CN1248345C - High performance battery plate grid alloy - Google Patents
High performance battery plate grid alloy Download PDFInfo
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- CN1248345C CN1248345C CNB031164137A CN03116413A CN1248345C CN 1248345 C CN1248345 C CN 1248345C CN B031164137 A CNB031164137 A CN B031164137A CN 03116413 A CN03116413 A CN 03116413A CN 1248345 C CN1248345 C CN 1248345C
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- cadmium
- lead
- antimony
- tin
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention discloses a slab lattice alloy material used for a fully-closed maintenance-free lead-acid accumulator and a preparation method thereof. The slab lattice alloy material has the components with the proportion of 1.5% to 2.0% of Cd, 1.5% to 2.0% of Sb and 0.01 to 0.05% of RE. Utilized RE has the components of 51 to 57 % of Ce, 21 to 27 % of La, 4 to 7 % of Pr and 15 to 17 % of Nd. Antimony, cadmium, misch metal, tin and other elements are added in lead to form Pb-Cd-Sb-Re-Sn alloy. The alloy has a fine crystallized structure, slab lattice corrosion is uniform, the alloy has high corrosion resistance, and deep cycle capability is enhanced. The problem that the corrosion resistance of the cadmium and antimony alloy is reduced due to blocky frame-shaped aliquation and nonuniform components of cadmium is solved. The specific preparation method of the alloy has the steps that first of all, a common crucible oven or an iron lead pot is used for making Pb-RE intermediate alloy at a temperature of 660 DEG C, and then lead is melted; the temperature is raised to 450 DEG C to 500 DEG C, the prepared antimony and the tin are added between the cadmium and Ph-RE after melted, and the qualified alloy after detection is cast into an ingot to further manufacture the slab lattice alloy for an accumulator.
Description
Affiliated technical field
The present invention relates to a kind of alloy material for slab lattice that is used for fully closed maintenance-free lead accumulator and preparation method thereof, this alloy is mainly used in the manufacturing of lead acid accumulator, is specially adapted to do the alloy material for slab lattice of dark circulation trailed model maintenance-free 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.
In recent years, coming into operation and the appearance of electric automobile of electric moving aid vehicle requires people to remove to seek a kind of novel grid alloy, and this new alloy must make storage battery possess dark circulation and corrosion resistant performance.At present, plumbous cadmium antimony alloy is praised highly with alloy especially as a kind of good lead acid accumulator plate grid, its reason is that this alloy makes storage battery have good electric property and casting technique performance, the lead acid accumulator of the trailed model that is particularly suitable for being applied to circulating deeply.Prior art can use clean preparation method to produce alloy, and the refuse battery grid that plumbous cadmium antimony alloy is made is carried out pollution-free regeneration reclaim, as number of patent application is 00127576.3, and name is called the document introduction of " a kind of smelting process of pollution-free leaded discarded object ".
Plumbous cadmium antimony alloy in use, when cadmium content in the grid alloy is in the 1.0%-2.0% scope, though increased grid intensity, but the crisp rigid of alloy also increases simultaneously, and when cadmium content in the alloy just begins to occur degradation situation under the corrosion resistance of the segregation of lumps shaped as frame, cadmium uneven components, alloy part greater than 1.5% the time, this has had influence on the result of use of alloy to a certain extent.
Summary of the invention
At the shortcoming of above-mentioned leaded cadmium antimony alloy, we have proposed a kind of accumulator plate grid alloy, add additive, are intended to further improve the good effect of cadmium in alloy, further improve the performance of grid alloy.
The present invention adds an amount of additive on the basis of plumbous cadmium antimony ternary alloy, solve the above-mentioned defective of plumbous cadmium antimony alloy.
Rare earth and tin as a kind of additive, are joined in the plumbous cadmium antimony alloy, and by weight percentage, its composition range is Cd:1.5%-2.0%, Sb:1.5%-2.0%, mishmetal: 0.01%-0.05%, Sn:0.01%-0.05%, and all the other are Pb.Wherein used mishmetal composition is Ce:51%-57%, La:21%-27%, Pr:4%-7%, Nd:15%-17%.
The invention has the beneficial effects as follows:
1, rare earth fining alloy grain, lumps shaped as frame segregation problem and crisp rigid problem have been solved, when rare earth element adds plumbous cadmium antimony alloy to, make the crystal grain of alloy become little and even, alloy aging intensity and corrosion resistance also obtain very big improvement, and its theory analysis is as follows: because the atomic radius of rare earth element big than lead all, among the crystal boundary and phase boundary that is generating when they are easy to be deposited on alloy graining, hamper growing up of crystal grain, make grain refinement.The high-melting-point rare earth metal and the compound thereof of the dispersion in dissolving and the melted alloy then are the nucleus that particle in suspension has served as heterogeneous forming core, have played the effect of alterant (nucleating agent).Micro-zone analysis to this alloy confirms: rare earth element only is slightly soluble in the α solid solution, and all the other then exist with the form of second phase, one lead base rare earth compound.Like this, rare earth increases the antimony content concentration of α in mutually, and the amount of separating out of β phase then reduces accordingly, so lamellar structure has obtained refinement, dispersion, the intensity and the decay resistance of alloy are improved, and alloy lumps shaped as frame segregation problem and crisp rigid problem have also obtained solution.
2, the interpolation of rare earth has improved the electrochemistry of alloy.
Rare earth has higher hydrogen and separates out overpotential, join plumbous cadmium antimony alloy after, its this performance has obtained continuity.Studies show that of chemical property: rare earth makes the hydrogen of plumbous cadmium antimony alloy separate out overpotential and increases, and can suppress plumbous dissolving certainly.
3, the interpolation of tin has reduced the loss of cadmium and to the pollution of environment
In process of production, cadmium is the element that a kind of ratio is easier to oxidization burning loss, and the volatilization of cadmium can not cause production environment to pollute to a certain extent yet.Add an amount of tin in plumbous cadmium antimony alloy after, the tin of lead alloy surface is easy to oxidation, generates the thin and sticking SnO that certain intensity is arranged
2Film has effectively been protected the cadmium additive in the lead alloy, and the density of tin is than cadmium, plumbous little many, and it can float over the surface of lead alloy, so the easily cadmium of scaling loss has been protected in the plumbous cadmium antimony alloy in the adding of tin, reduces the loss of cadmium in the production process.
4, the adding of tin helps the raising of the decay resistance of alloy
Tin has reduced the corrosion rate of plumbous cadmium antimony alloy, studies show that, in plumbous cadmium antimony alloy, tin makes the decay resistance of alloy improve 6-8 doubly.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 adds the preceding accumulator plate grid alloy phasor of rare earth.
Fig. 2 adds the preceding accumulator plate grid alloy phasor of rare earth.
Embodiment
The present invention is further described to use embodiment below again
The component of embodiments of the invention is as follows: alloying component (by weight percentage) embodiment 1 embodiment 2
| Plumbous Pb | Surplus | Surplus |
| Cadmium Cd | 1.60-1.80 | 1.60-1.80 |
| Antimony Sb | 1.50-1.70 | 1.50-1.70 |
| Tin Sn | 0.01-0.05 | |
| Mishmetal | 0.01-0.05 | |
| Silver Ag | 0-0.0005 | 0-0.0005 |
| Copper Cu | 0-0.0001 | 0-0.0001 |
| Bismuth Bi | 0-0.003 | 0-0.003 |
| Arsenic As | 0-0.0005 | 0-0.0005 |
| Tin Sn | 0-0.001 | |
| Zinc Zn | 0-0.0005 | 0-0.0005 |
| Iron Fe | 0-0.0005 | 0-0.0005 |
| The impurity summation | 0-0.006 | 0-0.006 |
The adding refinement of rare earth alloy grain, solved lumps shaped as frame segregation problem, and then decay resistance, deep-circulating performance and the chemical property etc. of alloy be significantly improved.Fig. 1 and Fig. 2 be add before and after the rare earth alloy phase diagram relatively, Pb-1.6% among Fig. 1 wherein, Pb-1.6%Sb-1.7%Cd-0.02% mishmetal among Sb-1.7%Cd Fig. 2.
Evidence, the battery cycle-index DoD60% that makes of the Pb-Cd-Sb-mixed rare earth alloy reaches more than 400 times, and DoD100% reaches more than 200 times, has longer life.Do storage battery self-discharge rate every day less than 0.15% with the Pb-Cd-Sb-mixed rare earth alloy, store 3 months residual capacities at 25 ℃ and reach more than 82%, open circuit voltage still reaches 12.80 volts.At small-capacity cells (13 thin plate grid, positive plate thickness L 7mm) on the pole plate (14.4*12.5cm), degree of depth 5h with 80% leads discharge, 8h leads charging and carries out the actual cycle test, the result shows, Pb-1.6% is housed, Sb-1.7%, the battery of Cd-0.02% mixed rare earth alloy grid capacity drop to rated capacity 80% before finished 225 circulations, scrapped before finishing 225 circulations and standard traction alloy grid battery is housed.Hence one can see that, and the Pb-Cd-Sb-mishmetal-(Sn) alloy is particularly useful for the deep discharge circulation.The adding of tin increased alloy decay resistance, reduced the loss of cadmium and, improved operational environment the pollution of environment, reduced the treating capacity of environmental protection equipment.
The concrete preparation method of alloy is as follows: it is standby to make lead-mishmetal intermediate alloy ingot bar with common crucible or market pot about 660 ℃ earlier, required lead is placed in the market pot, heat fused and be warming up to 450 ℃ ~ 500 ℃ after, add load weighted by weight percentage antimony and tin, after antimony tin has melted, add required cadmium metal and lead-mishmetal intermediate alloy again, treat that the whole fusings of alloy finish, and become ingot with the alloy mold after the assay was approved.
Claims (2)
1. accumulator plate grid alloy, it is characterized in that: by weight percentage, its composition comprises that Cd:1.5%-2.0%, Sb: 1.5%-2.0%, mishmetal: 0.01%-0.05%, Sn: 0.01%-0.05%, surplus are Pb, wherein said mishmetal composition contains Ce by weight percentage: 51%-57%, La: 21%-27%, Pr: 4%-7%, Nd: 15%-17%.
2. method of making the described a kind of accumulator plate grid alloy of claim 1, it is characterized in that: it is standby to make lead-mishmetal intermediate alloy ingot bar with common crucible or market pot about 660 ℃ earlier, required lead is placed in the market pot, heat fused and be warming up to 450 ℃ ~ 500 ℃ after, add load weighted by weight percentage antimony and tin, after antimony tin has melted, add required cadmium metal and lead-mishmetal intermediate alloy again, treat that the whole fusings of alloy finish, and become ingot with the alloy mold after the assay was approved.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031164137A CN1248345C (en) | 2003-04-15 | 2003-04-15 | High performance battery plate grid alloy |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031164137A CN1248345C (en) | 2003-04-15 | 2003-04-15 | High performance battery plate grid alloy |
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| CN1538544A CN1538544A (en) | 2004-10-20 |
| CN1248345C true CN1248345C (en) | 2006-03-29 |
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| CNB031164137A Expired - Fee Related CN1248345C (en) | 2003-04-15 | 2003-04-15 | High performance battery plate grid alloy |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100403593C (en) * | 2005-05-13 | 2008-07-16 | 陈有孝 | 6-HK(M)-55 type high-energy dry-charged sealed maintenance-free lead-acid battery |
| CN100416898C (en) * | 2005-11-07 | 2008-09-03 | 西安交通大学 | Preparation proces for regenerating lead-rare earth low antimony slab lattice alloy |
| CN101792873A (en) * | 2010-03-26 | 2010-08-04 | 如皋市天鹏冶金有限公司 | Low-stibium multicomponent lead alloy and production technology and applications thereof |
| CN101805836B (en) * | 2010-04-27 | 2011-08-24 | 天能电池(芜湖)有限公司 | Preparation method of Pb-Sb-Cd alloy used for positive plate of battery |
| CN103219523B (en) * | 2013-04-03 | 2015-07-01 | 江苏海德森能源有限公司 | Negative plate of lead-acid storage battery and preparation method of negative plate |
| CN103219522B (en) * | 2013-04-03 | 2015-08-05 | 江苏海德森能源有限公司 | Lead acid accumulator plate grid of a kind of top layer doped with rare-earth elements and preparation method thereof |
| CN108336360A (en) * | 2017-12-28 | 2018-07-27 | 广州倬粤动力新能源有限公司 | Grid composite fibre |
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2003
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