CN1294418A - Alloy material for lattice plate of deeply cyclic battery - Google Patents
Alloy material for lattice plate of deeply cyclic battery Download PDFInfo
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- CN1294418A CN1294418A CN99121258A CN99121258A CN1294418A CN 1294418 A CN1294418 A CN 1294418A CN 99121258 A CN99121258 A CN 99121258A CN 99121258 A CN99121258 A CN 99121258A CN 1294418 A CN1294418 A CN 1294418A
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
A lead-base alloy for the deeply cyclic lattice plate of lead-acid accumulator contains Ca (0.01-0.03%), Sn (0.8-2%), Al (0.01-0.03%), etc. Its advantages include better deep cycle performance and anticorrosion nature, no passivating membrane generation in discharge, long deep cyclic life, high hydrogen and oxygen educing overpotential, and high mechanical performance.
Description
The present invention relates to field of alloy material, especially relate to a kind of alloy material that is used for the sealed non-maintenance lead-acid accumulator cell grid.
In recent years, flourish along with telecommunications industry, maintenance-free lead accumulator industry also fast development is got up, and as the grid material of one of storage battery important component part, is also just experiencing unprecedented research tide.Grid is a topmost inactive ingredients in the battery, but essential, and it act as conduction current and supports active material, and is very big for the performance impact of battery.
The battery that traditional lead-antimony alloy grid is made is overcharging, is having when depositing a large amount of gas effusions, and this not only needs often to add water safeguards, and can cause certain corrosion to the equipment around the battery, and environment is caused harmful effect.The Pb-Ca-Sn-Al-Ba alloy that the Pb-As-Sn alloy that No. 2197342 patents of Britain propose, No. 9730183 patents of France propose, China's publication number is the Pb-Cd-Bi-As-Ce alloy that No. 1084578 patent application case proposes, and Chinese publication number is the Pb-Sb-Cd-Na that No. 1148628 patent application case proposes
2S
4(Na
2S
5-As-Sn-Cu alloy, Chinese publication number are that the Bb-Bi-Na-Se-Al-Sn alloy of No. 1132795 patent application case proposition, ultralow antimony Pp-Sb-Na-(K or Li)-S (Ag or S or Sn) alloy etc. that this patent application case of No. 1074949 of Chinese publication number proposes are all invented at the completely-sealed lead-acid battery, these batteries generally all are in charged stand-by state, often do not carry out charge and discharge cycles, thereby people value more is its float life.Along with marching of the past power market of lead-acid battery, the shortcoming of this battery shows soon: charge acceptance is poor, and cycle life is short, and early stage capacitance loss easily takes place.People have carried out a large amount of research to this.Lead-calcium alloy carried out surperficial rich Sn, rich Sb handle or the alloy addition face that adds other is new research focus.No. 10112325 patents of Japan, No. 05234596 patent have just proposed the technology at lead-calcium alloy surface injection Sb and metallic; No. 795918 patents in Europe propose to add dispersant particles such as the oxide nitrate that is insoluble to Pb and sulfuric acid or carbonate in alloy, improve alloy property by changing crystal size.These technologies are to the requirement height of equipment, and operation is more complicated also, therefore are subjected to certain restriction in actual applications.Reducing antimony content in traditional lead-antimony alloy, add other alloy addition simultaneously and guarantee that alloy has good casting properties, mechanical performance and deep-circulating performance, also is one of focus of research now.
The objective of the invention is to overcome the deficiency of existing grid alloy, provide a kind of corrosion impedance higher, corrosive film compact structure, good conductivity, good mechanical property, the alloy material for lattice plate of deeply cyclic battery that cycle life is long.
Another object of the present invention provides a kind of crystal region, the gel region electron conduction is good, and the hydrogen-evolution overpotential height, is beneficial to the alloy material for lattice plate of deeply cyclic battery of full sealed non-maintenance.
Purpose of the present invention can realize by following proposal:
The lattice plate of deeply cyclic battery alloy system is made up of Pb, Ca, Sn and Al, and its alloy composition weight ratio is: 0.03-0.10%Ca, and 0.80-2.0%Sn, 0.01-0.03%Al, all the other are Pb.
For the hydrogen-evolution overpotential that improves alloy and decay resistance etc., can in alloy of the present invention, add Ag and Bi, its alloying component weight ratio is 0.03-0.10%Ca, 0.80-2.0%Sn, 0.01-0.03%Ag, 0.01-0.15%Bi, all the other are Pb.
A kind of preferable alloying component weight ratio of the present invention is 0.03-0.05%Ca, 1.2-1.4%Sn, and 0.02-0.03%Al, all the other are Pb.
In addition, in aforementioned alloying component, the content that adds Ag and Bi further can be optimized, its alloying component weight ratio can also be optimized for respectively: 0.04-0.08%Ag and 0.02-0.06%Bi.The lead base grid alloy of Zu Chenging thus, the structure of the corrosive film that is generated in curing, generation and use is tightr, formed almost fissureless integral body, and the distribution of Sn in this film is more even.
Why technique scheme of the present invention can realize purpose of the present invention effectively, and its reason mainly can be explained according to following theory and analysis:
According to the Hume-Rothy theory, when two kinds of atoms of elements semidiameters greater than 15% the time, the solubility of a kind of element in another kind of element is very low, has only the close element of atomic radius could form solid solution widely.The present invention selects for use the difference of atomic radius and lead in 15%, can form the above-mentioned element of extensive solid solution as additive with lead.On the other hand, must have close electronegativity according to the theoretical two kinds of elements that form solid solution of Gordy, select for use alloy addition electronegativity and lead to differ in 0.4, form the element of compound probably with lead, the solubility of formed compound in lead is lower, in process of setting, preferentially separate out as nucleus, constitute the hard network, the alloy system mechanical strength is increased.
According to the crystal colloidal theory of Povlov, active material and corrosive film all are to have crystal region and gel region to constitute.Gel region is to be made of linear hydrated polymer chain, plays the connection electric action between crystal region, and its decomposition will be unfavorable for the prolongation of electrode life.The affinity of elements such as Sn, Bi, Ag and water is higher, and polymer chain is aquation to a certain extent, so the ion of these several elements is easy to form polymer network with the hydrated polymer chain combination, effect is just as adhesive, and these adhesives can the support polymer networks and stoped its variation owing to positive active material density to be decomposed.In addition, the oxidation product of these several elements can be mingled with in corrosive film, improves the conductivity of internal layer corrosive film, and high tin can stop the reduction of PbO in the corrosive film, reduction potential is born moved, thereby passivating film is generated.
Anode plate grid solidify, change into and subsequently use in all can corrode, generate corrosive film.This tunic plays the effect of bonding active material on the one hand, can stop further developing of corrosion again on the other hand.Corrosive film mainly is that the lead oxide by brown lead oxide and non-stoichiometric constitutes, and these materials can reduce in discharge process, generation PbSO
4Or PbO, if but these content of material are excessive, and internal resistance just increases, and just may make corrosion layer become the barrier layer of conduction current.Explain the corrosive film structure with crystal-colloidal theory, corrosive film is made of crystal region and gel region, crystal region mainly is that the oxide by non-stoichiometric lead constitutes, when stoichiometric number greater than 1.5 the time, the conductivity of PbO is suitable with the conductivity of PbO, and the n value depends primarily on institute and adds electrode potential and alloy addition type.Suitable alloy addition not only can carry out easily as the chemical reaction that catalyst increases the n value, and its corrosion product can improve the conductivity of corrosive film as doped semiconductor.Such as alloy additions such as Sn, Bi, Ag.Its corrosion back ion can mix and enter gel region, improve the formation network of linear hydrated polymer chain, this is because the affinity of these ions and water is higher, easier formation hydrated polymer, it stops polymer owing to the positive active material variable density is decomposed (its mechanism of action is referring to accompanying drawing 1) as adhesive support polymer chain.
When not having these elements, polymer network only just has good electrical conductivity when density polymer is higher, and along with the carrying out of circulation, positive active material density changes, the very fast decomposition of polymer chain, and gel region conductivity descends, and electrode capacity descends.So alloy additions such as Sn, Bi, Ag have not only improved the electron conduction of crystal region, also improved the electron conduction of gel region, the trend of its aquation had both been stablized the concentration of gel region, had improved the proton conductive of film again.
Select suitable grid alloy, improve the composition and the character of grid formed anode film during battery operated, make it have conductivity and stability preferably, can this be one of the present invention's key that be applied to the deep circulation power type energy.
Usually, help corroding the raising of impedance in the lead-calcium alloy along with the reduction of the increase of Sn content and Ca content.The corrosion impedance that contains the plumbous calcium quaternary alloy of low calcium 0.05% and Gao Xi 1.2% reaches the highest, and traditional relatively lead-calcium alloy improves 16.8%.The adding of metal Bi can be played the effect of grain refinement, and the crystalline particle average-size is reduced, and can form uniform corrosion product, and the corrosive film compact structure can prevent effectively that sulfuric acid solution from contacting with the further of metal under the film, thereby reduce corrosion.Be increased to 23.5% when the solid solubility of Bi in Pb can reach 18%, 184 ℃ of peritectic temperature under the room temperature, so theoretically, Bi can form good solid solution in Pb, and promptly Bi can increase the decay resistance of grid alloy.
The technology of the present invention is compared with conventional P b-Ca, because the increase of Sn content and the reduction of Ca content help the improvement of corrosive film performance.Also relatively evenly, Sn being mingled with in corrosion product will cause the reinforcement greatly of semiconductor conductivity in the distribution of Sn in corrosive film, plays an important role to improving corrosive film conductivity.In addition, the effect of relieve stresses has also been played in the increase of Sn content, and the corrosive film be full of cracks is disappeared.
Therefore, the present invention has following advantage:
1, there is the active colloidal skeleton ion that can improve corrosive film crystal-colloform texture in the alloy corrosion product, gel region density is kept relative stability; Semiconductor inclusion obviously improves the conductivity of corrosive film, has effectively prevented the generation of passivating film on grid and the reactive species interface, has prolonged battery life.
2, alloy has excellent corrosion resisting performance, and the weight-loss method analysis result shows that the decay resistance of above-mentioned alloy improves 20%-50% than conventional alloys.
3, alloy has high liberation of hydrogen, overpotential for oxygen evolution, can effectively suppress to overcharge, the separating out of gas when depositing, and makes battery accomplish full sealed non-maintenance.
4, there is Pb in the alloy system
3Ca, Pb
3Sn, Pb
3(Ca
xSn
1-x) the sclerosis network that constituted, alloy has good mechanical strength.
Fig. 1 is that gel region hydrated polymer chain passes through Sn among the present invention
4+Connection diagram.
Below by embodiment, material prescription of the present invention is further illustrated.
Alloy material for lattice plate of deeply cyclic battery can be by several composition the among Pb, Ca, Sn, Al, Bi, the Ag.Specifically multiple embodiments can be arranged.For example, every 100g alloying component can be listed as follows:
| Sequence number | Calcium (Ca) g | Tin (Sn) g | Aluminium (Al) g | Bismuth (Bi) g | Silver (Ag) g | Plumbous (Pb) g |
| ?1 | ?0．03 | 1．2 | ?0．01 | All the other are plumbous | ||
| ?2 | ?0．04 | 1．4 | ?0．02 | All the other are plumbous | ||
| ?3 | ?0．05 | 1．6 | ?0．02 | All the other are plumbous | ||
| ?4 | ?0．1 | ?1．8 | ?0．03 | All the other are plumbous | ||
| ?0．04 | ?1．2 | ?0．01 | ?0．02 | All the other are plumbous | ||
| ?6 | ?0．05 | ?1．4 | ?0．02 | ?0．08 | All the other are plumbous | |
| ?7 | ?0．06 | ?1．0 | ?0．03 | ?0．16 | All the other are plumbous | |
| ?8 | ?0．08 | ?0．8 | ?0．03 | ?0．12 | All the other are plumbous | |
| ?9 | ?0．05 | ?1．4 | ?0．02 | ?0．04 | All the other are plumbous | |
| ?10 | ?0．06 | ?2．0 | ?0．02 | ?0．20 | All the other are plumbous | |
| ?11 | ?0．05 | ?1．0 | ?0．02 | ?0．01 | All the other are plumbous | |
| ?12 | ?0．05 | ?1．4 | ?0．02 | ?0．04 | All the other are plumbous | |
| ?13 | ?0．08 | ?1．6 | ?0．03 | ?0．10 | All the other are plumbous | |
| ?14 | ?0．03 | ?1．2 | ?0．02 | ?0．02 | All the other are plumbous | |
| ?15 | ?0．04 | ?1．2 | ?0．02 | ?0．06 | All the other are plumbous | |
| ?16 | ?0．02 | ?0．8 | ?0．01 | ?0．15 | All the other are plumbous |
The manufacture method of grid material of the present invention can adopt direct addition method.More particularly, be that electrolytic lead is melted in general furnace, control plumbous liquid temp between 400 ℃-800 ℃, calcium and aluminium are added in the plumbous liquid simultaneously, stir immediately more than 5 minutes, and keep plumbous liquid temp constant.After stirring finishes, every in plumbous liquid the proportioning by each element of table 1 add tin, silver and bismuth respectively, promptly make alloy material of the present invention.
Claims (6)
1, a kind of alloy material for lattice plate of deeply cyclic battery, the percentage that it is characterized in that alloying component weight is 0.03-0.01%Ca, 0.80-2.0%Sn, 0.01-0.03%Al, all the other are Pb.
2, alloy material for lattice plate of deeply cyclic battery as claimed in claim 1, the percentage that it is characterized in that alloying component weight is 0.03-0.01%Ca, 0.80-2.0%Sn, 0.01-0.03%Al, 0.02-0.20%Ag, 0.01-0.15%Bi, all the other are Pb.
3, alloy material for lattice plate of deeply cyclic battery as claimed in claim 1 or 2, the percentage that it is characterized in that alloying component weight is 0.03-0.05%Ca, 1.20-1.40%Sn, 0.02-0.03%Al, all the other are Pb.
4, alloy material for lattice plate of deeply cyclic battery as claimed in claim 1 or 2, the percentage that it is characterized in that alloying component weight is 0.03-0.05%Ca, 1.20-1.40%Sn, 0.02-0.03%Al, 0.04-0.08%Ag, all the other are Pb.
5, alloy material for lattice plate of deeply cyclic battery as claimed in claim 1 or 2, the percentage that it is characterized in that alloying component weight is 0.03-0.05%Ca, 1.20-1.40%Sn, 0.02-0.03%Al, 0.02-0.06%Bi, all the other are Pb.
6, alloy material for lattice plate of deeply cyclic battery as claimed in claim 1 or 2, the percentage that it is characterized in that alloying component weight is 0.03-0.05%Ca, 1.20-1.40%Sn, 0.02-0.03%Al, 0.04-0.08%Ag, 0.02-0.06%Bi, all the other are Pb.
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| Application Number | Priority Date | Filing Date | Title |
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| CN99121258A CN1294418A (en) | 1999-10-23 | 1999-10-23 | Alloy material for lattice plate of deeply cyclic battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99121258A CN1294418A (en) | 1999-10-23 | 1999-10-23 | Alloy material for lattice plate of deeply cyclic battery |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100499227C (en) * | 2002-04-18 | 2009-06-10 | 古河电池株式会社 | Lead-based alloy, lead acid battery substrate and lead-acid battery |
| 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 |
| CN102646832A (en) * | 2012-05-10 | 2012-08-22 | 山东瑞宇蓄电池有限公司 | Lead plaster composition for manufacturing positive plate of lead-acid storage battery, positive plate of lead-acid storage battery and lead-acid storage battery |
| CN102660697A (en) * | 2012-04-27 | 2012-09-12 | 天能电池集团有限公司 | Lead-acid battery grid alloy for power |
| CN103700812A (en) * | 2013-10-15 | 2014-04-02 | 双登集团股份有限公司 | High temperature resisting deep-circulation lead acid battery |
| CN103715396A (en) * | 2012-09-29 | 2014-04-09 | 天能电池(芜湖)有限公司 | Formation process for electrode plate of lead-acid storage battery |
| CN104466119A (en) * | 2014-11-24 | 2015-03-25 | 天能电池集团（安徽）有限公司 | Special cast-weld alloy composition for lead-acid battery |
| CN105098195A (en) * | 2014-06-27 | 2015-11-25 | 浙江天能电池(江苏)有限公司 | Lead-calcium-stannum-aluminum positive grid alloy and preparation method thereof |
| CN109518017A (en) * | 2018-10-24 | 2019-03-26 | 山东久力工贸集团有限公司 | A kind of maintenance-free lead accumulator positive plate grid metal and preparation method thereof |
| CN109643804A (en) * | 2016-08-26 | 2019-04-16 | 日立化成株式会社 | Lead storage battery and casting grid and its manufacturing method |
| CN114790523A (en) * | 2022-03-09 | 2022-07-26 | 安徽力普拉斯电源技术有限公司 | Lead-calcium-tin-aluminum-silver-bismuth positive grid alloy and preparation method thereof |
-
1999
- 1999-10-23 CN CN99121258A patent/CN1294418A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100499227C (en) * | 2002-04-18 | 2009-06-10 | 古河电池株式会社 | Lead-based alloy, lead acid battery substrate and lead-acid battery |
| 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 |
| CN102660697A (en) * | 2012-04-27 | 2012-09-12 | 天能电池集团有限公司 | Lead-acid battery grid alloy for power |
| CN102660697B (en) * | 2012-04-27 | 2014-01-08 | 天能电池集团有限公司 | Lead-acid battery grid alloy for power |
| CN102646832A (en) * | 2012-05-10 | 2012-08-22 | 山东瑞宇蓄电池有限公司 | Lead plaster composition for manufacturing positive plate of lead-acid storage battery, positive plate of lead-acid storage battery and lead-acid storage battery |
| CN102646832B (en) * | 2012-05-10 | 2014-06-25 | 山东瑞宇蓄电池有限公司 | Lead plaster composition for manufacturing positive plate of lead-acid storage battery, positive plate of lead-acid storage battery and lead-acid storage battery |
| CN103715396A (en) * | 2012-09-29 | 2014-04-09 | 天能电池(芜湖)有限公司 | Formation process for electrode plate of lead-acid storage battery |
| CN103715396B (en) * | 2012-09-29 | 2016-03-02 | 天能电池(芜湖)有限公司 | Technology for forming plate electrode of lead-acid accumulator |
| CN103700812A (en) * | 2013-10-15 | 2014-04-02 | 双登集团股份有限公司 | High temperature resisting deep-circulation lead acid battery |
| CN105098195A (en) * | 2014-06-27 | 2015-11-25 | 浙江天能电池(江苏)有限公司 | Lead-calcium-stannum-aluminum positive grid alloy and preparation method thereof |
| CN104466119A (en) * | 2014-11-24 | 2015-03-25 | 天能电池集团（安徽）有限公司 | Special cast-weld alloy composition for lead-acid battery |
| CN109643804A (en) * | 2016-08-26 | 2019-04-16 | 日立化成株式会社 | Lead storage battery and casting grid and its manufacturing method |
| CN109518017A (en) * | 2018-10-24 | 2019-03-26 | 山东久力工贸集团有限公司 | A kind of maintenance-free lead accumulator positive plate grid metal and preparation method thereof |
| CN114790523A (en) * | 2022-03-09 | 2022-07-26 | 安徽力普拉斯电源技术有限公司 | Lead-calcium-tin-aluminum-silver-bismuth positive grid alloy and preparation method thereof |
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