CN101515645B - Slab lattice of storage battery, production method and application thereof - Google Patents

Slab lattice of storage battery, production method and application thereof Download PDF

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Publication number
CN101515645B
CN101515645B CN2009100777620A CN200910077762A CN101515645B CN 101515645 B CN101515645 B CN 101515645B CN 2009100777620 A CN2009100777620 A CN 2009100777620A CN 200910077762 A CN200910077762 A CN 200910077762A CN 101515645 B CN101515645 B CN 101515645B
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grid
storage battery
purity
composition
alloy
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CN101515645A (en
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窦传龙
陈红雨
李瑞珍
彭曙光
张伟
陈顺
匡立春
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South China Normal University
Zhuzhou Smelter Group Co Ltd
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South China Normal University
Zhuzhou Smelter Group Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The embodiment of the invention provides a slab lattice of a storage battery, a production method and application thereof, belonging to the field of storage batteries. Components of the slab lattice in terms of mass percent are 0.06-0.14% of Ca, 0.1-1.9% of Sn, 0.01-0.04% of Al, 0.01-0.1% of Zn, 0.001-0.1% of Sm, 0.001-0.1% of La, and the balance of Pb. The slab lattice of storage battery, the production method and application thereof have advantages of prolonging service life of the storage battery, improving mechanical strength of the slab lattice, widening application range of the slab lattice and increasing passivation resistance of the slab lattice.

Description

The grid of storage battery and production method thereof and application
Technical field
The present invention relates to the storage battery field, relate in particular to a kind of grid and production method and application of storage battery.
Background technology
Variation along with global climate, people are more and more higher to the consciousness of environment, fuel-engined vehicle exhaust emission urban environment and CO2 (CO2 in the whole world 20% the derives from automobile exhaust gas) global warming issue that causes causes the common concern of national governments day by day, the world petroleum resource storage is gradually few in addition, electric motor car has begun to take shape emerging industry as a kind of vehicles of green intelligent and high-efficiency at world wide.And the problem of electric motor car most critical is the cycle life of its storage battery, the cycle life key of storage battery is the material of the grid of storage battery, the material of the grid of the storage battery that prior art provides is mainly, the Pb-Ca-Sn-Al alloy, wherein the content of Ca is 0.08%, the content of Sn is 0.3-0.6%, and the content of Al is 0.02-0.03%.
In realizing process of the present invention, the inventor finds the technical scheme of prior art, and there are the following problems:
Because the content of the Ca in the grid of the prior art is lower, so its mechanical strength is relatively poor.And grid of the prior art is when deep discharge, the very high PbSO of a large amount of resistance values of surface production 4The barrier layer, and cause battery " early stage capacity descends ", have a strong impact on the useful life of storage battery.
Summary of the invention
In view of above-mentioned existing in prior technology problem, embodiment of the present invention provides a kind of grid and production method and application of storage battery, and described grid and production method thereof and application have the mechanical strength height, the advantage of long service life.
The specific embodiment of the present invention provides a kind of grid of storage battery, comprising: the composition of described grid and the mass percent of each composition are:
Calcium Ca:0.06%-0.14%;
Tin Sn:0.1%-1.9%;
Aluminium Al:0.01%-0.04%;
Zinc Zn:0.01%-0.1%;
Samarium Sm 0.001%-0.1%;
Lanthanum La 0.001%-0.1%;
Surplus is plumbous Pb.
The specific embodiment of the invention also provides a kind of application of grid of above-mentioned storage battery, and this grid is applied to the grid of electromobile battery.
The specific embodiment of the invention also provides a kind of production method of grid of above-mentioned storage battery, and this method comprises:
A, purity is at least 99.9% Ca, purity is at least 99.9% Al, purity and is at least 99.9% Sm and purity and is at least 99.9% La and is vacuumizing, carry out melting in the crucible furnace of logical nitrogen protection and configure intermediate alloy; The temperature of described crucible furnace is 600～900 ℃;
B, purity is at least 99.9% Pb, purity is at least 99.9% Sn and purity and is at least 99.9% Zn and adds described intermediate alloy, and the temperature of described crucible furnace is adjusted into 550～650 ℃, after treating that fusing finishes, stir, even, static, drag for slag and handle after, be incubated cooling after 0.5～3 hour, described cooling rate is 10 2K/S～10 5K/S.
By the above-mentioned technical scheme that provides as can be seen, the technical scheme of the embodiment of the invention is used lanthanum element, can obviously improve the tensile property of stereotype behind the use lanthanum element, improved the mechanical strength of the grid of storage battery greatly, and technique scheme has also been used the Zn element, after using the Zn element, can reduce and destroy PbSO 4The barrier layer has increased useful life of storage battery.
Description of drawings
Fig. 1 is the flow chart of the grid production method of the described storage battery of the specific embodiment of the invention.
Embodiment
Embodiment of the present invention provides a kind of grid of storage battery, and the composition of this grid and the mass percent of each composition are: calcium Ca:0.06%-0.14%; Tin Sn:0.1%-1.9%; Aluminium Al:0.01%-0.04%; Zinc Zn:0.01%-0.1%, samarium Sm 0.001%-0.1%, lanthanum La 0.001%-0.1%, surplus is plumbous Pb.And the concrete composition of the grid of this storage battery can be as shown in table 1:
Table 1:
Below by the theory analysis of each element technique effect to the grid of storage battery is described in detail.
Zinc is that silvery white metal is slightly blue, easily forms alloy.It is that periodic system II B element is the d p-block element p adjacent with the P p-block element p, has the character similar to the d p-block element p.Similar a bit to the P district metallic element in fourth, fifth, six cycles again in nature at some, zinc is the close-packed hexagonal metal, can form high plumbous eutectic alloy with lead, is fit to do the grid alloy of the maintenance free cell of dark circulation.The affiliation that adds of zinc destroys the PbSO that plumbous calcium grid surface is produced 4Passivation layer, particularly the Zn of adding 0.01%-0.1% in grid can significantly destroy the PbSO that the grid surface is produced 4Passivation layer, thus the conductivity of grid passivating film increased, can avoid the grid surface passivated membrane too fine and close, strengthen being connected of grid and active material, the prevention active material comes off.Mechanics Performance Testing is the result show, interpolation Zn element can improve the hardness of grid, the adding of zinc can improve the conductivity of active material and grid interfacial corrosion film, make contact between active material and the grid more firm, stability is better, improves intensity, and the performance such as anti-passivation of anode plate grid.
Samarium is silvery white rare earth metal, and is more stable in dry air, can form oxide skin(coating) in humid air.Samarium belongs to light rare earth (samarium group rare-earth), is 7.9 in the abundance of occurring in nature, ranks the 7th, it is high that its abundance ratio tin (Sn 2.2) is wanted, compared with high especially many of tungsten (W 1.0) and molybdenum (Mo 1.5), in the abundance ranking list in whole element earth's crust, rank 40, be the relatively abundanter element of nature.Electrode potential and the Ca of Sm are close.Sm (180.2pm) has similar atomic radius with Pb (175.0pm), and Sm has higher hardness and better mechanical strength than Pb, Ca, add the formation that samarium metal can suppress the non-stoichiometry lead oxide of poorly conductive in the grid corrosive film, grid corrosive film conductivity is strengthened, and improved the corrosion resistance of grid, so that eliminate the generation of premature capacity loss phenomenon.Add liberation of hydrogen and overpotential for oxygen evolution that samarium metal can improve grid, help the sealing of storage battery, the adding of rare earth samarium is the refinement alloy structure obviously, the plasticity of grid is increased, by samarium is joined in the grid, be implemented under the hot environment and the situation of overcharging under not dehydration of storage battery, solve storage battery in hot environment and when overcharging to battery performance, improve the useful life of storage battery.
In rare earth element family, lanthanum is a very important member beyond doubt, and abundance is 32ppm in its earth's crust, accounts for 14.1% of the total abundance of rare earth, is only second to cerium and neodymium, occupies the 3rd.Rare earth element is as typical metallic element, and its metal activity is only second to alkali metal and alkaline-earth metal, and rare earth uses with the form of norium or intermediate alloy usually as the purification and the alterant of metal material.And lanthanum is as the most active a member, removing nonmetallic inclusion and low-melting-point metal impurity such as lead, tin such as oxygen, sulphur, phosphorus, and aspect such as crystal grain thinning can be brought into play the effect that stands in the breach naturally, can obviously improve anti-folding and draw performance, make the grid mechanical strength improve hundreds of times, not only improve the stereotype shielding property, also enlarged the range of application of grid, and improved the mechanical strength of grid.Particularly in grid, increase the lanthanum of 0.001%-0.1%, can better reach above-mentioned technique effect.(0.9v) Pb[II when interpolation of lanthanum not only can suppress deep discharge] growth of oxide-film, and the growth of the anode PbO2 film of (1.3v) can suppress the floating charge current potential time.Can slow down the generation of corrosion, further increase the useful life of storage battery.
Another embodiment that embodiment of the present invention provides also provides a kind of grid of storage battery, and the composition of this grid and the mass percent of each composition are: calcium Ca:0.06%-0.14%; Tin Sn:0.1%-1.9%; Aluminium Al:0.01%-0.04%; Silver Ag:0.005%-0.2%, lanthanum La 0.001%-0.1%, surplus is plumbous Pb.And the concrete composition of the grid of this storage battery can be as shown in table 2:
Table 2:
Composition Embodiment 21 Embodiment 22 Embodiment 23 Embodiment 24 Embodiment 25 Embodiment 26
Ca(％)? 0.06? 0.08? 0.1? 0.12? 0.13? 0.14?
Sn(％)? 1.9? 1.5? 1.3? 0.8? 0.6? 0.1?
Al(％)? 0.01? 0.02? 0.025? 0.03? 0.035? 0.04?
Ag(％)? 0.2? 0.15? 0.08? 0.03? 0.01? 0.005?
La(％)? 0.1? 0.08? 0.05? 0.02? 0.01? 0.001?
Pb? Surplus Surplus Surplus Surplus Surplus Surplus
Below by the theory analysis of each element technique effect to the grid of the storage battery in the present embodiment is described in detail.
By in grid, adding the useful life that lanthanum can strengthen storage battery, can remove nonmetallic inclusion and low-melting-point metal impurity such as lead, tin such as oxygen, sulphur, phosphorus, and crystal grain thinning, and can improve the mechanical strength of grid.
And in grid, add Ag, can improve the intensity and the creep strength of grid, slow down grid overaging effect in use, Ag can also suppress the growth of grid alloy corrosion layer, increased the conductivity of corrosion layer, improved the decay resistance of alloy in sulfuric acid solution, Ag has increased overpotential of hydrogen evolution simultaneously, reduce the sensitiveness of oxygen evolution potential to temperature, add Ag thus, obviously improve the dark circulation ability of maintenance-free lead-acid battery, particularly overcharge and the severe environmental conditions of high temperature under, improved the cycle life of storage battery greatly.
The specific embodiment of the invention also provides a kind of application of grid of above-mentioned storage battery, and the grid of this storage battery is applied to the grid of electromobile battery.
The specific embodiment of the invention is applied to the grid of electromobile battery with the grid of above-mentioned storage battery, thereby has improved the performance of electromobile battery, has increased the useful life of electric motor car, and has also improved the working strength of electromobile battery grid.
The specific embodiment of the invention also provides a kind of production method of grid of above-mentioned storage battery, and this method comprises as shown in Figure 1:
Step 11, purity is at least 99.9% Ca, purity is at least 99.9% Al, purity and is at least 99.9% samarium and purity and is at least 99.9% lanthanum and is vacuumizing, carry out melting in the crucible furnace of logical nitrogen protection and configure intermediate alloy; The temperature of this crucible furnace melting can be 600～900 ℃;
Step 12, purity is at least 99.9% Pb, purity is at least 99.9% Sn and purity and is at least 99.9% Zn and adds this intermediate alloy, and the smelting temperature of this crucible furnace is adjusted into 550～650 ℃, after treating that fusing finishes, stir, even, static, drag for slag and handle after, be incubated after 0.5～3 hour the grid that cooling obtains a kind of storage battery that the invention embodiment provides, and the control cooling rate is 10 2K/S～10 5K/S.
Optionally, cooling specifically can also comprise after this was incubated 0.5～3 hour, to stir, alloy inspection by sampling even, static, after dragging for slag and handling qualified after, cooling after being incubated 0.5～3 hour, this is up to the standards and is the composition of the grid that this stirs, the mass percentage content of the composition of even, static, alloy after dragging for slag and handling and composition meets a kind of storage battery that the specific embodiment of the invention provides and the mass percent of composition.
The grid of the storage battery that the method that the specific embodiment of the invention provides is produced has and improves storage battery useful life, improves the grid mechanical strength, enlarges the range of application of grid, improves the advantage of the anti-passivation ability of grid.
In sum, the technical scheme that the specific embodiment of the invention provides has and improves storage battery useful life, improves the grid mechanical strength, enlarges the range of application of grid, improves the advantage of the anti-passivation ability of grid.
The above; only be the preferable embodiment of the present invention; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the embodiment of the invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection range of claim.

Claims (4)

1. the grid of a storage battery is characterized in that, the composition of described grid and the mass percent of each composition are:
Calcium Ca:0.06%-0.14%;
Tin Sn:0.1%-1.9%;
Aluminium Al:0.01%-0.04%;
Zinc Zn:0.01%-0.1%;
Samarium Sm 0.001%-0.1%;
Lanthanum La 0.001%-0.1%;
Surplus is plumbous Pb.
2. the application of the grid of a storage battery as claimed in claim 1 is characterized in that, described grid is applied to the grid of electromobile battery.
3. the production method of the grid of a storage battery as claimed in claim 1 is characterized in that, described method comprises:
A, purity is at least 99.9% Ca, purity is at least 99.9% Al, purity and is at least 99.9% Sm and purity and is at least 99.9% La and is vacuumizing, carry out melting in the crucible furnace of logical nitrogen protection and configure intermediate alloy; The temperature of described crucible furnace is 600～900 ℃;
B, purity is at least 99.9% Pb, purity is at least 99.9% Sn and purity and is at least 99.9% Zn and adds described intermediate alloy, and the temperature of described crucible furnace is adjusted into 550～650 ℃, after treating that fusing finishes, stir, even, static and drag for slag and handle after, be incubated cooling after 0.5～3 hour, described cooling rate is 10 2K/S～10 5K/S.
4. method as claimed in claim 3, it is characterized in that, described method specifically comprises: will stir, even, static and drag for slag and handle after the alloy inspection by sampling qualified after, be incubated after 0.5～3 hour cooling, described being up to the standards is the mass percent that describedly stirs, mass percent even, static and that drag for the composition of the alloy after slag is handled and each composition meets composition and each composition of grid as claimed in claim 1.
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Publication number Priority date Publication date Assignee Title
CN105958080A (en) * 2016-06-30 2016-09-21 济源市万洋绿色能源有限公司 Negative plate grid alloy prepared from secondary lead
CN107579255A (en) * 2017-07-29 2018-01-12 黄建平 A kind of positive electrode grid of lead storage battery alloy and preparation method thereof
CN110233245A (en) * 2019-04-23 2019-09-13 旭派电源有限公司 A kind of lead carbon battery cathode assists the preparation method of agent prescription and cathode

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CN1750311A (en) * 2005-08-31 2006-03-22 长沙丰日电气集团有限公司 Valve control type lead acid accumulator for metro vehicle

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CN1750311A (en) * 2005-08-31 2006-03-22 长沙丰日电气集团有限公司 Valve control type lead acid accumulator for metro vehicle

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