CN102945981A - Electrolyte for super lead acid battery - Google Patents
Electrolyte for super lead acid battery Download PDFInfo
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- CN102945981A CN102945981A CN2012104241898A CN201210424189A CN102945981A CN 102945981 A CN102945981 A CN 102945981A CN 2012104241898 A CN2012104241898 A CN 2012104241898A CN 201210424189 A CN201210424189 A CN 201210424189A CN 102945981 A CN102945981 A CN 102945981A
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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 the electrochemical energy storing device field.
Background technology
Electrokinetic cell is one of key technology of new-energy automobile, and is good by vast automobile and Automobile Parts Industry and investor.The 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 vehicle-mounted experiment.Lead-acid battery is as the longest battery of applicating history, in orthodox car widely as the electronic equipment power source, in the new-energy automobile field, it not only as the traction power source of compact car such as tour bus, radio car etc., is used in the 12V power supply of EV, HEV and plug-in especially widely.
Yet lead-acid battery is because the shortcomings such as specific energy low (35-40Wh/kg), volume are large, useful life short (300-800 time), quick charge difficulty have limited its application greatly.Many lead-acid battery new technologies had been developed in recent years, such 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 the lead-acid ultra-battery technology receives much concern.It is (to claim again superbattery by Australian Union's science and industrial research tissue (CSIRO) in a kind of Novel super lead-acid battery of exploitation in 2004, ultra battery), it is parallel to ultracapacitor and lead-acid battery in the monomer, the carbon resistance rod of lead-acid ultra-battery mainly absorbs and discharges electric charge, plays cushioning effect when vehicle launch and braking.It in lead-acid battery, when keeping " outside also " to improve power, extending battery life advantage, simplifies the circuit of battery with the high-specific-power of double electric layer capacitor, long-life blend of predominance, reduces total cost.Company of Furukawa Electronic is loaded into the lead-acid ultra-battery of researching and developing and has passed through 170,000 kilometers life test on the Honda Insight hybrid-electric car, battery is operational excellence still, and with use comparing with the money vehicle of Ni-MH battery, cost 40%, oil consumption and CO
2Discharge capacity all has to a certain degree minimizing.
But it should be noted that because the carbon surface hydrogen-evolution overpotential is more plumbous low, charcoal negative pole " also interior " must cause the battery liberation of hydrogen to increase, excessively liberation of hydrogen then can make concentration of electrolyte increase, even causes battery dehydration inefficacy, affects battery life.Therefore charcoal negative pole liberation of hydrogen is the key technical problem that lead-acid ultra-battery must solve.Both at home and abroad at present the hydrogen modification that presses down of Carbon Materials concentrated on the doping vario-property to Carbon Materials, although obtained some effects, complex process has increased the battery cost.This patent proposes a kind of method that hydrogen inhibitor realizes that lead-acid ultra-battery charcoal negative pole liberation of hydrogen suppresses of directly adding in electrolyte, the method technique is simple, and it is remarkable to press down the hydrogen effect, can effectively increase charcoal negative pole specific capacity when pressing down hydrogen, has good economy and adaptability.
Summary of the invention
The purpose of this invention is to provide a kind of lead-acid ultra-battery electrolyte, can make Carbon Materials effectively be used for the lead-acid ultra-battery operational environment, greatly reduce the gassing rate of battery.
The objective of the invention is to realize in the following manner:
A kind of lead-acid ultra-battery electrolyte, described electrolyte are by sulfuric acid, and liberation of hydrogen inhibitor and additive form;
The molar concentration of described sulfuric acid is 5mol/L; Contain liberation of hydrogen inhibitor 0.001-20g, additive 0.001-10g in every liter of electrolyte; Described liberation of hydrogen inhibitor is at least a in metallic compound or the organic substance;
Described metallic compound is at least a in oxide, salt, hydroxide or the ionic complex of metal.
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 any mixture of 1-3 kind.
Described metallic compound also comprises Bi
3+Or Bi
5+Metallic compound.The salt of described metal is a kind of in sulfate, nitrate, phosphate, the carbonate.
The part of the ionic complex of described metal is amino (NH
3), cyano group (CN) or thiocyanogen (at least a SCN).
The organic substance of described liberation of hydrogen inhibitor is 1-METHYLPYRROLIDONE, sodium carboxymethylcellulose, aniline, acid amides, rosin amine, thiocarbamide and thiourea derivative, cinnamic acid, furfural, amyl group 1, a kind of or any two kinds mixture in two (the dimethyl amine)-acetone of 2-, heterocycle ketoamine, dehydrogenated rosin imidazoline, N-vinylpyridine polymer, alkyl pyridine xanthates, pyridine and pyridine derivate, quinoline, isoquinolin, the isoquinilone derivatives.
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 a in the nitrilotriacetic acid disodium.
The invention has the advantages that:
(1) in solution, add hydrogen inhibitor, simple by carbon cathode material itself is pressed down the hydrogen modification, be conducive to the increase of practical application and Cost reduction, economy is strong;
(2) part of the metal ion in the hydrogen inhibitor is high overpotential of hydrogen evolution metal, and it can hinder the carbon surface hydrogen ion discharge in cathode surface absorption or after cathodic reduction, increases overpotential of hydrogen evolution; And the organic macromolecule in the hydrogen inhibitor can adsorb and is attached to the charcoal negative terminal surface, forms unimolecule or polymolecular rete, increases the impedance of charcoal negative terminal surface liberation of hydrogen, thereby increases overpotential of hydrogen evolution.Simultaneously, metal ion forms complex compound can reduce hydrogen ion activity in the electrolyte, further increases overpotential of hydrogen evolution;
(3) hydrogen inhibitor mix to use, and advantage that can comprehensive all kinds of hydrogen inhibitors reaches larger inhibition liberation of hydrogen effect;
(4) some organic macromolecule and metal ion can produce fake capacitance when the charcoal negative terminal surface is adsorbed, thereby can increase the charcoal capacity of negative plates when suppressing liberation of hydrogen.
Description of drawings
Accompanying drawing 1 is embodiment 2, the electrolyte of 3 preparations and the polarization curve of traditional electrolyte.
Accompanying drawing 2 is embodiment 11,18,20, the electrolyte of 23 preparations and the polarization curve of traditional electrolyte.
Among Fig. 1, curve 1 is the polarization curve of traditional electrolyte; Curve 2 is polarization curves of the electrolyte of embodiment 2 preparations; Curve 3 is polarization curves of the electrolyte of embodiment 3 preparations;
Among Fig. 2, curve 1 is the polarization curve of traditional electrolyte; Curve 4 is polarization curves of the electrolyte of embodiment 11 preparations;
The polarization curve that accompanying drawing 1,2 provides (LSV) can reacting phase with AC electrode instantaneous liberation of hydrogen size of current under the different potentials in different electrolytes.Can find out from accompanying drawing 1,2, the electrolyte of the present invention preparation under high potential (0.4V ~-0.65V) do not suppress the effect of liberation of hydrogen, but electronegative potential (0.65V ~-0.9V) under, can obviously reduce electrode surface liberation of hydrogen electric current.Different formulations electrolyte and traditional electrolysis liquid phase reduce about 50% ~ 80% than liberation of hydrogen, the effect highly significant.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but these embodiment must not be interpreted as limiting the scope of the invention.
In 5M sulfuric acid, allocate 100ppmPb (NO into
3)
2And the 0.1g/L citric acid is made electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in the 8:1:1 ratio, in mortar, fully grind after the 30min, add solvent NMP and continue to grind a period of time, again mixed slurry is applied on the collector, be pressed into pole plate, oven dry obtains activated carbon negative electrode.
The assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, with the sweep speed of 10mV/s-0.9 ~-the 0.4V scope in the liberation of hydrogen characteristic of investigation activated carbon electrodes.Compare with common electrolyte superbattery, novel electrolyte lead-acid ultra-battery charcoal negative pole liberation of hydrogen reduces 10%-20%.
In 5M sulfuric acid, allocate 100ppmPb (NO into
3)
2, 20g/LZnSO
4And the 5g/L citric acid is made electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in the 8:1:1 ratio, in mortar, fully grind after the 30min, add solvent NMP and continue to grind a period of time, again mixed slurry is applied on the collector, be pressed into pole plate, oven dry obtains activated carbon negative electrode.
The assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, with the sweep speed of 10mV/s-0.9 ~-the 0.4V scope in the liberation of hydrogen characteristic of investigation activated carbon electrodes.Compare with common electrolyte superbattery, novel electrolyte lead-acid ultra-battery charcoal negative pole liberation of hydrogen reduces about 20%.
In 5M sulfuric acid, allocate 100ppmBi into
2O
3, 100ppmPb (NO
3)
2, 1g/LZnSO
4And the 5g/L citric acid is made electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in the 8:1:1 ratio, in mortar, fully grind after the 30min, add solvent NMP and continue to grind a period of time, again mixed slurry is applied on the collector, be pressed into pole plate, oven dry obtains activated carbon negative electrode.
The assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, with the sweep speed of 10mV/s-0.9 ~-the 0.4V scope in the liberation of hydrogen characteristic of investigation activated carbon electrodes.Compare with common electrolyte superbattery, novel electrolyte lead-acid ultra-battery charcoal 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 the 8:1:1 ratio, in mortar, fully grind after the 30min, add solvent NMP and continue to grind a period of time, again mixed slurry is applied on the collector, be pressed into pole plate, oven dry obtains activated carbon negative electrode.
The assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, with the sweep speed of 10mV/s-0.9 ~-the 0.4V scope in the liberation of hydrogen characteristic of investigation activated carbon electrodes.Test is found, compares with common electrolyte superbattery, and novel electrolyte lead-acid ultra-battery charcoal negative pole liberation of hydrogen reduces 30%-40%.
Allocate 100ppm isoquinolin in 5M sulfuric acid into, the 200ppm thiocarbamide is allocated 5g/L (NH into as hydrogen inhibitor
4)
2SO
4Make electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in the 8:1:1 ratio, in mortar, fully grind after the 30min, add solvent NMP and continue to grind a period of time, again mixed slurry is applied on the collector, be pressed into pole plate, oven dry obtains activated carbon negative electrode.
The assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, with the sweep speed of 10mV/s-0.9 ~-the 0.4V scope in the liberation of hydrogen characteristic of investigation activated carbon electrodes.Test is found, compares with common electrolyte superbattery, and novel electrolyte lead-acid ultra-battery charcoal negative pole liberation of hydrogen reduces 10%-20%.
In 5M sulfuric acid, allocate 200ppmPb (NO into
3)
2, 5g/L (NH
4)
2SO
4Be mixed with electrolyte, can form a certain amount of [Pb (NH in the solution
3)
2]
2+Complex.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in the 8:1:1 ratio, in mortar, fully grind after the 30min, add solvent NMP and continue to grind a period of time, again mixed slurry is applied on the collector, be pressed into pole plate, oven dry obtains activated carbon negative electrode.
The assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, with the sweep speed of 10mV/s-0.9 ~-the 0.4V scope in the liberation of hydrogen characteristic of investigation activated carbon electrodes.Test is found, compares with common electrolyte superbattery, and novel electrolyte lead-acid ultra-battery charcoal negative pole liberation of hydrogen reduces 20%-30%.
Allocate 100ppm four sulphur cyanogen two ammoniums into and close chromium in 5M sulfuric acid, the 5g/L natrium citricum is mixed with electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in the 8:1:1 ratio, in mortar, fully grind after the 30min, add solvent NMP and continue to grind a period of time, again mixed slurry is applied on the collector, be pressed into pole plate, oven dry obtains activated carbon negative electrode.
The assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, with the sweep speed of 10mV/s-0.9 ~-the 0.4V scope in the liberation of hydrogen characteristic of investigation activated carbon electrodes.Test is found, compares with common electrolyte superbattery, and novel electrolyte lead-acid ultra-battery charcoal negative pole liberation of hydrogen reduces 30%-50%.
Embodiment 8
In 5M sulfuric acid, allocate 100ppmBi into
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 the 8:1:1 ratio, in mortar, fully grind after the 30min, add solvent NMP and continue to grind a period of time, again mixed slurry is applied on the collector, be pressed into pole plate, oven dry obtains activated carbon negative electrode.
The assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, with the sweep speed of 10mV/s-0.9 ~-the 0.4V scope in the liberation of hydrogen characteristic of investigation activated carbon electrodes.Test is found, compares with common electrolyte superbattery, and novel electrolyte lead-acid ultra-battery charcoal negative pole liberation of hydrogen reduces 30%-50%.
Embodiment 9
In 5M sulfuric acid, add 200ppmBi
2O
3, 200pm isoquinolin, the NTA that 200ppm four sulphur cyanogen two ammoniums close chromium and 1g/L is mixed with electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in the 8:1:1 ratio, in mortar, fully grind after the 30min, add solvent NMP and continue to grind a period of time, again mixed slurry is applied on the collector, be pressed into pole plate, oven dry obtains activated carbon negative electrode.
The assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, with the sweep speed of 10mV/s-0.9 ~-the 0.4V scope in the liberation of hydrogen characteristic of investigation activated carbon electrodes.Test is found, compares with common electrolyte superbattery, and novel electrolyte lead-acid ultra-battery charcoal negative pole liberation of hydrogen reduces 30%-60%, and simultaneously, charcoal negative pole specific capacity improves about 30%.
Embodiment 10
In 5M sulfuric acid, allocate 1g/L Pb (NO into
3)
2And the 0.1g/L citric acid is made electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in the 8:1:1 ratio, in mortar, fully grind after the 30min, add solvent NMP and continue to grind a period of time, again mixed slurry is applied on the collector, be pressed into pole plate, oven dry obtains activated carbon negative electrode.
The assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, with the sweep speed of 10mV/s-0.9 ~-the 0.4V scope in the liberation of hydrogen characteristic of investigation activated carbon electrodes.Compare with common electrolyte superbattery, novel electrolyte lead-acid ultra-battery charcoal negative pole liberation of hydrogen reduces 10%-20%.
Embodiment 11
In 5M sulfuric acid, allocate 1g/L Pb (NO into
3)
2, 1g/L ZnSO
4And the 5g/L citric acid is made electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in the 8:1:1 ratio, in mortar, fully grind after the 30min, add solvent NMP and continue to grind a period of time, again mixed slurry is applied on the collector, be pressed into pole plate, oven dry obtains activated carbon negative electrode.
The assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, with the sweep speed of 10mV/s-0.9 ~-the 0.4V scope in the liberation of hydrogen characteristic of investigation activated carbon electrodes.Compare with common electrolyte superbattery, novel electrolyte lead-acid ultra-battery charcoal negative pole liberation of hydrogen reduces about 20%.
Embodiment 12
In 5M sulfuric acid, allocate 1g/LBi into
2O
3, 1g/L Pb (NO
3)
2, 1g/L ZnSO
4And the 5g/L citric acid is made electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in the 8:1:1 ratio, in mortar, fully grind after the 30min, add solvent NMP and continue to grind a period of time, again mixed slurry is applied on the collector, be pressed into pole plate, oven dry obtains activated carbon negative electrode.
The assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, with the sweep speed of 10mV/s-0.9 ~-the 0.4V scope in the liberation of hydrogen characteristic of investigation activated carbon electrodes.Compare with common electrolyte superbattery, novel electrolyte lead-acid ultra-battery charcoal negative pole liberation of hydrogen reduces about 20%.
Embodiment 13
In 5M sulfuric acid, allocate the 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 the 8:1:1 ratio, in mortar, fully grind after the 30min, add solvent NMP and continue to grind a period of time, again mixed slurry is applied on the collector, be pressed into pole plate, oven dry obtains activated carbon negative electrode.
The assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, with the sweep speed of 10mV/s-0.9 ~-the 0.4V scope in the liberation of hydrogen characteristic of investigation activated carbon electrodes.Test is found, compares with common electrolyte superbattery, and novel electrolyte lead-acid ultra-battery charcoal negative pole liberation of hydrogen reduces 10%-20%.
Embodiment 14
Allocate 1g/L isoquinolin in 5M sulfuric acid into, the 1g/L thiocarbamide is allocated the 10g/L natrium citricum into as hydrogen inhibitor, 10g/L (NH
4)
2SO
4Make electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in the 8:1:1 ratio, in mortar, fully grind after the 30min, add solvent NMP and continue to grind a period of time, again mixed slurry is applied on the collector, be pressed into pole plate, oven dry obtains activated carbon negative electrode.
The assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, with the sweep speed of 10mV/s-0.9 ~-the 0.4V scope in the liberation of hydrogen characteristic of investigation activated carbon electrodes.Test is found, compares with common electrolyte superbattery, and novel electrolyte lead-acid ultra-battery charcoal negative pole liberation of hydrogen reduces 10%-20%.
Embodiment 15
In 5M sulfuric acid, allocate 1g/LPb (NO into
3)
2, 1g/LGa
2O
3, 2g/LIn
2O
3, 5g/L (NH
4)
2SO
4Be mixed with electrolyte, can form a certain amount of [Pb (NH in the solution
3)
2]
2+Complex.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in the 8:1:1 ratio, in mortar, fully grind after the 30min, add solvent NMP and continue to grind a period of time, again mixed slurry is applied on the collector, be pressed into pole plate, oven dry obtains activated carbon negative electrode.
The assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, with the sweep speed of 10mV/s-0.9 ~-the 0.4V scope in the liberation of hydrogen characteristic of investigation activated carbon electrodes.Test is found, compares with common electrolyte superbattery, and novel electrolyte lead-acid ultra-battery charcoal negative pole liberation of hydrogen reduces 30%-40%.
Embodiment 16
Allocate 1g/L four sulphur cyanogen two ammoniums into and close chromium in 5M sulfuric acid, the 20g/L natrium citricum is mixed with electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in the 8:1:1 ratio, in mortar, fully grind after the 30min, add solvent NMP and continue to grind a period of time, again mixed slurry is applied on the collector, be pressed into pole plate, oven dry obtains activated carbon negative electrode.
The assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, with the sweep speed of 10mV/s-0.9 ~-the 0.4V scope in the liberation of hydrogen characteristic of investigation activated carbon electrodes.Test is found, compares with common electrolyte superbattery, and novel electrolyte lead-acid ultra-battery charcoal negative pole liberation of hydrogen reduces 30%-50%.
Embodiment 17
In 5M sulfuric acid, allocate 1g/LBi into
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 the 8:1:1 ratio, in mortar, fully grind after the 30min, add solvent NMP and continue to grind a period of time, again mixed slurry is applied on the collector, be pressed into pole plate, oven dry obtains activated carbon negative electrode.
The assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, with the sweep speed of 10mV/s-0.9 ~-the 0.4V scope in the liberation of hydrogen characteristic of investigation activated carbon electrodes.Test is found, compares with common electrolyte superbattery, and novel electrolyte lead-acid ultra-battery charcoal negative pole liberation of hydrogen reduces 30%-50%.
Embodiment 18
In 5M sulfuric acid, add 100ppmBi
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 the 8:1:1 ratio, in mortar, fully grind after the 30min, add solvent NMP and continue to grind a period of time, again mixed slurry is applied on the collector, be pressed into pole plate, oven dry obtains activated carbon negative electrode.
The assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, with the sweep speed of 10mV/s-0.9 ~-the 0.4V scope in the liberation of hydrogen characteristic of investigation activated carbon electrodes.Test is found, compares with common electrolyte superbattery, and novel electrolyte lead-acid ultra-battery charcoal negative pole liberation of hydrogen reduces 30%-60%, and simultaneously, charcoal negative pole specific capacity improves about 30%.
Embodiment 19
In 5M sulfuric acid, add 200ppmBi
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 the 8:1:1 ratio, in mortar, fully grind after the 30min, add solvent NMP and continue to grind a period of time, again mixed slurry is applied on the collector, be pressed into pole plate, oven dry obtains activated carbon negative electrode.
The assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, with the sweep speed of 10mV/s-0.9 ~-the 0.4V scope in the liberation of hydrogen characteristic of investigation activated carbon electrodes.Test is found, compares with common electrolyte superbattery, and novel electrolyte lead-acid ultra-battery charcoal negative pole liberation of hydrogen reduces 40%-60%, and simultaneously, charcoal negative pole specific capacity improves about 30%.
Embodiment 20
In 5M sulfuric acid, add 20g/L ZnSO
4, the NTA that adds again 5g/L dehydrogenated rosin imidazoline and 100ppm is mixed with electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in the 8:1:1 ratio, in mortar, fully grind after the 30min, add solvent NMP and continue to grind a period of time, again mixed slurry is applied on the collector, be pressed into pole plate, oven dry obtains activated carbon negative electrode.
The assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, with the sweep speed of 10mV/s-0.9 ~-the 0.4V scope in the liberation of hydrogen characteristic of investigation activated carbon electrodes.Test is found, compares with common electrolyte superbattery, and novel electrolyte lead-acid ultra-battery charcoal negative pole liberation of hydrogen reduces about 30%.
Embodiment 21
In 5M sulfuric acid, allocate 50ppmCd (OH) into
2, 5g/LZnSO
4Add again 1g/L isoquinolin and the 1g/L natrium citricum is mixed with electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in the 8:1:1 ratio, in mortar, fully grind after the 30min, add solvent NMP and continue to grind a period of time, again mixed slurry is applied on the collector, be pressed into pole plate, oven dry obtains activated carbon negative electrode.
The assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, with the sweep speed of 10mV/s-0.9 ~-the 0.4V scope in the liberation of hydrogen characteristic of investigation activated carbon electrodes.Test is found, compares with common electrolyte superbattery, and novel electrolyte lead-acid ultra-battery charcoal 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)
2The Na that adds again 1g/L isoquinolin and 5g/L
2SO
4, 5g/L (NH
4)
2SO
4Be mixed with electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in the 8:1:1 ratio, in mortar, fully grind after the 30min, add solvent NMP and continue to grind a period of time, again mixed slurry is applied on the collector, be pressed into pole plate, oven dry obtains activated carbon negative electrode.
The assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, with the sweep speed of 10mV/s-0.9 ~-the 0.4V scope in the liberation of hydrogen characteristic of investigation activated carbon electrodes.Test is found, compares with common electrolyte superbattery, and novel electrolyte lead-acid ultra-battery charcoal negative pole liberation of hydrogen reduces 60%-85%.
Embodiment 23
In 5M sulfuric acid, allocate respectively 100ppmBi into
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, the 1g/L phosphorylated ligand is made electrolyte.
Active carbon, conductive agent, bonding agent (PVDF) are prepared in the 8:1:1 ratio, in mortar, fully grind after the 30min, add solvent NMP and continue to grind a period of time, again mixed slurry is applied on the collector, be pressed into pole plate, oven dry obtains activated carbon negative electrode.
The assembling lead-acid ultra-battery, take carbon resistance rod as work electrode, saturated calomel electrode is reference electrode, with the sweep speed of 10mV/s-0.9 ~-the 0.4V scope in the liberation of hydrogen characteristic of investigation activated carbon electrodes.Test is found, compares with common electrolyte superbattery, and novel electrolyte lead-acid ultra-battery charcoal negative pole liberation of hydrogen reduces 62%-85%.
Claims (8)
1. lead-acid ultra-battery electrolyte, described electrolyte are by sulfuric acid, and liberation of hydrogen inhibitor and additive form; The molar concentration of described sulfuric acid is 5mol/L; Contain liberation of hydrogen inhibitor 0.001-20g, additive 0.001-10g in every liter of electrolyte; Described liberation of hydrogen inhibitor is at least a in organic substance or the metallic compound; Described metallic compound is at least a in oxide, salt, hydroxide or the ionic complex of metal.
2. a kind of lead-acid ultra-battery electrolyte according to claim 1 is characterized in that: the salt of metal is a kind of in sulfate, nitrate, phosphate, the carbonate.
3. a kind of lead-acid ultra-battery electrolyte according to claim 1 is characterized in that: the part of the ionic complex of metal is amino (NH
3), cyano group (CN) or thiocyanogen (at least a SCN).
4. according to claim 1,2 or 3 described a kind of lead-acid ultra-battery electrolyte, it is characterized in that: 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 any mixture of 1-3 kind.
5. a kind of lead-acid ultra-battery electrolyte according to claim 4, it is characterized in that: described metallic compound also comprises Bi
3+Or Bi
5+Metallic compound.
6. a kind of lead-acid ultra-battery electrolyte according to claim 4, it is characterized in that: the organic substance of described liberation of hydrogen inhibitor is 1-METHYLPYRROLIDONE, sodium carboxymethylcellulose, aniline, acid amides, rosin amine, thiocarbamide and thiourea derivative, cinnamic acid, furfural, amyl group 1, a kind of or any two kinds mixture in two (the dimethyl amine)-acetone of 2-, heterocycle ketoamine, dehydrogenated rosin imidazoline, N-vinylpyridine polymer, alkyl pyridine xanthates, pyridine and pyridine derivate, quinoline, isoquinolin, the isoquinilone derivatives.
7. a kind of lead-acid ultra-battery electrolyte according to claim 5, it is characterized in that: the organic substance of described liberation of hydrogen inhibitor is 1-METHYLPYRROLIDONE, sodium carboxymethylcellulose, aniline, acid amides, rosin amine, thiocarbamide and thiourea derivative, cinnamic acid, furfural, amyl group 1, a kind of or any two kinds mixture in two (the dimethyl amine)-acetone of 2-, heterocycle ketoamine, dehydrogenated rosin imidazoline, N-vinylpyridine polymer, alkyl pyridine xanthates, pyridine and pyridine derivate, quinoline, isoquinolin, the isoquinilone derivatives.
8. a kind of lead-acid ultra-battery electrolyte according to claim 6, it is characterized in that: 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 a in the nitrilotriacetic acid disodium.
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| CN104505538A (en) * | 2014-12-24 | 2015-04-08 | 福州大学 | Electrolyte additive for inhibiting hydrogen evolution of negative plate for lead-acid storage battery |
| CN105336945A (en) * | 2015-09-29 | 2016-02-17 | 双登集团股份有限公司 | High specific energy lead-acid battery production method |
| CN105428599A (en) * | 2015-11-23 | 2016-03-23 | 江苏海德森能源有限公司 | Method for producing long-life lead-carbon battery plate by modified activated carbon |
| CN106816643A (en) * | 2017-03-23 | 2017-06-09 | 福建省闽华电源股份有限公司 | A kind of lead-acid battery electrolyte containing betaine type amphoteric surfactant |
| CN108899591A (en) * | 2018-05-23 | 2018-11-27 | 淄博火炬能源有限责任公司 | Power type valve-regulated lead acid battery electrolyte and preparation method thereof |
| CN112640153A (en) * | 2018-05-07 | 2021-04-09 | 提卜斯研发有限公司 | Method of forming carbon-based active layer for anode of lead-carbon battery and active layer formed thereby |
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| 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 |
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| CN112640153A (en) * | 2018-05-07 | 2021-04-09 | 提卜斯研发有限公司 | Method of forming carbon-based active layer for anode of lead-carbon battery and active layer formed thereby |
| CN108899591A (en) * | 2018-05-23 | 2018-11-27 | 淄博火炬能源有限责任公司 | Power type valve-regulated lead acid battery electrolyte and preparation method thereof |
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| CN102945981B (en) | 2015-05-20 |
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