CN101792873A - Low-stibium multicomponent lead alloy and production technology and applications thereof - Google Patents
Low-stibium multicomponent lead alloy and production technology and applications thereof Download PDFInfo
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- CN101792873A CN101792873A CN 201010133258 CN201010133258A CN101792873A CN 101792873 A CN101792873 A CN 101792873A CN 201010133258 CN201010133258 CN 201010133258 CN 201010133258 A CN201010133258 A CN 201010133258A CN 101792873 A CN101792873 A CN 101792873A
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Abstract
The invention discloses a low-stibium multicomponent lead alloy and a production technology and applications thereof. The low-stibium multicomponent lead alloy contains 1.1-1.8% of stibium, 0.0009-0.004% of arsenic, 0.0009-0.005% of ytterbium and the balance lead. The alloy also contains at least one of cobalt, aluminum and selenium, and the weight percentages of cobalt, aluminum and selenium are separately 0.009-0.03%, 0.009-0.1% and 0.009-0.05%. The production technology of the alloy comprises the following steps: firstly placing electrolytic lead and antimony ingot in a pit-type resistance furnace to melt at 400-800 DEG C, secondly pumping liquid lead-antimony alloy with a lead pump to an alloy kettle, stirring and cooling while adding other alloys. The prepared low-stibium multicomponent lead alloy of the invention is used in the grid and bus of the lead-acid accumulator and is characterized by easy casting process, high strength and high corrosion resistance; and the prepared accumulator has less water loss and longer service life in use.
Description
Technical field:
The invention belongs to chemical field, relate to a kind of low-stibium multicomponent lead alloy and production technique thereof and application.
Background technology:
Lead acid cell shared ratio in China's gross national product is approximately 0.22% according to incompletely statistics, communications and transportation, and industry such as electricity power, communication, post and telecommunications, military affairs all be can't do without it.Along with the fast development of information-based industry, automotive industry, its effect is with increasing.
Lead acid cell is except housing (groove), lid, dividing plate and electrolytic solution, and major portion all is plumbous or plumbous oxide compound, sulfide.Following table has provided one group of typical lead acid cell parts list, can see the ratio that various component roughly account for from table: lead and lead alloy account for ratio in the battery up to 60-70%.
| Title | Grid | Active substance | Web member | Electrolytic solution | Groove, lid, dividing plate |
| Material | Lead alloy | Pb (20%), lead oxides (80%) | Lead alloy | ??H 2SO 4??H 2O | ABS, PP, bakelite, glass fibre |
| Shared ratio | About 24% | About 36% | About 5% | About 27% | About 8% |
Lead antimony alloy is the widely used a kind of alloy of present lead-acid cell industry, and its principal feature is that the adding of antimony can effectively improve plumbous mechanical property, castability, and is bigger to battery grid and the contribution of omnibus bar ratio of briquetting simultaneously.But as the metallic antimony price height of alloying constituent, add high-load antimony in the lead alloy and make that the production cost of alloy is higher, and high-load antimony (more than 3%) can cause that store battery continues dehydration, the maintenance cost of increase battery.But antimony content is low (below 2%), and the mechanical property of alloy descends obviously, insufficient strength, and alloying element is not easy to be uniformly dispersed simultaneously.
Summary of the invention:
The purpose of this invention is to provide a kind of low-stibium multicomponent lead alloy.
Another object of the present invention provides the preparation technology of this low-stibium multicomponent lead alloy.
A further object of the invention provides this low-stibium multicomponent lead alloy in the grid of lead acid cell and the application in the omnibus bar.
A kind of low-stibium multicomponent lead alloy is characterized in that, described lead alloy comprises the composition of following mass percentage content: antimony: 1.1-1.8%; Arsenic: 0.0009-0.004%, ytterbium: 0.0009-0.005%; Surplus is plumbous.Described lead alloy preferably includes the composition of following mass percentage content: antimony: 1.1-1.5%; Arsenic: 0.001-0.003%, ytterbium: 0.001-0.003%; Surplus is plumbous.
Above-mentioned lead alloy also can contain at least a in cobalt, aluminium, 3 kinds of elements of selenium, and its quality percentage composition is respectively cobalt: 0.009-0.03%, aluminium: 0.009-0.1%, selenium: 0.009-0.05%.Preferred cobalt: 0.009-0.02%, aluminium: 0.009-0.03%, selenium: 0.009-0.02%.Described lead, antimony, cobalt, aluminium, selenium, arsenic, ytterbium purity are more than 99%.
The production technique of above-mentioned low-stibium multicomponent lead alloy is carried out according to following steps:
A. at first lead pig, antimony slab are put in the well formula resistance furnace lead pan, heat temperature raising fusing continues to heat up after waiting to be liquid while stirring, reaches 400-800 ℃ until temperature, obtains the lead antimony alloy liquation;
B. with plumbous pump the lead antimony alloy liquation is evacuated in the alloy still, adds all the other alloy raw materials while stir, after raw material all melted, stir speed (S.S.) was controlled at 1000-2000 rev/min, churning time 15-120 minute.
After alloying process is finished, alloy liquid is emitted ingot casting, cooling, moulding from tap hole.
In described " A " step, temperature preferably is controlled at 400-650 ℃, most preferably 550-650 ℃, in described " B " step, after raw material all melts, continues churning time and preferably is controlled at most preferably 35 minutes 30-50 minute.Low-stibium multicomponent lead alloy of the present invention can be used in the grid of lead acid cell and omnibus bar, and the grid that is used in particular for valve-regulated lead-acid battery is made.
In addition, the present invention adopts high density alloying element and lower concentration alloying element to separate the method that adds, and measures few alloying element and adds under the powerful stirring of alloy still high speed, makes alloying element disperse more evenly in plumbous mother liquor.
Need avoid the existence at the stirring dead angle in the lead pan, the lead antimony alloy liquation among the present invention to be transferred to from market pot by plumbous pump in the process of alloy still for the dispersion of antimony metal in plumbous mother liquor of high density and solve this problem.And the dispersion of the alloying element of lower concentration is mainly stirred by powerful, and the agitator speed in the alloy still can be guaranteed the homogeneity of alloy up to 2000 rev/mins.
Beneficial effect of the present invention: the present invention is used a certain amount of multiple element, remedy the insufficient shortcoming of low-antimony-lead alloy physical strength, can improve the castability of low-antimony-lead alloy, and the adding of element arsenic and ytterbium improves the corrosion resistance of low-antimony-lead alloy, and effect is remarkable in the grid of lead acid cell and omnibus bar.Plurality of advantages such as in addition, the store battery that the low-stibium multicomponent lead alloy that the present invention produced is made in use has little moisture loss, and the life-span is long.
Embodiment
Embodiment 1
Take by weighing 55.61kg, purity and be 99.9% antimony slab; 0.51kg, 99% cobalt powder; 0.51kg, 99.9% aluminium powder; 0.51kg, 99.9% selenium piece; 51g, 99.9% arsenic; 51g, 99% ytterbium; 4992kg, 99.99% lead pig.
Lead pig and antimony slab are joined in the well-type electric furnace, heat up, 330 ℃ of left and right sides lead pigs begin fusing, and antimony slab progressively is dissolved in the plumbous fused solution.Continue to heat up while stirring this moment, treats that melt temperature rises to 400 ℃, and (high carbon steel is material of main part with plumbous pump mixed molten liquid to be evacuated to the alloy still, be with two agitators) in, open agitator, rotating speed transfers to 1000 rev/mins, adds the cobalt powder, aluminium powder, selenium piece, arsenic, the ytterbium that weigh up.Metal to be added is kept 1000 rev/mins mixing speed after all melting, and continues to stir 30 minutes, forms alloy.
Plumbous mouthful the alloy liquation is put into pig moulding machine from putting of alloy still, cooling goes out the alloy lead pig.
Embodiment 2
Take by weighing 56.81kg, purity and be 99.9% antimony slab; 1.02kg, 99% cobalt powder; 0.51kg, 99.9% aluminium powder; 0.51kg, 99.9% selenium piece; 102g, 99.9% arsenic; 51g, 99% ytterbium; 4991kg, 99.99% lead pig.
Lead pig and antimony slab are joined in the well-type electric furnace, heat up.330 ℃ of left and right sides lead pigs begin fusing, and antimony slab progressively is dissolved in the plumbous fused solution.Continue to heat up while stirring this moment, treats that melt temperature rises to 480 ℃, with plumbous pump mixed molten liquid is evacuated in the alloy still, opens agitator, and rotating speed transfers to 1200 rev/mins, adds the cobalt powder, aluminium powder, selenium piece, arsenic, the ytterbium that weigh up.Metal to be added is kept 1500 rev/mins mixing speed after all melting, and continues to stir 35 minutes, forms alloy.
Plumbous mouthful the alloy liquation is put into pig moulding machine from putting of alloy still, cooling goes out the alloy lead pig.
Embodiment 3
Take by weighing 55.61kg, purity and be 99.9% antimony slab; 0.88kg, 99% cobalt powder; 0.60kg, 99.9% aluminium powder; 60g, 99.9% arsenic piece; 55g, 99% ytterbium, 4992kg, 99.99% lead pig,
Lead pig and antimony slab are joined in the well-type electric furnace, heat up.330 ℃ of left and right sides lead pigs begin fusing, and antimony slab progressively is dissolved in the plumbous fused solution.Continue to heat up while stirring this moment, treats that melt temperature rises to 580 ℃, with plumbous pump mixed molten liquid is evacuated in the alloy still, opens agitator, and rotating speed transfers to 1500 rev/mins, adds the cobalt powder, aluminium powder, arsenic piece, the ytterbium that weigh up.Metal to be added is kept 1500 rev/mins mixing speed after all melting, and continues to stir 85 minutes, forms alloy.
Plumbous mouthful the alloy liquation is put into pig moulding machine from putting of alloy still, cooling goes out the alloy lead pig.
Embodiment 4
Take by weighing 56.21kg, purity and be 99.9% antimony slab; 0.90kg, 99.9% aluminium powder; 0.90kg, 99.9% selenium piece; 171g, 99% ytterbium; 180g, 99.9% arsenic piece; 4991kg, 99.99% lead pig.
Lead pig and antimony slab are joined in the well-type electric furnace, heat up.330 ℃ of left and right sides lead pigs begin fusing, and antimony slab progressively is dissolved in the plumbous fused solution.Continue to heat up while stirring this moment, treats that melt temperature rises to 650 ℃, with plumbous pump mixed molten liquid is evacuated in the alloy still, opens agitator, and rotating speed transfers to 2000 rev/mins, adds the cobalt powder, aluminium powder, selenium piece, arsenic, the ytterbium that weigh up.Metal to be added is kept 2000 rev/mins mixing speed after all melting, and continues to stir 50 minutes, forms alloy.
Plumbous mouthful the alloy liquation is put into pig moulding machine from putting of alloy still, cooling goes out the alloy lead pig.
Embodiment 5
With the alloy for preparing among the embodiment 1, hereinafter referred to as the S1 alloy, under 325 ℃ of temperature, be cast into the thick grid of 120 * 150 * 7mm length and width, being placed on proportion is 1.28g/cm
3Sulfuric acid in soak, behind the 350h, the grid surface stain, the non-cracking obscission takes place.
Embodiment 6
With the alloy for preparing among the embodiment 2, hereinafter referred to as the S2 alloy, under 325 ℃ of temperature, be cast into the thick grid of 120 * 150 * 7mm length and width, be placed on the smooth stainless steel table top, use sectional area 110cm
2The weight of heavy 25N is from 0.7 meter high freely falling body frontal impact alloy grid, and 17 times repeatedly, grid ruptures.
Comparative Examples 1
Press the method among the embodiment 2, purity is that 99% ytterbium addition changes 25g into, makes alloy, hereinafter referred to as the S3 alloy, under 325 ℃ of temperature, is cast into the thick grid of 120 * 150 * 7mm length and width, is placed on the smooth stainless steel table top, uses sectional area 110cm
2The weight of heavy 25N is from 0.7 meter high freely falling body frontal impact alloy grid, and 11 times repeatedly, grid ruptures.
Claims (9)
1. a low-stibium multicomponent lead alloy is characterized in that, described lead alloy comprises the composition of following mass percentage content:
Antimony: 1.1-1.8%; Arsenic: 0.0009-0.004%, ytterbium: 0.0009-0.005%; Surplus is plumbous.
2. low-stibium multicomponent lead alloy according to claim 1 is characterized in that described lead alloy comprises the composition of following mass percentage content: antimony: 1.1-1.5%; Arsenic: 0.001-0.003%, ytterbium: 0.001-0.003%; Surplus is plumbous.
3. low-stibium multicomponent lead alloy according to claim 1, it is characterized in that, described lead alloy also contains at least a in cobalt, aluminium, 3 kinds of elements of selenium, and its quality percentage composition is respectively cobalt: 0.009-0.03%, aluminium: 0.009-0.1%, selenium: 0.009-0.05%.
4. the production technique of a claim 1,2 or 3 described low-stibium multicomponent lead alloys is characterized in that this technology prepares according to following steps:
A. lead pig, antimony slab are put in the well formula resistance furnace lead pan, heat temperature raising fusing continues to heat up after waiting to be liquid while stirring, reaches 400-800 ℃ until temperature, obtains the lead antimony alloy liquation;
B. with plumbous pump the lead antimony alloy liquation is evacuated in the alloy still, adds all the other alloy raw materials while stir, after raw material all melted, stir speed (S.S.) was controlled at 1000-2000 rev/min, continues churning time 15-120 minute.
5. the production technique of low-stibium multicomponent lead alloy according to claim 4 is characterized in that temperature is controlled at 400-650 ℃ in described " A " step.
6. the production technique of low-stibium multicomponent lead alloy according to claim 5 is characterized in that temperature is controlled at 550-650 ℃ in described " A " step.
7. the production technique of low-stibium multicomponent lead alloy according to claim 4 is characterized in that in described " B " step, after raw material all melts, continues churning time and is controlled at 30-50 minute.
8. the production technique of low-stibium multicomponent lead alloy according to claim 7 is characterized in that in described " B " step, continues churning time and is controlled at 35 minutes.
9. claim 1,2 or 3 described low-stibium multicomponent lead alloys are in the grid of lead acid cell and the application in the omnibus bar.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105603224A (en) * | 2015-12-25 | 2016-05-25 | 河南豫光金铅股份有限公司 | Smelting method for preparing lead-antimony alloy from lead-containing waste |
| CN109439959A (en) * | 2018-12-24 | 2019-03-08 | 双登集团股份有限公司 | Low-stibium multicomponent lead alloy and smelting process |
| CN113611870A (en) * | 2021-07-08 | 2021-11-05 | 江苏海宝电池科技有限公司 | Lead-based alloy for punched grid and preparation method and application thereof |
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| CN109439959A (en) * | 2018-12-24 | 2019-03-08 | 双登集团股份有限公司 | Low-stibium multicomponent lead alloy and smelting process |
| CN113611870A (en) * | 2021-07-08 | 2021-11-05 | 江苏海宝电池科技有限公司 | Lead-based alloy for punched grid and preparation method and application thereof |
| CN113611870B (en) * | 2021-07-08 | 2022-12-27 | 江苏海宝电池科技有限公司 | Lead-based alloy for punched mesh grid and preparation method and application thereof |
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