CN1447467A - Plumbum-rare earth mulaticomponent alloy being used as positive plate grid of lead accumulator and its preparation method - Google Patents
Plumbum-rare earth mulaticomponent alloy being used as positive plate grid of lead accumulator and its preparation method Download PDFInfo
- Publication number
- CN1447467A CN1447467A CN03116132A CN03116132A CN1447467A CN 1447467 A CN1447467 A CN 1447467A CN 03116132 A CN03116132 A CN 03116132A CN 03116132 A CN03116132 A CN 03116132A CN 1447467 A CN1447467 A CN 1447467A
- Authority
- CN
- China
- Prior art keywords
- alloy
- lead
- rare earth
- aluminium
- rare
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
Landscapes
- Cell Electrode Carriers And Collectors (AREA)
Abstract
A multicomponent alloy is composed of large numbers of plumbum, a smell quantity of stannum and aluminium as well as an amount of rare earth metal. The manufacturing method includes two steps: first, plumbum-aluminium-rare earth interalloy is made by using vacuum melting method; then, the plumbum-aluminium-stannum alloy melted in advance is added into the above said alloy to form the mulaticomponent alloy. The mulaticomponent alloy prepared by the invention possesses excellent corrosion-resisting properties and low anode corrosion impedance. Thus, the accumulator made from the alloy has good charging and discharging properties and long service life.
Description
Technical field
The invention belongs to metallurgy and technical field of electrochemistry, be specifically related to a kind of NEW Pb one rare earth multicomponent alloy and manufacture method thereof as the positive electrode grid of lead storage battery material.
Background technology
At present, the positive electrode grid of lead storage battery material adopts plumbous antimony or lead-calcium alloy mostly.Lead-antimony alloy has machine casting performance preferably and dark charge and discharge ability, but Sb
3+Ion easily moves between dividing plate and deposits in negative terminal surface, thereby has reduced the overpotential of hydrogen evolution on the negative pole, makes battery very easily gassing dehydration under charging or overcharge condition, and this will cause the dry too early and termination life-span of battery; Though it is little that lead-calcium alloy has the gassing dehydration, battery need not add advantages such as water maintenance, in charging process, and very easily the grow high-resistance anodic attack layer of one deck and serious intercrystalline corrosion takes place of its anode plate grid surface.Thus, greatly influence battery and filled, put performance deeply, shortened the useful life of battery.Though above-mentioned two kinds of alloys respectively have its advantage, all are difficult to satisfy long-life instructions for use of battery, the urgent need exploitation is a kind of can eliminate antimony gas dehydration easy to break, can avoid calcium easily to produce the novel no antimony of the defective of high resistance corrosion layer, no calcium positive grid alloy again.
Summary of the invention
The objective of the invention is to propose a kind of corrosion resistance and good, again positive electrode grid of lead storage battery material of gas dehydration not easy to break and preparation method thereof.
The material as positive electrode grid of lead storage battery that the present invention proposes is a kind of lead-rare earth multicomponent alloy, by a large amount of lead, and a small amount of tin and aluminium, an amount of rare earth metal is formed, and its mixture ratio by weight percent is:
Tin (Sn) is 0.15-10%,
Aluminium (Al) is 0.02-3.0%,
Rare earth metal is 0.01-5.0%,
Surplus is plumbous.
Here, rare earth metal is one or more in lanthanum (La) series rare earth element.
In the multicomponent alloy of the present invention, the element of each component should have suitable purity.Generally, plumbous purity is greater than 99.994%, and the purity of tin, aluminium, rare earth is 99.5～99.9%.
The preparation method of above-mentioned lead-rare earth multicomponent alloy is as follows:
Adopt vacuum melting method to prepare lead-aluminium-rare-earth intermediate alloy earlier, (proportioning of intermediate alloy is about: lead: (17-99) % to add aforementioned lead-aluminium-rare-earth intermediate alloy again in the Lead-tin alloy of fusion in advance, aluminium: (0.01-3.0) %, rare earth metal: (1-80) %, total amount satisfies 100%), and, make the aluminium-rare-earth multicomponent alloy of forming by lead, aluminium, tin and rare earth element by the above-mentioned desired content dilution of each element.
Above-mentioned preparation method's concrete steps are:
Take by weighing lead, aluminium and rare earth metal at first in proportion, in vacuum equipment, be heated to 800 ℃ more than-1600 ℃, make its congruent melting.This moment, rare earth metal and lead, aluminium formed lead (Pb)-aluminium (the Al)-rare earth intermediate alloy of high rare-earth content in the congruent melting process according to eutectic point decline principle.
Secondly, take by weighing Pb, Sn and the Pb-Al-rare earth intermediate alloy of required weight respectively by the content ratio of each element in the required work alloy.In lead melting furnace, terne metal is melted in advance and stir, be warming up to subsequently more than 600 ℃, again the Pb-Al-rare earth intermediate alloy of required weight is sunk to Pb-Sn alloy melt in furnace and fully stir; Inject the lead pig mould at last and make Pb-Al-rare earth multicomponent work alloy (being called for short lead-rare earth multicomponent alloy).When needs prepare anode plate grid, be about to this alloy pig fusing and the required proper temperature of control grid casting, molten alloy is injected the grid mould, promptly get the anode plate grid of required alloy composition after the demoulding.
Owing to contain Pb, Sn and rare earth element in the new lead-rare earth multicomponent alloy component that proposes of the present invention, carry out the congruent melting smelting by usual way and will run into following difficulty: (1). the fusing point of above-mentioned element has nothing in common with each other.Fusing point plumbous and tin is very low, be respectively 327 ℃ and 232 ℃, and rare earth element is finished up to 1000～1800 ℃, and three's fusing point differs greatly, the alloying difficulty; (2). the density of rare earth element is plumbous much lower.When alloying, after low-melting plumbous fusing, lighter high-melting-point rare earth metal can not dissolve and float on plumbous bath surface, at high temperature very fast oxidized scaling loss.For this reason, the present invention selects metallic element aluminium (Al), as the additive of intermediate alloy, has both helped the fusion of rare earth alloy, plays the protective effect that prevents rare-earth oxidation again.
Congruent melting and intermediate alloy transition method in the vacuum proposed by the invention have successfully solved the smelting problem of lead-rare earth multicomponent alloy.
Prepared lead-rare earth multicomponent the alloy of the present invention has superior corrosion resistance energy and low anodic attack layer impedance.The lead acid accumulator that adopts this alloy to make as anode plate grid, can overcoming the aluminium-antimony alloy grid, to be easy to dehydration dry, and lead-calcium alloy is easy to defectives such as growing high resistant etch resistant layer, has improved the discharge performance of battery, has prolonged the useful life of battery.Its cycle performance is assigned more than 875 times at 60%DOD, and its float life is at capability retention 〉=80%C
10The time, increase more than 1 times than the Pb-Ca-Sn alloy.
Lead proposed by the invention-rare earth multicomponent alloy, not only can be applicable to the anode plate grid material of floating charge communication battery and electric bicycle electrokinetic cell, but also can be applied to the required positive electrode grid of lead storage battery of various fields such as vehicle launch, UPS, electric power system and storage of solar energy and conversion.
Embodiment
Embodiment 1, the manufacturing of lead-aluminium-rare-earth intermediate alloy
Take by weighing No. 1 electrolytic lead (purity 99.994%) of 100kg, the metal aluminum shot of 8kg (purity＞99.5%), the rare earth metal lutetium (Lu) (purity＞99.5%) of 80kg, place vacuum melting furnace, under vacuum condition, be heated to 1350 ℃, treat that alloy melts altogether after, insulation was also stirred 10-30 minute continuously, make that each element is evenly distributed in the alloy, under vacuum condition, cast the alloy pig of every 20kg1 piece subsequently.
Embodiment 2, the manufacturing of lead-aluminium-rare-earth intermediate alloy
No. 1 electrolytic lead of 100kg, the metallic aluminium of 15kg, the rare earth metal (Tb) of 1kg. (purity of lead, aluminium and rare earth metal is with example 1) 1250 ℃ of of of of of and fully of .With above-mentioned metal derby mix be placed in the vacuum melting furnace be heated to stir evenly after, under vacuum condition, cast the alloy pig of the about 10kg of every ingot.
Embodiment 3, the preparation of lead-rare earth multicomponent alloy (work alloy):
Take by weighing No. 1 electrolytic lead (purity 99.994%) of 1000kg, electrolytic tin 5kg (purity 99.5%), in lead melting furnace, be heated to more than 400 ℃, be warming up to after the congruent melting about 550 ℃, take by weighing intermediate alloy weight in example 1 or the example 2 in the ratio of aluminium in the required work alloy and rare earth metal, add in the Lead-tin alloy of congruent melting in advance, under atmospheric environment, melt, be stirred to evenly.Pure lead and a spot of tin with demand adds smelting furnace to regulate the percentage by weight of alloy at last.After reaching the ratio of required work alloy, get final product when ingot casting is waited to make grid and use.
Claims (4)
1. lead-rare earth multicomponent alloy as positive electrode grid of lead storage battery is characterized in that composition proportioning by weight percentage is as follows:
Tin (Sn) is 0.15-10%,
Aluminium (Al) is 0.02-3.0%,
Rare earth metal is 0.01-5.0%,
Surplus is plumbous;
Here, rare earth metal is one or more in the lanthanide series rare-earth elements.
2, lead according to claim 1-rare earth multicomponent alloy is characterized in that plumbous purity greater than 99.994%, and the purity of tin, aluminium, rare earth metal is 99.5-99.9%.
3, the preparation method of a kind of lead as claimed in claim 1, rare earth multicomponent alloy, it is characterized in that adopting vacuum melting method to prepare lead-aluminium-rare-earth intermediate alloy earlier, in the Lead-tin alloy of fusion in advance, add aforementioned lead-aluminium-rare-earth intermediate alloy again, and, make lead-rare earth multicomponent alloy of forming by lead, aluminium, tin and rare earth element by each element desired content dilution.
4, preparation method according to claim 3 is characterized in that taking by weighing lead, aluminium and rare earth metal at first in proportion, is heated to 800 ℃ more than-1800 ℃ in vacuum equipment, makes its congruent melting; Form the lead-aluminium-rare-earth intermediate alloy of high rare-earth content; Secondly, take by weighing Pb, Sn and the Pb-Al-rare earth intermediate alloy of required weight respectively by the content ratio of each element in the required work alloy; In lead melting furnace, terne metal is melted in advance and stir, be warming up to subsequently more than 600 ℃, again the Pb-Al-rare earth intermediate alloy of required weight is sunk to Pb-Sn alloy melt in furnace and fully stir; Inject the lead pig mould at last and make Pb-Al-rare earth multicomponent work alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031161324A CN1208860C (en) | 2003-04-03 | 2003-04-03 | Plumbum-rare earth mulaticomponent alloy being used as positive plate grid of lead accumulator and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031161324A CN1208860C (en) | 2003-04-03 | 2003-04-03 | Plumbum-rare earth mulaticomponent alloy being used as positive plate grid of lead accumulator and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1447467A true CN1447467A (en) | 2003-10-08 |
| CN1208860C CN1208860C (en) | 2005-06-29 |
Family
ID=28050502
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031161324A Expired - Fee Related CN1208860C (en) | 2003-04-03 | 2003-04-03 | Plumbum-rare earth mulaticomponent alloy being used as positive plate grid of lead accumulator and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1208860C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105925840A (en) * | 2016-06-14 | 2016-09-07 | 界首市南都华宇电源有限公司 | Process for preparing rare earth alloy for lead-acid storage batteries |
| CN108467968A (en) * | 2018-02-06 | 2018-08-31 | 天能电池集团有限公司 | A kind of preparation method of lead accumulator grid alloy |
| CN110423917A (en) * | 2018-07-31 | 2019-11-08 | 荷贝克电池有限责任及两合公司 | Metal, electrode and battery |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101901911B (en) * | 2009-05-27 | 2012-07-04 | 中国科学院金属研究所 | Special industrial pure lead for lead-acid batteries |
-
2003
- 2003-04-03 CN CNB031161324A patent/CN1208860C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105925840A (en) * | 2016-06-14 | 2016-09-07 | 界首市南都华宇电源有限公司 | Process for preparing rare earth alloy for lead-acid storage batteries |
| CN108467968A (en) * | 2018-02-06 | 2018-08-31 | 天能电池集团有限公司 | A kind of preparation method of lead accumulator grid alloy |
| WO2019153795A1 (en) * | 2018-02-06 | 2019-08-15 | 天能电池集团有限公司 | Method for preparing grid alloy of lead battery |
| US11851732B2 (en) | 2018-02-06 | 2023-12-26 | Tianneng Battery Group Co., Ltd. | Method for preparing grid alloy of lead battery |
| CN110423917A (en) * | 2018-07-31 | 2019-11-08 | 荷贝克电池有限责任及两合公司 | Metal, electrode and battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1208860C (en) | 2005-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101656312B (en) | Alloy material for high-energy accumulator grid and preparation method thereof | |
| CN111455248B (en) | Magnesium air battery anode material and preparation method thereof | |
| CN101510609A (en) | Alloy material for accumulator positive slab lattice and preparation method thereof | |
| CN102660697B (en) | Lead-acid battery grid alloy for power | |
| CN112952211B (en) | Liquid metal battery and preparation method thereof | |
| CN101685863A (en) | Rare-earth alloy lead plate grid material for accumulator | |
| CN102329982B (en) | Lead-antimony rare-earth positive grid alloy and preparation method thereof | |
| CN103985879B (en) | A kind of plumbous calcium stannum aluminum positive grid alloy and preparation method thereof | |
| CN109786754B (en) | Lead-acid storage battery positive grid made of lead-calcium-tin-copper rare earth alloy and manufacturing method thereof | |
| CN107579255A (en) | A kind of positive electrode grid of lead storage battery alloy and preparation method thereof | |
| CN1216163C (en) | Multicomponent Pb-Sn-RE alloy for positive slab lattice of lead accumulator | |
| CN1208860C (en) | Plumbum-rare earth mulaticomponent alloy being used as positive plate grid of lead accumulator and its preparation method | |
| CN1262028C (en) | Rareearth lead based grid alloy and mfg. process thereof | |
| CN105024083A (en) | Manufacturing method of lead-carbon positive grid for lead-acid storage battery | |
| CN101824562A (en) | Positive grid alloy material for lead-acid storage battery | |
| CN108808010A (en) | A kind of Moped Scooter positive electrode grid of lead storage battery alloy and preparation method thereof | |
| CN102427138A (en) | Preparation method for electric bicycle storage battery grid alloy | |
| CN86103370A (en) | Grid alloy of battery and production method thereof | |
| Prengaman | Current-collectors for lead–acid batteries | |
| CN115132960A (en) | Aluminum-air battery cathode and preparation method thereof | |
| CN101604754A (en) | A kind of storage battery Pb-Sb grid material | |
| CN110819835A (en) | Long-life high-power storage battery and grid alloy | |
| CN116287858B (en) | Lead-based barium sodium aluminum alloy for negative grid of lead-acid storage battery, and preparation method and application thereof | |
| CN110212255B (en) | Liquid battery and preparation method thereof | |
| CN102403487A (en) | Preparation method of lead-acid storage battery anode for electric bike |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |