of hydrogen characteristic of activated carbon electrodes with the sweep speed of 10mV/s in-0.9 ~-0.4V scope.Test finds, compared with general electrolytic liquid superbattery, novel electrolyte super lead-acid battery negative pole liberation of hydrogen reduces 30%-60%, and meanwhile, charcoal cathode specific capacity improves about 30%.
Embodiment 10
1g/L Pb (NO is allocated in 5M sulfuric acid
3)
2and 0.1g/L citric acid makes electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in 8:1:1 ratio, fully grind after 30min in mortar, add solvent NMP and continue grinding a period of time, then mixed slurry is applied on collector, be pressed into pole plate, dry and obtain activated carbon negative electrode.
Assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, investigates the liberation of hydrogen characteristic of activated carbon electrodes with the sweep speed of 10mV/s in-0.9 ~-0.4V scope.Compared with general electrolytic liquid superbattery, novel electrolyte super lead-acid battery negative pole liberation of hydrogen reduces 10%-20%.
Embodiment 11
1g/L Pb (NO is allocated in 5M sulfuric acid
3)
2, 1g/L ZnSO
4and 5g/L citric acid makes electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in 8:1:1 ratio, fully grind after 30min in mortar, add solvent NMP and continue grinding a period of time, then mixed slurry is applied on collector, be pressed into pole plate, dry and obtain activated carbon negative electrode.
Assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, investigates the liberation of hydrogen characteristic of activated carbon electrodes with the sweep speed of 10mV/s in-0.9 ~-0.4V scope.Compared with general electrolytic liquid superbattery, novel electrolyte super lead-acid battery negative pole liberation of hydrogen reduces about 20%.
Embodiment 12
1g/LBi is allocated in 5M sulfuric acid
2o
3, 1g/L Pb (NO
3)
2, 1g/L ZnSO
4and 5g/L citric acid makes electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in 8:1:1 ratio, fully grind after 30min in mortar, add solvent NMP and continue grinding a period of time, then mixed slurry is applied on collector, be pressed into pole plate, dry and obtain activated carbon negative electrode.
Assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, investigates the liberation of hydrogen characteristic of activated carbon electrodes with the sweep speed of 10mV/s in-0.9 ~-0.4V scope.Compared with general electrolytic liquid superbattery, novel electrolyte super lead-acid battery negative pole liberation of hydrogen reduces about 20%.
Embodiment 13
In 5M sulfuric acid, allocate 1g/L furfural into as hydrogen inhibitor, allocate 5g/L(NH into
4)
2sO
4make electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in 8:1:1 ratio, fully grind after 30min in mortar, add solvent NMP and continue grinding a period of time, then mixed slurry is applied on collector, be pressed into pole plate, dry and obtain activated carbon negative electrode.
Assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, investigates the liberation of hydrogen characteristic of activated carbon electrodes with the sweep speed of 10mV/s in-0.9 ~-0.4V scope.Test finds, compared with general electrolytic liquid superbattery, novel electrolyte super lead-acid battery negative pole liberation of hydrogen reduces 10%-20%.
Embodiment 14
In 5M sulfuric acid, allocate 1g/L isoquinolin into, 1g/L thiocarbamide, as hydrogen inhibitor, allocates 10g/L natrium citricum into, 10g/L (NH
4)
2sO
4make electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in 8:1:1 ratio, fully grind after 30min in mortar, add solvent NMP and continue grinding a period of time, then mixed slurry is applied on collector, be pressed into pole plate, dry and obtain activated carbon negative electrode.
Assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, investigates the liberation of hydrogen characteristic of activated carbon electrodes with the sweep speed of 10mV/s in-0.9 ~-0.4V scope.Test finds, compared with general electrolytic liquid superbattery, novel electrolyte super lead-acid battery negative pole liberation of hydrogen reduces 10%-20%.
Embodiment 15
1g/LPb (NO is allocated in 5M sulfuric acid
3)
2, 1g/LGa
2o
3, 2g/LIn
2o
3, 5g/L (NH
4)
2sO
4be mixed with electrolyte, a certain amount of [Pb (NH in solution, can be formed
3)
2]
2+complex.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in 8:1:1 ratio, fully grind after 30min in mortar, add solvent NMP and continue grinding a period of time, then mixed slurry is applied on collector, be pressed into pole plate, dry and obtain activated carbon negative electrode.
Assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, investigates the liberation of hydrogen characteristic of activated carbon electrodes with the sweep speed of 10mV/s in-0.9 ~-0.4V scope.Test finds, compared with general electrolytic liquid superbattery, novel electrolyte super lead-acid battery negative pole liberation of hydrogen reduces 30%-40%.
Embodiment 16
In 5M sulfuric acid, allocate 1g/L tetra-sulphur cyanogen two ammonium into close chromium, 20g/L natrium citricum is mixed with electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in 8:1:1 ratio, fully grind after 30min in mortar, add solvent NMP and continue grinding a period of time, then mixed slurry is applied on collector, be pressed into pole plate, dry and obtain activated carbon negative electrode.
Assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, investigates the liberation of hydrogen characteristic of activated carbon electrodes with the sweep speed of 10mV/s in-0.9 ~-0.4V scope.Test finds, compared with general electrolytic liquid superbattery, novel electrolyte super lead-acid battery negative pole liberation of hydrogen reduces 30%-50%.
Embodiment 17
1g/LBi is allocated in 5M sulfuric acid
2o
3, 5g/LGa (OH)
2, 5g/LZnSO
4, 10g/L (NH
4)
2sO
4be mixed with electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in 8:1:1 ratio, fully grind after 30min in mortar, add solvent NMP and continue grinding a period of time, then mixed slurry is applied on collector, be pressed into pole plate, dry and obtain activated carbon negative electrode.
Assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, investigates the liberation of hydrogen characteristic of activated carbon electrodes with the sweep speed of 10mV/s in-0.9 ~-0.4V scope.Test finds, compared with general electrolytic liquid superbattery, novel electrolyte super lead-acid battery negative pole liberation of hydrogen reduces 30%-50%.
Embodiment 18
100ppmBi is added in 5M sulfuric acid
2o
3, 10g/L isoquinolin, 10g/LPb (NO
3)
2and the NTA of 1g/L is mixed with electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in 8:1:1 ratio, fully grind after 30min in mortar, add solvent NMP and continue grinding a period of time, then mixed slurry is applied on collector, be pressed into pole plate, dry and obtain activated carbon negative electrode.
Assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, investigates the liberation of hydrogen characteristic of activated carbon electrodes with the sweep speed of 10mV/s in-0.9 ~-0.4V scope.Test finds, compared with general electrolytic liquid superbattery, novel electrolyte super lead-acid battery negative pole liberation of hydrogen reduces 30%-60%, and meanwhile, charcoal cathode specific capacity improves about 30%.
Embodiment 19
200ppmBi is added in 5M sulfuric acid
2o
3, 10g/L CMC(sodium carboxymethylcellulose), the NTA of 5g/L dehydrogenated rosin imidazoline and 1g/L, 100ppmCaSO
4, 200ppm glutamic acid is mixed with electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in 8:1:1 ratio, fully grind after 30min in mortar, add solvent NMP and continue grinding a period of time, then mixed slurry is applied on collector, be pressed into pole plate, dry and obtain activated carbon negative electrode.
Assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, investigates the liberation of hydrogen characteristic of activated carbon electrodes with the sweep speed of 10mV/s in-0.9 ~-0.4V scope.Test finds, compared with general electrolytic liquid superbattery, novel electrolyte super lead-acid battery negative pole liberation of hydrogen reduces 40%-60%, and meanwhile, charcoal cathode specific capacity improves about 30%.
Embodiment 20
20g/L ZnSO is added in 5M sulfuric acid
4, then the NTA adding 5g/L dehydrogenated rosin imidazoline and 100ppm is mixed with electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in 8:1:1 ratio, fully grind after 30min in mortar, add solvent NMP and continue grinding a period of time, then mixed slurry is applied on collector, be pressed into pole plate, dry and obtain activated carbon negative electrode.
Assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, investigates the liberation of hydrogen characteristic of activated carbon electrodes with the sweep speed of 10mV/s in-0.9 ~-0.4V scope.Test finds, compared with general electrolytic liquid superbattery, novel electrolyte super lead-acid battery negative pole liberation of hydrogen reduces about 30%.
Embodiment 21
50ppmCd (OH) is allocated in 5M sulfuric acid
2, 5g/LZnSO
4add 1g/L isoquinolin again and 1g/L natrium citricum is mixed with electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in 8:1:1 ratio, fully grind after 30min in mortar, add solvent NMP and continue grinding a period of time, then mixed slurry is applied on collector, be pressed into pole plate, dry and obtain activated carbon negative electrode.
Assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, investigates the liberation of hydrogen characteristic of activated carbon electrodes with the sweep speed of 10mV/s in-0.9 ~-0.4V scope.Test finds, compared with general electrolytic liquid superbattery, novel electrolyte super lead-acid battery negative pole liberation of hydrogen reduces 60%-80%.
Embodiment 22
Difference 5g/L pyridine in 5M sulfuric acid, 10g/L thiocarbamide, 3g/L quinoline, 100ppmBi
2o
3, 100ppmPb (NO
3)
2add the Na of 1g/L isoquinolin and 5g/L again
2sO
4, 5g/L (NH
4)
2sO
4be mixed with electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in 8:1:1 ratio, fully grind after 30min in mortar, add solvent NMP and continue grinding a period of time, then mixed slurry is applied on collector, be pressed into pole plate, dry and obtain activated carbon negative electrode.
Assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, investigates the liberation of hydrogen characteristic of activated carbon electrodes with the sweep speed of 10mV/s in-0.9 ~-0.4V scope.Test finds, compared with general electrolytic liquid superbattery, novel electrolyte super lead-acid battery negative pole liberation of hydrogen reduces 60%-85%.
Embodiment 23
100ppmBi is allocated into respectively in 5M sulfuric acid
2o
3, 100ppmPb (NO
3)
2, 5g/L In
2o
3, 5g/LN-methyl pyrrolidone, the Na of 1g/L isoquinolin and 5g/L
2sO
4, 5g/L (NH
4)
2sO
4, 1g/L phosphorylated ligand makes electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in 8:1:1 ratio, fully grind after 30min in mortar, add solvent NMP and continue grinding a period of time, then mixed slurry is applied on collector, be pressed into pole plate, dry and obtain activated carbon negative electrode.
Assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, investigates the liberation of hydrogen characteristic of activated carbon electrodes with the sweep speed of 10mV/s in-0.9 ~-0.4V scope.Test finds, compared with general electrolytic liquid superbattery, novel electrolyte super lead-acid battery negative pole liberation of hydrogen reduces 62%-85%.
Claims (1)
1. a lead-acid ultra-battery electrolyte, described electrolyte is by sulfuric acid, and liberation of hydrogen inhibitor and additive form; The molar concentration of described sulfuric acid is 5mol/L; Containing liberation of hydrogen inhibitor 0.001-20 g, additive 0.001-10 g in often liter of electrolyte; Described liberation of hydrogen inhibitor is the mixture of organic substance and metallic compound composition;
Described metallic compound is Pb
2+, Pb
4+, Zn
2+, Ag
+, Cd
2+, Ba
2+, Ca
2+, Al
3+, As
3+, As
5+, Sb
3+, Sb
5+, In
+, In
3+, Ga
3+, Hg
+, Bi
3+, Bi
5+oxide, salt, the mixture of 1-3 kind arbitrarily in hydroxide or ionic complex;
The salt of metal is the one in sulfate, nitrate, phosphate, carbonate;
The part of the ionic complex of metal is amino (-NH
3), at least one in cyano group (-CN) or thiocyanogen (-SCN);
Described organic substance is the mixture of a kind of in 1-METHYLPYRROLIDONE, sodium carboxymethylcellulose, aniline, acid amides, rosin amine, thiocarbamide and thiourea derivative, cinnamic acid, furfural, amyl group 1,2-two (dimethyl amine)-acetone, heterocycle ketoamine, dehydrogenated rosin imidazoline, N-vinylpyridine polymer, alkyl pyridine xanthates, pyridine and pyridine derivate, quinoline, isoquinolin, isoquinilone derivatives or any two kinds;
Described additive is CoSO
4, Na
2sO
4, (NH
4)
2sO
4, glutamic acid, aspartic acid, phosphoric acid, citric acid, natrium citricum, at least one in nitrilotriacetic acid disodium.
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| CN104505538B (en) * | 2014-12-24 | 2017-03-08 | 福州大学 | A kind of lead-acid accumulator suppresses the electrolysis additive of negative plate liberation of hydrogen |
| CN105336945B (en) * | 2015-09-29 | 2018-05-15 | 双登集团股份有限公司 | A kind of high specific energy lead-acid battery production method |
| CN105428599B (en) * | 2015-11-23 | 2018-01-16 | 江苏海德森能源有限公司 | A kind of production method of the long-life lead carbon battery pole plate of modified activated carbon |
| CN106816643B (en) * | 2017-03-23 | 2020-04-10 | 福建省闽华电源股份有限公司 | Lead-acid battery electrolyte containing betaine surfactant |
| WO2019217381A1 (en) * | 2018-05-07 | 2019-11-14 | Teebs R&D, Llc | A method of forming a composition and the composition formed therefrom |
| 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 |
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