CN1028439C - Ultra-low antimony slab lattice alloy material for maintenance-free closed lead-acid battery - Google Patents
Ultra-low antimony slab lattice alloy material for maintenance-free closed lead-acid battery Download PDFInfo
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- CN1028439C CN1028439C CN92100587A CN92100587A CN1028439C CN 1028439 C CN1028439 C CN 1028439C CN 92100587 A CN92100587 A CN 92100587A CN 92100587 A CN92100587 A CN 92100587A CN 1028439 C CN1028439 C CN 1028439C
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- alloy material
- maintenance
- ultra
- acid battery
- alloy
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- 239000000956 alloy Substances 0.000 title claims abstract description 32
- 239000002253 acid Substances 0.000 title claims abstract description 15
- 229910052787 antimony Inorganic materials 0.000 title abstract description 10
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 16
- 229910045601 alloy Inorganic materials 0.000 claims description 25
- 239000002141 low-antimony alloy Substances 0.000 claims description 12
- 238000012423 maintenance Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 abstract description 4
- 229910052709 silver Inorganic materials 0.000 abstract description 4
- 238000005728 strengthening Methods 0.000 abstract description 4
- 229910052718 tin Inorganic materials 0.000 abstract description 4
- 238000005266 casting Methods 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 239000001999 grid alloy Substances 0.000 abstract 1
- 229910052745 lead Inorganic materials 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000003623 enhancer Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- 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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- Cell Electrode Carriers And Collectors (AREA)
Abstract
The present invention belongs to an ultra-low antimony grid alloy material for a maintenance-free sealed lead-acid battery. The alloy material consists of 0.3-0.75% of Pb-Sb and strengthening matrix elements, wherein the strengthening matrix elements can be K, Na, Ll, Sn, S, Ag, Cu and Al. The alloy material has good mechanical property, corrosion resistance, casting manufacturability and excellent electrochemical property. The series of storage batteries of 4V8Ah to 12V40Ah can be assembled by using the battery pack, and all performance indexes of the batteries exceed the standard requirements.
Description
The present invention relates to the lead 2-base alloy material, especially for the ultra-low-antimony alloy material for slab lattice of sealed lead-acid battery free of maintenance.
Employed lead base contains antimony slab lattice alloy in the lead acid cell, its antimony content generally is higher than 6%, the physical strength of this alloy is higher, and because the content of Sb is higher, make the corrosion-resistant of alloy, the hydrogen-separating quantity height, thereby can't in closed accumulator, use, in recent years, both at home and abroad in this research, it is 1.8～4% low antimony alloy that employing contains the antimony amount, yet along with the reduction of Sb content, the actual freezing range of alloy broadens, form very wide two-phase region, alloy shows mobile rapid decline, even produces micro-crack in process of setting, causes the alloy physical strength to descend.For this reason, people add the metacrystal agent based on As, produce the Pb-Sb-As alloy, and As and oxide compound thereof are highly toxic substances, are subjected to the strictness restriction of environment protection, and the adding of As has simultaneously seriously influenced the toughness of alloy again, and the manufacturability of material is descended.
Purpose of the present invention is provides Sb content low, strengthens the ultra-low-antimony alloy material for slab lattice scheme that matrix element does not contain Toxic matter, to satisfy the requirement of sealed lead-acid battery free of maintenance to grid material.
The object of the present invention is achieved like this.
Non-maintaining airtight acid accumulator ultra-low-antimony alloy material for slab lattice is made up of Pb, Sb and reinforcement matrix element.Its alloy composition (weight) can be respectively:
(1) Sb0.4%, Li0.08%, S0.02%, all the other are Pb.
(2) Sb0.6%, K0.04%, Na0.05%, Sn0.2%, all the other are Pb.
(3) Sb0.4%, Na0,1%, Cu0.05%, all the other are Pb.
(4) Sb0.75%, Ag0.02%, Na0.05%, all the other are Pb.
(5) Sb0.3%, Li0.05%, Ag0.1%, Sn0.1%, all the other are Pb.
(6) Sb0.4%, Na0.2%, K0.5%, Cu0.3%, S0.5%, Sn0.2%, all the other are Pb.
(7) Sb0.56%～0.75%, Na0.05%～0.1%, Cu0.05%～0.2%, Sn0.3～0.5%, all the other are Pb.
This alloy material grid can make by following method: Pb and Sb are gone in the crucible, be heated to 480～500 ℃ with electric furnace, form alloy solution, yet again will be by Na, Cu, Sn, K, Li, S, the composite enhancer that Ag or Al form adds, prepare, and be incubated 11 minutes, then alloy solution is poured into graphite jig and make grid, through 3-5 days change into the time, promptly can be used to assembling accumulator again.
Composite enhancer among the present invention is to be the ternary metal compound of one with metacrystal, reinforcement, increase flowability, and when the Pb-Sb alloy solution that is dissolved in 0.3～0.75%, composite enhancer and Pb, Sb are heavy cohesive process.The alterant element Cu of trace, S or Ag and Pb can form difficult dissolved matter and separate out, in solution, form a large amount of solid phase particles as the heteromorphic nucleus core, selected alterant element Cu, S, Ag and Pb belong to a kind of lattice types together, and matching degree, modification effect are good, thereby give alloy with good toughness, make the fine and close refinement of alloy structure, improved anticorrosive power; Strengthening element Li in the composite enhancer, K or Na can exist certain solid solubility with the lead base body, and the part element enters plumbous lattice, forms sosoloid, and the solid solution atom produces distortion greater than the octahedral interstice of Pb, cause the reinforcement of material.
The selection of strengthening phase element is according to adaptability to changes and sosoloid stability relationship, the element of less atomic radius enters the lead base body, just can carry out more stable sosoloid, and the part solute element is separated out when alloy cools off, make the metal compound object point be distributed in the lead base body, formed PbA
3The hardness of type compound is far longer than pure Pb.Grain boundary precipitate is to influence crystal boundary to move the principal element of moving, and adding tin can influence plumbous crystal boundary translational speed, and along with the content of tin in lead increases, the crystal boundary translational speed decreases, thereby the pinning of crystal boundary obviously improves the intensity of material.Because the content of antimony is very little, also makes alloy have higher overpotential of hydrogen evolution.Pass through the x-ray photoelectron spectroscopy analytical proof in addition, the corrosion product of alloy is the good PbO of active substance contact
2Corrosive film, and do not contain PbSO
4
The ultralow antimony slab lattice alloy of sealed lead-acid battery free of maintenance provided by the present invention has the favorable mechanical performance, erosion resistance, and casting manufacturability is with seldom excellent electrochemical properties such as hydrogen-separating quantity.Through the actual measurement proof, its capacity reaches 107.3 with its enclosed cell that is assembled into 12VAh; High rate discharge reaches 31 hours, and sealed reaction efficient reaches 99.3%; Dark cycle life is up to 420 times.
Alloy material of the present invention can have multiple embodiments, as:
(1) Sb0.4%, Na0.05%, Li0.08%, all the other Pb.
(2) Sb0.56%, Na0.1%, Cu0.2%, Sn0.3%, all the other Pb.
(3) Sb0.36%, Li0.09%, all the other Pb.
(4) Sb0.4%, Na0.08%, all the other Pb.
(5) Sb0.36%, K0.06%, Cu0.05%, all the other Pb.
(6) Sb0.75%, Cu0.05%, Ag0.03%, Al0.02%, all the other Pb.
(7) Sb0.3%, K0.01%, S0.02%, all the other Pb.
(8) Sb0.3%, K0.2%, S0.4%, all the other Pb of Sn0.05%.
(9) Sb0.6%, Na0.1%, K0.2%, Li0.2%, Cu0.2%, S0.4%, Ag0.1%, Sn0.4%, all the other Pb.
(10) Sb0.75%, Na0.05%, Cu0.05%, Sn0.5%, all the other Pb.
Adopt the alloy in the foregoing description to burn the positive and negative electrode screen that casting is finished through fusing, can assemble the serial enclosed non-maintenance store battery from 4V8Ah to 12V40Ah, its technical indicator all can reach: capacity 98～106; High rate discharge 28～31 hours, airtight reflection efficient 93～99%; 360～405 hours life-spans.
Claims (8)
1, a kind of ultra-low-antimony alloy material for slab lattice of sealed lead-acid battery free of maintenance is characterized in that alloy composition (weight) is: Sb0.4%, and Ll0.08%, S0.02%, all the other are Pb.
2, a kind of ultra-low-antimony alloy material for slab lattice of sealed lead-acid battery free of maintenance is characterized in that alloy composition (weight) is: Sb0.6%, and K0.04%, Na0.05%, Sn0.2%, all the other are Pb.
3, a kind of ultra-low-antimony alloy material for slab lattice of sealed lead-acid battery free of maintenance is characterized in that alloy composition (weight) is: Sb0.4%, and Na0.1%, Cu0.05%, all the other are Pb.
4, a kind of ultra-low-antimony alloy material for slab lattice of sealed lead-acid battery free of maintenance is characterized in that alloy composition (weight) is: Sb0.75%, and Ag0.02%, Na0.05%, all the other are Pb.
5, a kind of ultra-low-antimony alloy material for slab lattice of sealed lead-acid battery free of maintenance is characterized in that alloy composition (weight) is: Sb0.3%, and Li0.05%, Ag0.1%, Sn0.1%, all the other are Pb.
6, a kind of ultra-low-antimony alloy material for slab lattice of sealed lead-acid battery free of maintenance is characterized in that alloy composition (weight) is: Sb0.4%, Na0.2%, K0.5%, Cu0.3%, S0.5%, Sn0.2%, all the other Pb.
7, a kind of ultra-low-antimony alloy material for slab lattice of sealed lead-acid battery free of maintenance is characterized in that alloy composition (weight) is Sb0.56%～0.75%, Na0.05%～0.1%, and Cu0.05%～0.2%, Sn0.3～0.5%, all the other are Pb.
8,, it is characterized in that alloy composition (weight) is according to the described alloy material of claim 7: Sb0.75%, Na0.05%, Cu0.05%, Sn0.5%, all the other are Pb.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92100587A CN1028439C (en) | 1992-01-31 | 1992-01-31 | Ultra-low antimony slab lattice alloy material for maintenance-free closed lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92100587A CN1028439C (en) | 1992-01-31 | 1992-01-31 | Ultra-low antimony slab lattice alloy material for maintenance-free closed lead-acid battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1074949A CN1074949A (en) | 1993-08-04 |
| CN1028439C true CN1028439C (en) | 1995-05-17 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92100587A Expired - Fee Related CN1028439C (en) | 1992-01-31 | 1992-01-31 | Ultra-low antimony slab lattice alloy material for maintenance-free closed lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1028439C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039922C (en) * | 1995-12-22 | 1998-09-23 | 陈有孝 | Ultra-calcium alloy material |
| CN110144494B (en) * | 2019-06-06 | 2021-08-06 | 江苏海瑞电源有限公司 | High-performance lead-based alloy for sheath and preparation method thereof |
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1992
- 1992-01-31 CN CN92100587A patent/CN1028439C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1074949A (en) | 1993-08-04 |
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