CN1819312A - Accumulator plate grid alloy with lead, calcium, strontium and rare earth - Google Patents
Accumulator plate grid alloy with lead, calcium, strontium and rare earth Download PDFInfo
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- CN1819312A CN1819312A CNA2005100239117A CN200510023911A CN1819312A CN 1819312 A CN1819312 A CN 1819312A CN A2005100239117 A CNA2005100239117 A CN A2005100239117A CN 200510023911 A CN200510023911 A CN 200510023911A CN 1819312 A CN1819312 A CN 1819312A
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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
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- Y02E60/10—Energy storage using batteries
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Abstract
The alloy is composed of 0.06-0.08% by weight Ca, 0.80-2.50% by weight Sn, 0.02-0.05% by weight Sr, and lead in amount of margin. Appropriate amount of Sr is added to improve corrosion-resistance and creep-resistance of the alloy, and to last useful life, and to improve age hardening speed, hardness and mechanic properties, and also to improve the early capacity loss and poor deep cycle ability.
Description
Affiliated technical field
The present invention relates to a kind of slab lattice alloy of lead-acid battery.
Background technology
The development of the reform of industrial structure, environmental protection, utilization of resources and resource regeneration etc. has proposed many new requirements to lead acid accumulator.To this, countries in the world are all at the high performance battery of research and development, solve the reliability of lead acid accumulator, non-maintaining property, dark circulation, problem such as corrosion-resistant.And grid alloy more plays an important role in the development process of storage battery as the main part of storage battery.
Present some slab lattice alloy of lead-acid battery that use, because dark circulation ability is poor, decay resistance is lower, and then the dark charge and discharge cycles useful life of having reduced maintenance free cell.
Summary of the invention
At the shortcoming of above-mentioned grid alloy, the present invention proposes the accumulator plate grid alloy of a kind of decay resistance and creep-resistant property.
Among the present invention, an amount of strontium is joined in the lead-calcium alloy, the two complements one another to make calcium and strontium, improves the deficiency such as dilatancy, poor corrosion resistance of calcium with the superiority of strontium, and the hardness with calcium constituent solves the defective that grid feels like jelly simultaneously.
The percentage by weight that the present invention includes alloying component is 0.06～0.08%Ca, 0.80～2.50%Sn, 0.02～0.05%Sr, plumbous surplus.
Beneficial effect of the present invention:
(1), adds an amount of Preparation of Metallic Strontium, in order to decay resistance and the creep-resistant property that improves alloy, prolong the useful life of alloy, improve aging hardening speed, hardness and the mechanical performance of alloy, can effectively improve the early stage capacitance loss of lead-calcium alloy and the problem of dark circulation ability difference.
(2), the interpolation of rare earth element, refinement alloy grain, improved the hot-working character of alloy, increased the toughness and the creep-resistant property of alloy, thereby improved the decay resistance of grid alloy.
(3), the interpolation of rare earth element, improved the anode film impedance operator, controlled PbSO in the corrosive film effectively
4Formation and reduce the thickness of corrosive film, improved the conductivity of anode plate grid and active material, and then improved the dark charge and discharge cycles useful life of maintenance free cell.
(4), the adding of silver in the alloy, can improve the mechanical property and the creep-resistant property of grid alloy, and can significantly improve the dark circulation ability of maintenance-free lead-acid battery and increase useful life of grid.
(5), the Pb that exists in the alloy of the present invention
3Ca, Pb
3Sr, Pb
3Sn, Pb
3(Ca
xSn
1-x) high melting compound, played the effect of alterant (nucleating agent), hindered grain growth, refinement crystal grain, make alloy have good mechanical strength.
Embodiment
The present invention is further described to use embodiment below again
Theoretical foundation of the present invention:
(1), addition element strontium (Sr) in alloy
Strontium and calcium are congenerss, and strontium is slightly soluble in liquid lead, can form rich lead compound SrPb with lead under certain condition
3Lead strontium alloy is similar to lead-calcium alloy, but it does not have the shortcoming of lead-calcium alloy, so people are more active to the research of lead strontium alloy in recent years.
Add an amount of strontium, can improve the aging hardening speed and the hardness of alloy.When replacing calcium to add in the Pb-Sn-Al alloy with strontium, not only the flowability of alloy and castability are better than lead-calcium alloy, but also have overcome the weakness of lead-calcium alloy early strength difference.The lead strontium alloy hardening mechanism is similar to lead-calcium alloy, promptly form the fine grain precipitation in lead base matter, but harder than calcium alloy, and have the fast characteristics of timeliness, this tensile strength of alloys reaches 53.23MPa, and (and the tensile strength of Pb-Ca-Sn-Al alloy only is 44.4 ~ 44.8MPa), and percentage elongation is 15%; Brinell hardness after 24 hours is 10.9 ~ 14.3kgf/mm
2, be 15.3 ~ 16.6kgf/mm after 35 days
2
Compare with lead-calcium alloy, lead strontium alloy has littler discharge resistance, the low-temperature startup performance of the storage battery made from it, shelf-life, decay resistance all is better than lead-calcium alloy, the life of storage battery has prolonged a year and a half, and it has the damage by water consumption similar to lead-calcium alloy and the performance of self discharge.In the use, lead strontium alloy can not form the lead sulfate passivation layer of dark circulation ability difference, thereby makes storage battery have better maintenance-free performance.
Strontium alloy is similar to the calcium series alloy, also is intercrystalline corrosion, but plumbous strontium Sn-Al alloy has than the better decay resistance of lead-calcium alloy.The lead strontium alloy creep-resistant property is better than lead-calcium alloy.
The development work of being engaged in mainly was to substitute under the situation of calcium fully with strontium, adopting higher content of strontium in the past.But effect is run counter to desire, and exposes the weakness that tested alloys is felt like jelly, and has obliterated the superiority of lead strontium alloy.Among the present invention, we change traditional research, but an amount of strontium is joined in the lead-calcium alloy, and the two complements one another to make calcium and strontium, improve the deficiency such as dilatancy, poor corrosion resistance of calcium with the superiority of strontium, the hardness with calcium constituent solves the defective that grid feels like jelly simultaneously.
The cost performance of comprehensive strontium, this alloy formula is defined as 0.02%～0.05% with content of strontium.
(2) interpolation of alloy middle rare earth element
Rare earth element and lead can form the high-melting point metal compound, can improve the intergranular of lead alloy and tear phenomenon, improve the hot-workability of alloy, the toughness of increase grid alloy and creep-resistant property etc.In lead-calcium-tin alloy, add rare earth, can increase the age-hardening effect of lead-calcium alloy, can improve mechanical performance, chemical property and the decay resistance of non-maintenance lead-acid accumulator grid alloy.
At first, join rare earth in the lead-calcium alloy after, can make alloy grain careful, structure is tight, is similar to draw in the net the used diecasting alloys of grid, thereby makes the anticorrosive chemical property that waits of grid alloy obtain very big improvement.This is because the atomic radius of rare earth element is bigger than plumbous, among the crystal boundary and phase boundary that is generating when they are easy to be deposited on alloy graining, hinders growing up of crystal grain, makes grain refinement.High-melting-point rare earth metal and the compound thereof of dispersing and dissolving in alloy then is the nucleus that particle in suspension has served as heterogeneous forming core, played the effect of alterant (nucleating agent).Micro-zone analysis to this alloy confirms: rare earth element only is slightly soluble in αGu Rongti, and all the other are then with second phase---and the form of lead base rare earth compound exists.Thereby refinement alloy grain, the intensity of alloy and decay resistance are significantly improved.
Aspect electrochemistry, the mensuration of the anodic attack product of the lead-calcium alloy that contains rare earth is confirmed: the rare earth of adding, can obviously reduce the AC impedance of alloy, the linear potential scanning result shows that corrosion product is PbO
2Rather than PbSO
4, rare earth has effectively been controlled PbSO in the corrosive film
4Formation, reduce the thickness of corrosive film, it is even to make the particle of corrosive film be tending towards refinement, and obviously reduce in the hole in the corrosive film, the corrosive film of this structure can alleviate preferably because the stress that change in volume produces, the phenomenon that can cause corrosive film to break and peel off does not make active material closely contact with grid.Thereby can improve the conductivity between anode plate grid and the active material, help prolonging the deep discharge cycle life of battery.This characteristic of rare earth is vital for the maintenance free cell that is used for dark circulation---lead-calcium alloy tends to because corrosion product has more PbSO
4And the formation passivating film causes the too early termination of the life of storage battery, and the lead-calcium alloy that adds rare earth does not then have this phenomenon and occurs.
On the addition of rare earth element, the amount of rare earth should be not too high, because rare earth element can increase the age-hardening of lead-calcium alloy, but it has reduced the initial hardness of foundry goods.
Comprehensive above-mentioned theory analysis, the addition of rare earth is defined as: 0.01%～0.05%, rare earth element adopts not separated mishmetal.Rare earth (Re) means the mixture of any rare earth element, two or more rare earth elements, the not separated mishmetal of composition.
(3), in alloy, add argent
When adding silver in the lead-calcium alloy, can improve the mechanical property and the creep resistance of foundry goods, and can significantly improve the dark circulation ability of maintenance-free lead-acid battery.The raising of silver content can prolong the life-span of storage battery under adverse circumstances, adds silver and lower calcium content the life of storage battery is significantly improved.Ag can reduce Pb as alloy addition and be oxidized to PbO
2Speed, reduced PbO
2Ratio in grid surface corrosion layer increases the conductivity of corrosion layer, has also reduced the sensitiveness of the current potential of oxygen evolution reaction to temperature simultaneously.Sn and Ag are to the influence (seeing the following form) of Pb-Ca alloy corrosion resistance.Along with the raising of Sn content and the interpolation of Ag, alloy corrosion resistance is significantly improved.
Sn, Ag are to the influence of Pb-Ca alloy corrosion resistance
| Corrosion weight loss (mg/cm 2) | ||||
| Sn(％) | 0.6 | 1.2 | 1.5 | 3.0 |
| 0.1Ca | 126 | 80 | 76 | 54 |
| 0.08Ca | 75 | 37 | 33 | 32 |
| 0.08Ca+0.05Ag | 39 | 32 | - | - |
Embodiment: following is the percetage by weight meter.
| Sequence number | Pb | Calcium (Ca) | Tin (Sn) | Strontium (Sr) | Rare earth (Re) | Silver (Ag) | Aluminium (Al) |
| 1 | Surplus | 0.08 | 1.20 | 0.01 | 0.03 | 0.02 | |
| 2 | Surplus | 0.06 | 1.20 | 0.02 | 0.02 | 0.02 | |
| 3 | Surplus | 0.08 | 0.80 | 0.02 | 0.04 | 0.02 | |
| 4 | Surplus | 0.06 | 2.0 | 0.05 | 0.01 | 0.10 | 0.02 |
| 5 | Surplus | 0.08 | 1.5 | 0.03 | 0.003 |
| 6 | Surplus | 0.06 | 2.0 | 0.03 | 0.03 | ||
| 7 | Surplus | 0.08 | 1.2 | 0.04 | 0.05 | 0.03 | |
| 8 | Surplus | 0.06 | 2.5 | 0.03 | 0.05 | 0.05 | 0.03 |
The accumulator plate grid alloy with lead, calcium, strontium and rare earth manufacture method:
Alloy material for slab lattice of the present invention adopts the mode of intermediate alloy to join in the middle of the plumbous liquid.Be specially: in alloy pot, lead is heated to 500～800 ℃, then proportionally, successively add aluminium, tin, plumbous calcium intermediate alloy, plumbous strontium intermediate alloy, plumbous rare earth intermediate alloy etc., alloy melting stirs after finishing, and sampling is analyzed the alloy composition with the direct reading spectroscopic instrument, carry out the alloy composition adjustment according to the sample composition, qualified until the alloy composition.
Claims (5)
1, a kind of lead acid accumulator grid alloy, the percentage by weight that it is characterized in that alloying component is 0.06～0.08%Ca, 0.80～2.50%Sn, 0.02～0.05%Sr, plumbous surplus.
2, lead acid accumulator grid alloy according to claim 1 is characterized in that described alloying component also comprises 0.02～0.10%Ag.
3, lead acid accumulator grid alloy according to claim 1 and 2 is characterized in that described alloying component also comprises 0.01～0.05%Re.
4, lead acid accumulator grid alloy according to claim 1 and 2 is characterized in that described alloying component also comprises 0.003～0.03%Al.
5, lead acid accumulator grid alloy according to claim 3 is characterized in that described alloying component also comprises 0.003～0.03%Al.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100239117A CN100483811C (en) | 2005-02-07 | 2005-02-07 | Accumulator plate grid alloy with lead, calcium, strontium and rare earth |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100239117A CN100483811C (en) | 2005-02-07 | 2005-02-07 | Accumulator plate grid alloy with lead, calcium, strontium and rare earth |
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| Publication Number | Publication Date |
|---|---|
| CN1819312A true CN1819312A (en) | 2006-08-16 |
| CN100483811C CN100483811C (en) | 2009-04-29 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105134858A (en) * | 2015-08-06 | 2015-12-09 | 中国电力科学研究院 | Spring cement shock absorber |
| CN106532063A (en) * | 2016-09-07 | 2017-03-22 | 湖北金洋冶金股份有限公司 | Multi-element lead-based grid alloy and production method thereof |
| CN107641733A (en) * | 2017-10-12 | 2018-01-30 | 河北工业大学 | A kind of PbCaSnAlCeAg grid alloys |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4343872A (en) * | 1977-05-31 | 1982-08-10 | General Battery Corporation | Calcium-strontium-lead grid alloy for use in lead-acid batteries |
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2005
- 2005-02-07 CN CNB2005100239117A patent/CN100483811C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105134858A (en) * | 2015-08-06 | 2015-12-09 | 中国电力科学研究院 | Spring cement shock absorber |
| CN105134858B (en) * | 2015-08-06 | 2018-06-26 | 中国电力科学研究院 | A kind of spring clay damper |
| CN106532063A (en) * | 2016-09-07 | 2017-03-22 | 湖北金洋冶金股份有限公司 | Multi-element lead-based grid alloy and production method thereof |
| CN107641733A (en) * | 2017-10-12 | 2018-01-30 | 河北工业大学 | A kind of PbCaSnAlCeAg grid alloys |
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| CN100483811C (en) | 2009-04-29 |
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Granted publication date: 20090429 Termination date: 20130207 |