CN1039726C - Process for making high-energy density amorphous lead alloy sheet and its usage - Google Patents
Process for making high-energy density amorphous lead alloy sheet and its usage Download PDFInfo
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- CN1039726C CN1039726C CN94104329A CN94104329A CN1039726C CN 1039726 C CN1039726 C CN 1039726C CN 94104329 A CN94104329 A CN 94104329A CN 94104329 A CN94104329 A CN 94104329A CN 1039726 C CN1039726 C CN 1039726C
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- lead alloy
- alloy sheet
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/68—Selection of materials for use in lead-acid accumulators
- H01M4/685—Lead alloys
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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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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The present invention relates to a high-energy density amorphous lead alloy sheet material, a production method and application thereof. The sheet is formed by selectively matching Pb with the elements of Ca, Sr, Na, Sb, As, Al, Ag, Bi, S, Se, Cu, etc. An alloy material is quenched and solidified through the supercooling degree of 300 DEG C to form the sheet in an amorphous structure. The sheet can be made into a closed storage battery grid when covered on both sides of a plastic supporting plate. The sheet has favorable corrosion resistance; when used for making the grid, the sheet can greatly reduce the weight of storage batteries so that the gravimetric specific energy of the storage batteries can reach 45 Wh/kg.
Description
The present invention relates to the material in lead acid cell field, particularly a kind of high-energy density amorphous lead alloy sheet, manufacturing process and application thereof.
Lead acid cell was from its invention existing more than 130 year so far, its performance has had significant raising over more than 100 year, Application Areas also more and more widely and closed lead acid accumulator occurs over nearly more than 30 years, more makes this class battery occupy dominant position in the secondary cell field.Yet, the shortcoming of lead acid cell maximum be weight energy than low, be 20-37Wh/kg only, and ickel-cadmium cell is 40-45Wh/kg, nickel metal hydride battery is 50-55Wh/kg.And weight energy is that the weight of grid self is big than low major cause, accounts for 1/2 of pole plate, accounts for 30% of entire cell.For this problem, normally unsurmountable.This be because, grid is as the carrier and the electrical conductor of plate active material because the grain boundary corrosion of lead alloy is the main source of corrosion of grid, and the corrosion of grid can cause peeling off of plate active material, thereby causes the decline and the inefficacy of battery performance.In order to improve the corrosion resistance of grid, people have adopted the alloying means, for example add Ag, As, Se, Ca, S, Cu or the like alterant, try hard to change the grain boundary structure of alloy, crystal grain thinning, but its effect is limited, thereby people still have to improve corrosion resistance by increasing slab lattice thickness, thereby cause increasing considerably of battery weight.
Purpose of the present invention is intended to for overcoming the defective of prior art, and a kind of high-energy-density lead alloy sheet and manufacture method and purposes with amorphous alloy combination is provided, to improve the weight energy ratio of lead acid cell.
Purpose of the present invention can realize by following proposal.
High-energy density amorphous lead alloy sheet chemical ingredients (weight) is:
(1) 0.06-8%Ca or 0.1-8%Sr, 1.8-8%Sb, 0.08-8%Na;
(2) 0.05-1%S or 0.02-1%Se;
(3) 0.02-1%Cu or 0.08-1%Bi;
(4) surplus Pb.
Can also contain (weight): 0-1%As or Sn in the high-energy density amorphous lead alloy sheet chemical ingredients.
Can also contain (weight): 0-1%Al or Ag in the high-energy density amorphous lead alloy sheet chemical ingredients.
The manufacturing of amorphous lead alloy sheet is undertaken by following step: (1) with described Pb, Ca or Sr, Sb, Na, As or Sn, Al or Ag, S or Se, Cu or Bi alloy material are heated to 500-550 ℃ of fusing, cast the 1-2.5mm left and right thickness, as the leads of grid width; (2) leads was annealed 10 hours under 280 ℃ of-300 ℃ of temperature; (3) melt leads with dielectric heating oven, controlled temperature is at 520 ℃, and makes its outlet from 0.1-0.5mm flow to the drum surface of a rotation, in the cylinder with the liquefied ammonia refrigeration, drum surface temperature＜0 ℃; (4) form the amorphous lead alloy sheet of 0.1-0.5mm thickness at last.
Non-crystalline state lead closes thin plate can be used for making lead acid accumulator plate grid.Grid is made through pressing to glue with spot welding by the amorphous lead alloy sheet of intermediary plastic support board and both sides.
Describe the present invention in detail below in conjunction with embodiment and accompanying drawing.
Fig. 1 grid synoptic diagram;
Fig. 2 grid sectional view.
The amorphous alloy component can be just like all the other 0.09 0.4 0.02 0.1 0.052 ＂, 0.06 0.6 0.01 0.05 0.083 ＂, 0.12 0.3 0.03 0.14 0.024 ＂, 0.1 0.3 0.03 0.08 0.055 ＂, 0.14 0.6 0.05 0.03 0.026 ＂, 0.12 0.6 0.05 0.05 0.057 ＂, 5.7 0.02 0.01 0.02 0.038 ＂, 1.8 0.15 0.02 0.02 0.059 ＂, 2.7 0.12 0.01 0.03 0.0210 ＂, 7 0.02 0.02 0.0511 ＂, 8 0.02 0.0212 ＂, 1.8 0.15 0.02 0.1 0.0513 ＂, 0.08 0.3 0.03 0.12 0.0514 ＂, 0.08 0.6 0.01 0.1 0.0215 ＂, 0.14 0.2 0.01 0.0516 ＂, 0.10 0.8 0.05 0.1 0.0517 ＂, 0.08 0.2 0.8 0.0518 ＂ 0.20 0.2 0.05 0.15 0.05 of the routine Pb Ca Sr of prescription (% of unit) Sb Na As Sn Al Ag Bi Cu S Se1 of following table
Make high-energy density amorphous lead alloy sheet, can be that the alloy material of fusing is cast the thick 1mm that is, wide is the leads of the needed width of grid, the back is carried out homogenizing annealing and is handled under 280-300 ℃ of temperature, heating rapidly on high-frequency induction furnace then, fusing back by one long be the grid width, height is the cast gate of 0.1-0.5mm, be thrown to a drum surface, cylinder rotates with 15 meters/minute speed.The furnace outlet temperature is at 520 ℃, in the cylinder with the liquefied ammonia refrigeration, its surface temperature＜0 ℃, thus cause condensate depression greater than 300 ℃, alloy is solidified suddenly, form the non-crystalline state thin plate.
The present invention is prepared into amorphous lead alloy with the common lead alloy, is to have utilized in metal and the alloy microstructure, and amorphous microstructure has this performance of very high corrosion resistance nature with respect to the crystalline state tissue.This method can be produced the lead 2-base alloy of highly corrosion resistant, reduces the weight of grid, improves the gravimetric specific energy of lead acid cell.
Alloy atom under liquid is a random alignment, and in crystallisation process, atom needs reconstruct, and restructuring procedure is the process of a typical diffusion, and energy need be provided.The manufacture method of thin plate of the present invention, with high condensate depression liquid metal is solidified in moment, atom has little time diffusion, just stay original position, thereby form non-crystalline state, within the long-range scope, non-crystalline state is uniform, no grain boundary defects, so it is much smaller to form the chance of little galvanic cell, corrosion resistance nature is more much higher than crystalline state.
The invention of this energy density amorphous lead alloy sheet, created condition for producing light-duty lead alloy grid, the thickness of this grid is identical with former grid thickness, and plastic support board 1 is big or small identical with grid, thickness is lead alloy sheet 2 thickness that total thickness deducts twice, is approximately 1.6mm.When injection moulding, with the end of a lead alloy lug 3 casting, during making, between plastic plate and lead alloy sheet, be coated with one deck acid-proof cement simultaneously at plastic plate, after use 2940N/cm
2The pressure pressing; Yet, with the spot welding mode thin plate and lead alloy are welded together at the lug place; At last, shape on demand stamps out grid with grid.
The present invention is by making non-crystalline state high-energy-density lead alloy sheet, and is applied to the fully-closed, common and safeguard less on the acid accumulator grid that can reduce the weight of grid greatly, its weight only is equivalent to about 30% of common lead alloy grid of all size.The store battery gravimetric specific energy of making is up to 45Wh/kg, and because the amorphous alloy structure has high corrosion resistance, the life-span of grid can not reduce because of the minimizing of plumbous consumption.
Claims (13)
1, a kind of high-energy density amorphous lead alloy sheet is characterized in that thin plate chemical ingredients (weight) is:
(1) 0.06-8% Ca or 0.1-8%Sr, 1.8-8%Sb, 0.08-8%Na;
(2) 0.05-1%S or 0.02-1%Se;
(3) 0.02-1%Cu or 0.08-1%Bi;
(4) surplus Pb.
2, according to the described lead alloy sheet of claim 1, it is characterized in that can also containing (weight): 0-1%As or Sn in the thin plate chemical ingredients.
3, according to claim 1 or 2 described lead alloy sheets, it is characterized in that to contain (weight): 0-1%Al or Ag in the thin plate chemical ingredients.
4, according to the described lead alloy sheet of claim 1, it is characterized in that thin plate chemical ingredients (weight) is 8%Sb, 0.02%Cu, 0.02%Se and Pb surplus are formed.
5,, it is characterized in that thin plate chemical ingredients (weight) is according to the described lead alloy sheet of claim 2: 0.08%Na, 0.2%Sn, 0.8%Bi, 0.05%Se and Pb surplus are formed.
6,, it is characterized in that thin plate chemical ingredients (weight) is according to the described lead alloy sheet of claim 3: 7%Sb, 0.02%Ag, 0.02%Cu, 0.05%S and Pb surplus are formed.
7,, it is characterized in that thin plate chemical ingredients (weight) is according to the described lead alloy sheet of claim 3: 0.09%Ca, 0.4%Sn, 0.02%Al, 0.05%Se, 0.1%Bi and Pb surplus are formed.
8,, it is characterized in that thin plate chemical ingredients (weight) is according to the described lead alloy sheet of claim 3: 0.1Sr, 0.3%Sn, 0.03%Al, 0.05%S, 0.08%Bi and Pb surplus are formed.
9,, it is characterized in that thin plate chemical ingredients (weight) is according to the described lead alloy sheet of claim 3: 0.12%Na, 0.6%Sn, 0.05%Al, 0.05%Se, 0.05%Cu and Pb surplus are formed.
10,, it is characterized in that thin plate chemical ingredients (weight) is according to the described lead alloy sheet of claim 3: 5.7%Sb, 0.02%Sn, 0.01%Ag, 0.03%Se, 0.02%Cu and Pb surplus are formed.
11,, it is characterized in that thin plate chemical ingredients (weight) is according to the described lead alloy sheet of claim 3: 1.8%Sb, 0.15%As, 0.02%Ag, 0.05%Se, 0.02%Cu and Pb surplus are formed.
12, the manufacture method of the described high-energy density amorphous lead alloy sheet of a kind of claim 1, it is characterized in that (1) is with described Pb, Ca or Sr, Sb, Na, As or Sn, Al or Ag, S or Se, Cu or Bi alloy material are heated to 500-550 ℃ of fusing, cast thick 1-2.5mm, wide is the leads of grid width; (2) leads was annealed 10 hours under 280-300 ℃ of temperature; (3) melt leads with dielectric heating oven, controlled temperature is at 520 ℃, and makes its outlet from 0.1-0.5mm flow to the drum surface of a rotation, in the cylinder with the liquefied ammonia refrigeration, drum surface temperature＜0 ℃; (4) amorphous lead alloy sheet of formation 0.1-0.5mm thickness.
13, the purposes of the described high-energy density amorphous lead alloy sheet of a kind of claim 1 is characterized in that thin plate is used as lead acid accumulator plate grid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94104329A CN1039726C (en) | 1994-04-29 | 1994-04-29 | Process for making high-energy density amorphous lead alloy sheet and its usage |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94104329A CN1039726C (en) | 1994-04-29 | 1994-04-29 | Process for making high-energy density amorphous lead alloy sheet and its usage |
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| CN1095114A CN1095114A (en) | 1994-11-16 |
| CN1039726C true CN1039726C (en) | 1998-09-09 |
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| CN94104329A Expired - Fee Related CN1039726C (en) | 1994-04-29 | 1994-04-29 | Process for making high-energy density amorphous lead alloy sheet and its usage |
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| CN100401935C (en) * | 2002-10-10 | 2008-07-16 | 陈有孝 | Solar warming boots used in cold zone |
| CN101280433B (en) * | 2007-12-31 | 2010-06-02 | 浙江工业大学 | Connecting method of titanium-based noble metal electrode and cathode in electrolytic apparatus, and alloy material |
| CN102082257B (en) * | 2010-12-22 | 2013-10-30 | 风帆股份有限公司 | Lead pipe of lead-acid battery for starting automobile and manufacturing method |
| CN102244248A (en) * | 2011-06-10 | 2011-11-16 | 江苏双登集团有限公司 | Positive plate of lead storage battery for electric bicycle |
| CN102424921B (en) * | 2011-11-14 | 2016-05-18 | 华文蔚 | Preparation method of storage battery grid alloy of electric bicycle |
| RU2584699C1 (en) * | 2015-04-21 | 2016-05-20 | Общество с ограниченной ответственностью "Авто-Лидер" | Lead-acid battery |
| CN105957574B (en) * | 2016-07-17 | 2018-05-15 | 江苏中海华核电材料科技有限公司 | A kind of preparation method of nuke rubbish packing device |
| EP3432394A4 (en) * | 2016-08-26 | 2019-06-12 | Hitachi Chemical Company, Ltd. | Lead acid storage battery, forged grid and method for producing same |
| CN108808010A (en) * | 2018-06-12 | 2018-11-13 | 河北超威电源有限公司 | A kind of Moped Scooter positive electrode grid of lead storage battery alloy and preparation method thereof |
| CN115094267B (en) * | 2022-05-20 | 2023-04-28 | 江苏海瑞电源有限公司 | Lead-based bearing alloy |
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