CN102593529A - Variable-polarity lead-acid battery and using method thereof - Google Patents
Variable-polarity lead-acid battery and using method thereof Download PDFInfo
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- CN102593529A CN102593529A CN2012100431840A CN201210043184A CN102593529A CN 102593529 A CN102593529 A CN 102593529A CN 2012100431840 A CN2012100431840 A CN 2012100431840A CN 201210043184 A CN201210043184 A CN 201210043184A CN 102593529 A CN102593529 A CN 102593529A
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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
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- 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 a variable-polarity lead-acid battery and a using method of the variable-polarity lead-acid battery. Positive and negative plates of the lead-acid battery consist of the same grids and lead plasters, and after one or more times of charge-discharge cycle of the battery, the polarities of the positive and negative plates are exchanged. The variable-polarity lead-acid battery has the advantages that the problem of vitriolization of an ordinary lead-acid battery can be solved, the service life of the battery is prolonged, and the utilization ratio of active substances is increased at the same time, so that the charge receptivity and the discharge capacity of the battery are greatly improved.
Description
Technical field
The invention discloses a kind of Variable Polarity lead-acid battery and method for using thereof, belong to the electrochemical energy storing device field.
Background technology
After Gai Si in 1859 rose Prandtl invention lead acid accumulator, lead acid accumulator was the most widely used product of field of batteries always, as all adopting lead acid accumulator on automobile, locomotive, steamer, aircraft, mobile communication and the reserve power supply unit.In the decades that novel batteries such as nickel-cadmium cell, nickel-hydrogen cell, lithium ion battery go on the market in succession, it still can occupy most of market share securely, and this has embodied the advantage of lead-acid battery at aspects such as cost, fail safes fully.At present, in miniature hybrid power type electric automobile and extraordinary electric motor car, all be to use lead-acid battery more than 95%.As the miniature and slight hybrid electric vehicle of oil electric mixed dynamic automobile, lead-acid battery has also obtained successful application as chemical power source.
But lead-acid battery cycle life is short, and the single cycle cost is high, is the one of the main reasons that the lead-acid battery development is under suspicion.In the electrokinetic cell application facet, complicated driving process often makes and causes negative pole promptly " irreversible sulfation " by the lead-acid battery super-charge super-discharge, battery life is terminated too early especially.According to statistics, in the failure mode of power type VRLA lead-acid battery, have 70～80%, battery " irreversible sulfation " causes.Therefore, sulfation is that the lead-acid battery industry endeavours to want the problem that solves always.People have carried out big quantity research to lead-acid battery negative electrode grid composition, structure and active material composition, coating method etc. and have improved, and all can only slow down to a certain extent and can't fundamentally eliminate " sulfation " problem.For addressing the above problem, we need the reason of anticathode sulfation to inquire into.The lead-acid battery charge and discharge process reacts as follows:
(1) anodal reaction
Charging: PbSO
4+ 2e
-+ 2H
2O=PbO
2+ 4H
++ SO
4 2-
Discharge: PbO
2+ 2e
-+ SO
4 2-+ 4H
+=PbSO
4(R)+2H
2O
(2) negative reaction
Charging: PbSO
4+ 2e
-=Pb+SO
4 2-
Discharge: Pb-2e
-+ SO
4 2-=PbSO
4(O)
If with PbO
2The PbSO that reduction generates
4Be defined as PbSO
4(R), the PbSO that the Pb oxidation is generated
4Be defined as PbSO
4(O).Discover PbSO
4(O) rete intermediate ion migration impedance is PbSO
4(R) 5-10 times, i.e. the PbSO of the anodal formation of lead-acid battery
4(R) PbSO that forms than negative pole
4(O) active much higher, just because of negative pole PbSO
4(O) low activity, PbSO
4(O) charging process can't be reduced to Pb fully, gathers serious obstruction battery charging and discharging at negative pole gradually, finally causes the battery sulfation and loses efficacy.If therefore can make negative pole low activity PbSO
4(O) → process of Pb becomes high activity PbSO
4(R) → and Pb, must greatly improve the charge acceptance of negative pole, improve the negative electrode active material utilance, and reduce the negative pole sulfation, and the conversion battery polar can reach this purpose.Use in the lead-acid battery activation process after conversion lead-acid battery polarity lost efficacy to sulfation in early days; Inefficacy lead-acid battery after the reverse charging activation can regain capacity and charge-discharge performance preferably in a short time; But because lead-acid battery both positive and negative polarity composition exists than big-difference; Some additives in the reverse charging process in the former negative pole can be oxidized and lost efficacy, and makes that the battery life after the reverse significantly shortens, so common lead-acid battery is forbidden the both positive and negative polarity reversal connection.
The present invention is based on the microcosmic mechanism of lead-acid battery reaction, proposed the notion with the lead-acid battery reverse first, the composition of the formation anode of selecting for use and the battery grid material of negative pole and lead plaster all can satisfy the reaction requirement after the both positive and negative polarity conversion; And battery pole plates designed again; Purpose is thoroughly to eliminate " negative pole sulfation " problem of puzzlement lead-acid battery industry a century; And can greatly improve active material utilization; Increase battery charge ability to accept and large current discharging capability, improve lead-acid battery cycle life and charge/discharge capacity.
Summary of the invention
One of the object of the invention provides a kind ofly can eliminate lead-acid battery negative pole sulfation problem; Improve the negative pole charge acceptance; Improve the large current charge performance of lead-acid battery; Improve the negative plate discharge capability, improve the lead-acid battery heavy-current discharge performance, and the method for using of the lead-acid battery that increases the service life and this battery.
A kind of Variable Polarity lead-acid battery, described battery is made up of grid and lead plaster, and the battery grid material that constitutes anode and negative pole is consistent, and the composition and the content of the lead plaster of formation anode and negative pole are consistent.
Described battery grid is stereotype grid, lead alloy grid, lead plating grid or porous grid.
Alloying element in the said lead alloy grid comprises at least a among Ca, Al, Sn, Ag, Bi, Sb, Te, Ce, La, Nd, Sm, Gd, Pr, Tb, Yb, Y, the Eu, and its quality percentage composition is no more than 10%.
Said lead plating grid is made up of matrix and lead alloy coating; Wherein matrix is a kind of among glass fiber, Cu, Al, Ti and the C; Alloying element comprises at least a among Ca, Al, Sn, Ag, Bi, Sb, Te, Ce, La, Nd, Sm, Gd, Pr, Tb, Yb, Y, the Eu in the said lead alloy coating, and its quality percentage composition is no more than 10%.
Said porous grid is porous lead grid or porous lead plating grid.
Said porous lead plating grid is made up of porous matrix and lead alloy coating; Wherein, said porous matrix is a kind of in porous glass fiber, porous C u, porous Al, porous Ti and the porous charcoal; Alloying element comprises at least a among Ca, Al, Sn, Ag, Bi, Sb, Te, Ce, La, Nd, Sm, Gd, Pr, Tb, Yb, Y, the Eu in the said lead alloy coating, and its quality percentage composition is no more than 10%.
Said lead plaster is except that the Pb powder with the sulfuric acid, also comprises at least a in raw material of wood-charcoal material, metal oxide and the additive; The quality percentage composition of said each component of lead plaster is respectively: raw material of wood-charcoal material 0～20%, and metal oxide 0～20%, additive 0～10%, surplus is Pb powder and sulfuric acid; Wherein,
Said raw material of wood-charcoal material comprises at least a in carbon black, active carbon, charcoal fiber, graphite, acetylene black, CNT, charcoal-aero gel, the Graphene;
Said metal oxide comprises Ru
2O
3, PbO
2, TiO
2, MnO
2, ZnO, Cr
2O
3, V
2O
5, NiO, ZrO
2, MoO
3, WO
3In at least a;
Said additive is Na
2SO
4, K
2SO
4, CaSO
4, MgSO
4, BaSO
4, CoSO
4, (NH
4)
2SO
4, (NH
4)
2Cr
2O
7, SnO, Bi
2O
3, CMC, sodium lignosulfonate, RSO
3H with gather at least a in propionitrile fiber, polypropylene fibre, the terylene.
The both positive and negative polarity of described battery can exchange.
Above-mentioned battery is every in use through both positive and negative polarity is exchanged once.
When common lead-acid battery was used, charge and discharge process positive electrode material conversion process was: PbSO
4(R) (charging) → PbO
2(discharge) → PbSO
4(R) (charging) The negative material transition process is: PbSO
4(O) (charging) → Pb (discharge) → PbSO
4(O) (charging) ...Be that positive pole is PbO always
2/ PbSO
4(R) transform each other, negative pole is Pb/PbSO always
4(O).And the present invention is through carrying out creationary improvement to grid and lead plaster, and polarity can be exchanged when lead-acid battery used, and the material transformation process is on the electrode: Pb (discharge) → PbSO
4(O) (pole-changing charging) → PbO
2(discharge) → PbSO
4(R) (pole-changing charging) → Pb (discharge) ...
The present invention has the following advantages:
(1) because both positive and negative polarity conversion always PbSO can not occur
4Gathering (O) fundamentally eliminated negative pole sulfation problem, extending battery life;
(2) owing to adopt novel same sex pole plate, the cell active materials utilance reaches 80-90%, and the cell capacity is enhanced about more than once;
(3) negative pole is by PbSO
4(O) become PbSO
4(R), can reduce the polarization of charging process negative pole, reduce the current potential of constant current charge process, thereby reduce liberation of hydrogen;
(4) the negative pole charging all is PbSO in any one circulation
4(R) → and Pb, because PbSO
4(R) high activity, the charge acceptance of negative pole can improve 3-5 doubly, thereby improve the lead-acid battery charge acceptance;
(5) because positive/negative plate is identical, can simplify the preparation technology of battery, thereby reduce manufacturing cost.
Embodiment
Below in conjunction with embodiment, the present invention is done further explain, but must not these embodiment be interpreted as the restriction to protection range of the present invention.
Embodiment 1:
Get carbon black 5%, charcoal fiber 2%, CNT 0.5% gathers propionitrile short fiber 2%, MnO
22%, sodium lignosulfonate 0.2%, BaSO
40.3%, surplus is Pb powder and H
2SO
4(allocate 1.4g/LH into by pure sour 42g/kgPb standard flour
2SO
4) and cream after on the Pb-2%Sb alloy grid, be pressed into pole piece, under 75 ℃ of high humiditys (RH100%) condition, solidify 24h, adopt the outer technology that changes into a battery lead plate part that makes is changed into to be that positive pole, a part change into and to be to be assembled into battery at last by negative pole.Manual switch primary cell polarity after per 3 charge and discharge cycles.
With battery with 0.5I
3The A constant current charge is to the 2.4V/ monomer, again with the 2.4V constant voltage charge to current stabilization, leave standstill 30min, then with I
3A current discharge to 1.65V/ monomer stops, and more than is a charge and discharge cycles.Test finds that in 400 circulations, common lead-acid battery capacity is downward trend gradually; It is about 20% that 400 circulation times, first cyclic discharge capacity descend, and Variable Polarity lead-acid battery discharge capacity is in circulation initial stage ascendant trend gradually; 400 times the first discharge capacity of circulation time has improved about 20%; 800 when circle capacity still have 105% of initial capacity, show that the Variable Polarity battery can eliminate the sulfation of negative pole, and significantly improve the cell active materials utilance.
After the Variable Polarity battery changed polarity, charge fully, leave standstill 5h, again under 25 ℃ environment with 3I
3A current discharge to 1.50V/ monomer stops, and writes down discharge time.Test finds that common plumbic acid battery discharge time is 55min, and Variable Polarity lead-acid battery discharge time is 80min, show change polarity after the cell active materials utilance rise, large current discharging capability strengthens.
With battery with 0.5I
3The A constant current charge is to the 2.4V/ monomer, then with 0.25I
3The A electric current continues charging 5h, record charging process potential value.Test finds that common plumbic acid cell potential sharply rises to about 2.5-2.6V, and the Variable Polarity battery remains near the 2.4V, shows that the Variable Polarity battery polarization is less, and correspondingly its liberation of hydrogen must reduce.
Embodiment 2:
Get acetylene black 10%, charcoal fiber 3%, Graphene 2% gathers propionitrile short fiber 3%, TiO
210%, BaSO
42%, surplus is Pb powder and H
2SO
4(allocate 1.4g/LH into by pure sour 42g/kgPb standard flour
2SO
4); With on the Pb-5%Sn-0.1%Ca-Ce0.05% alloy grid, be pressed into pole piece behind the cream, under 75 ℃ of high humiditys (RH100%) condition, solidify 24h, adopt the outer technology that changes into a battery lead plate part that makes is changed into to be positive pole; A part changes into and is to be assembled into battery at last by negative pole.Polarity of manual switch after per 10 charge and discharge cycles.
With battery with 0.5I
3The A constant current charge is to the 2.4V/ monomer, again with the 2.4V constant voltage charge to current stabilization, leave standstill 30min, then with I
3A current discharge to 1.65V/ monomer stops, and more than is a charge and discharge cycles.Test is found; In 400 circulations; Common lead-acid battery capacity is downward trend gradually; 400 circulation times; The first cyclic discharge capacity of common lead-acid battery capacity descends about 15%; And Variable Polarity lead-acid battery discharge capacity all has rising after each change polarity, and 400 circulation time discharge capacities still are about 140% of first discharge capacity.
Embodiment 3:
Get active carbon 10%, charcoal-aero gel 5%, carbon nanotube 2% gathers propionitrile short fiber 2%, RuO
25%, ZnO5%, BaSO
41%, surplus is Pb powder and H
2SO
4(allocate 1.4g/LH into by pure sour 42g/kgPb standard flour
2SO
4) and cream after on porous lead grid (Pb-Sn10%), be pressed into pole piece, under 75 ℃ of high humiditys (RH100%) condition, solidify 24h, adopt the outer technology that changes into a battery lead plate part that makes is changed into to be that positive pole, a part change into and to be to be assembled into battery at last by negative pole.Manual switch primary cell polarity after per 3 degree of depth charge and discharge cycles.
With battery with 0.5I
3The A constant current charge is to the 2.4V/ monomer, again with the 2.4V constant voltage charge to current stabilization, leave standstill 30min, then with I
3A current discharge to 1.65V/ monomer stops, and more than is a charge and discharge cycles.Test finds that in 400 circulations, common lead-acid battery capacity is downward trend gradually; 400 circulation times; It is about 15% that first cyclic discharge capacity descends, and Variable Polarity lead-acid battery discharge capacity rises gradually, and 400 circulation time discharge capacities are 135% of first discharge capacity; After 800 circulations, battery capacity does not still have obvious decline.
Embodiment 4:
Get acetylene black 10%, active carbon 5%, Graphene 5% gathers propionitrile short fiber 4%, Cr
2O
310%, (NH
4)
2Cr
2O
72%, BaSO
45%, surplus is Pb powder and H
2SO
4(allocate 1.4g/LH into by pure sour 42g/kgPb standard flour
2SO
4) and cream after on Al base lead plating alloy grid, be pressed into pole piece, under 75 ℃ of high humiditys (RH100%) condition, solidify 24h, adopt the outer technology that changes into a battery lead plate part that makes is changed into to be that positive pole, a part change into and to be to be assembled into battery at last by negative pole.Polarity of manual switch after per 10 degree of depth charge and discharge cycles.
With battery with 0.5I
3The A constant current charge is to the 2.4V/ monomer, again with the 2.4V constant voltage charge to current stabilization, leave standstill 30min, then with I
3A current discharge to 1.65V/ monomer stops, and more than is a charge and discharge cycles.Test finds that in 400 circulations, Variable Polarity lead-acid battery discharge capacity rises gradually, and 400 circulation time discharge capacities are 142% of first discharge capacity, and after 800 circulations, battery capacity does not still have obvious decline.
Embodiment 5:
Get charcoal fiber 7%, gather propionitrile short fiber 3%, Ru
2O
310%, MnO
210%, BaSO
40.5%, Bi
2O
30.5%, surplus is Pb powder and H
2SO
4(allocate 1.4g/LH into by pure sour 42g/kgPb standard flour
2SO
4) and cream after on porous aluminum lead plating grid, be pressed into pole piece, under 75 ℃ of high humiditys (RH100%) condition, solidify 24h, adopt the outer technology that changes into a battery lead plate part that makes is changed into to be that positive pole, a part change into and to be to be assembled into battery at last by negative pole.Polarity of manual switch after per 3 degree of depth charge and discharge cycles.
With battery with 0.5I
3The A constant current charge is to the 2.4V/ monomer, again with the 2.4V constant voltage charge to current stabilization, leave standstill 30min, then with I
3A current discharge to 1.65V/ monomer stops, and more than is a charge and discharge cycles.Test finds that 400 circulation time discharge capacities of Variable Polarity lead-acid battery are 130% of first discharge capacity.After 800 circulations, battery capacity does not still have obvious decline.
The Variable Polarity battery is charged fully, leaves standstill 5h, again under 25 ℃ environment with 3I
3A current discharge to 1.50V/ monomer stops, and writes down discharge time.Test finds that the plumbous Variable Polarity lead-acid battery of foam reaches 100min discharge time, show change polarity after the cell active materials utilance rise, large current discharging capability strengthens.
Claims (9)
1. a Variable Polarity lead-acid battery is characterized in that, described battery is made up of grid and lead plaster, and the battery grid material that constitutes anode and negative pole is consistent, and the composition and the content of the lead plaster of formation anode and negative pole are consistent.
2. battery according to claim 1 is characterized in that, described battery grid is stereotype grid, lead alloy grid, lead plating grid or porous grid.
3. battery according to claim 2; It is characterized in that: the alloying element in the said lead alloy grid comprises at least a among Ca, Al, Sn, Ag, Bi, Sb, Te, Ce, La, Nd, Sm, Gd, Pr, Tb, Yb, Y, the Eu, and its quality percentage composition is no more than 10%.
4. battery according to claim 2 is characterized in that: said lead plating grid is made up of matrix and lead alloy coating; Wherein, said matrix is a kind of among glass fiber, Cu, Al, Ti and the C; Alloying element comprises at least a among Ca, Al, Sn, Ag, Bi, Sb, Te, Ce, La, Nd, Sm, Gd, Pr, Tb, Yb, Y, the Eu in the said lead alloy coating, and its quality percentage composition is no more than 10%.
5. battery according to claim 2 is characterized in that: said porous grid is porous lead grid or porous lead plating grid.
6. battery according to claim 5 is characterized in that: said porous lead plating grid is made up of porous matrix and lead alloy coating; Wherein, said porous matrix is a kind of in porous glass fiber, porous C u, porous Al, porous Ti and the porous charcoal; Alloying element comprises at least a among Ca, Al, Sn, Ag, Bi, Sb, Te, Ce, La, Nd, Sm, Gd, Pr, Tb, Yb, Y, the Eu in the said lead alloy coating, and its quality percentage composition is no more than 10%.
7. battery according to claim 1 is characterized in that: said lead plaster is except that the Pb powder with the sulfuric acid, also comprises at least a in raw material of wood-charcoal material, metal oxide and the additive; The quality percentage composition of said each component of lead plaster is respectively: raw material of wood-charcoal material 0～20%, and metal oxide 0～10%, additive 0～10%, surplus is Pb powder and sulfuric acid; Wherein,
Said raw material of wood-charcoal material comprises at least a in carbon black, active carbon, charcoal fiber, graphite, acetylene black, CNT, charcoal-aero gel, the Graphene;
Said metal oxide comprises Ru
2O
3, PbO
2, TiO
2, MnO
2, ZnO, Cr
2O
3, V
2O
5, NiO, ZrO
2, MoO
3, WO
3In at least a;
Said additive is Na
2SO
4, K
2SO
4, CaSO
4, MgSO
4, BaSO
4, CoSO
4, (NH
4)
2SO
4, (NH
4)
2Cr
2O
7, SnO, Bi
2O
3, CMC, sodium lignosulfonate, RSO
3H with gather at least a in propionitrile fiber, polypropylene fibre, the terylene.
8. battery according to claim 1 is characterized in that the both positive and negative polarity of described battery can exchange.
9. the method for using of any described battery of claim 1-8 is characterized in that, and is every through both positive and negative polarity is exchanged once when described battery uses.
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|---|---|---|---|
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| CN103227316A (en) * | 2013-04-03 | 2013-07-31 | 江苏海德森能源有限公司 | Positive electrode plate of lead-acid battery and preparation method thereof |
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