CN104377365A - Positive-electrode plate alloy for lead-acid storage battery - Google Patents
Positive-electrode plate alloy for lead-acid storage battery Download PDFInfo
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- CN104377365A CN104377365A CN201410668368.5A CN201410668368A CN104377365A CN 104377365 A CN104377365 A CN 104377365A CN 201410668368 A CN201410668368 A CN 201410668368A CN 104377365 A CN104377365 A CN 104377365A
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- alloy
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- earth
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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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C11/00—Alloys based on lead
- C22C11/06—Alloys based on lead with tin as the next major constituent
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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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention discloses a positive-electrode plate alloy for a lead-acid storage battery. The novel rare-earth alloy is formed by adding a lanthanide (rare earth) into the existing lead-calcium-tin-aluminum alloy. The novel rare-earth alloy comprises the following components in percent by weight: 0.07-0.11% of calcium, 1.0-1.2% of tin, 0.001%-0.003% of aluminum, 0.01-0.03% of lanthanum (rare earth) and the balance of lead, wherein the lanthanum (rare earth) is rhenium. The crystalline grains of the novel rare-earth alloy disclosed by the invention are fine and distributed uniformly, thus the novel rare-earth alloy has excellent overall performance such as high strength, high toughness, good resistance to fatigue and corrosion and good electrical conductivity, and the lead-acid storage battery adopting the positive-electrode plate alloy has high deep cycle performance and long service life and is particularly suitable for the start-stop system of an automobile.
Description
Technical field
The present invention relates to a kind of process for positive slab lattice of lead-acid accumulator alloy for automobile start-stop system, belong to lead acid accumulator field.
Background technology
The lead-acid battery used in the market, the anode plate grid lead alloy that it adopts, can be divided into lead-antimony alloy and Pb-Ca-Sn-Al alloy.Lead-antimony alloy has the advantages such as deep-circulating performance is good, cost is lower, and shortcoming is that its overpotential of hydrogen evolution is lower, easy dehydration.Although add cadmium can improve overpotential of hydrogen evolution, cadmium is to the pollution of environment, and along with the enhancing of people's environmental consciousness and national environmental protection control the raising of dynamics, lead acid accumulator to be inevitable development trend without cadmium.And the Pb-Ca-Sn-Al alloy of high tin, there is the problems such as premature capacity loss, useful life is short.Lead acid accumulator for automobile start-stop system has higher requirement to maintenance-free performance, environmental-protecting performance and deeper cavity life-span, and existing battery can not be satisfied the demand, and particularly the positive grid alloy of battery is anxious to be modified.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of and improve battery deep-circulating performance, extend the process for positive slab lattice of lead-acid accumulator alloy for automobile start-stop system of battery.
Technical scheme of the present invention adds lanthanide series rare-earth elements in original Pb-Ca-Sn-Al alloy, form a kind of rare earth alloy, the weight percent content of each constituent of this alloy is: calcium 0.07% ~ 0.11%, tin 1.0% ~ 1.2%, aluminium 0.001% ~ 0.003%, lanthanide series rare-earth elements 0.01% ~ 0.03%, all the other are plumbous.
Described lanthanide series rare-earth elements is rhenium (Re).
The interpolation of rare earth elements of the present invention adopt content be 1% rare earth alloy be mixed with the rare earth alloy that ree content is 0.01% ~ 0.03%.Rare earth element additive, crystal grain thinning, helpful to the mechanical property, decay resistance, casting character etc. of grid alloy.Composite additive can significantly improve the electric conductivity of alloy, intensity, hardness and creep resistance, and can improve the deep discharge cycle performance of battery.
Accompanying drawing explanation
Fig. 1 is rare earth alloy metallograph.
Fig. 2 is original Pb-Ca-Sn-Al alloy metallograph.
Fig. 3 is the research (peak current and spike potential in 0.9 V lower linear scanning) of grid surface passivating film.
Embodiment
1, original Pb-Ca-Sn-Al alloy adds lanthanide series Re, and being made into sample, is 1# alloy;
2, choosing former Pb-Ca-Sn-Al alloy as blank sample, is 2# alloy;
1# and 2# alloying component content is as following table:
%
Below be all weight percentage.
3, two kinds of samples are carried out to hardness test, metallographic experiment, the existing scanning of liberation of hydrogen respectively, analyse the detection of the projects such as oxygen AC impedance, alloy surface passivating film, constant current corrosion, and contrast.
Contrast and analysis, known beneficial effect of the present invention:
1, rare earth alloy is smoothly more clear than traditional lead-calcium alloy crystal boundary, and crystal grain is tiny, regular, distribution uniform, as shown in Figure 1, Figure 2.Under same deformation condition, the deflection of rare earth alloy is dispersed in more crystal grain and carries out, make the distortion of each crystal grain also more even and unlikely phenomenon producing the component of stress and concentrate, be conducive to preventing alloy recrystallization simultaneously, strengthen the mechanical performance of alloy.Therefore rare earth alloy has better toughness, plasticity, crushing resistance.
2, rare earth alloy makes alloy liberation of hydrogen, overpotential for oxygen evolution raise because of the effect of rare earth element and composite additive, effectively can suppress the precipitation of hydrogen and oxygen.Rare earth alloy has good liberation of hydrogen oxygen evolve, can reduce the generation of lead acid accumulator damage by water consumption and self discharge, improve its maintenance-free performance.
3, rare earth alloy effectively inhibits the generation of the oxide such as PbO in passivating film.Fig. 3 is the research of grid surface passivating film, and the b peak-to-peak electricity ratio 1# alloy of 2# alloy is large, and illustrate that 2# generates more Pb when film forming, rare earth alloy can suppress the growth of alloy surface passivating film compared with traditional lead-calcium alloy.Rare earth alloy changes the structure of lead alloy because of the interpolation of rare earth element and composite additive element, form thinner corrosion product, fine and close corrosion layer, effective prevention electrolyte corrodes grid alloy substrate further, alleviate the intercrystalline corrosion of grid alloy, prevent the outbreak-crash of grid, make it have good decay resistance.Simultaneously due to the reduction of PbO content in corrosion layer and passivating film, improve the conductivity on grid alloy surface, early stage capacitance loss can be prevented, contribute to the raising of lead acid accumulator deep-circulating performance, extend the useful life of lead acid accumulator.
4, rare earth alloy rare earth elements and composite additive element combine and have played better alloying effect, compared with traditional lead-calcium alloy, novel rare-earth lead-calcium alloy has very excellent plasticity, toughness and anti-fatigue performance, avoid the impact of intermetallic compound, improve the hardness of alloy.In grid foundry production, find that rare earth alloy embodies fine mechanical strength, casting character, particularly reach good age-hardening effect.
Rare earth alloy remains traditional Pb-Ca-Sn-Al alloy lot of advantages, turn avoid many shortcomings of traditional Pb-Ca-Sn-Al alloy simultaneously, Pb-Sb-Cd alloy or traditional Pb-Ca-Sn-Al alloy can be replaced for the anode plate grid material of the lead acid accumulator of applicable automobile start-stop system.
Claims (2)
1. a process for positive slab lattice of lead-acid accumulator alloy, for Pb-Ca-Sn-Al alloy, it is characterized in that adding lanthanide series rare-earth elements in this alloy, the weight percent content of each constituent is: calcium 0.07% ~ 0.11%, tin 1.0% ~ 1.2%, aluminium 0.001% ~ 0.003%, lanthanide series rare-earth elements 0.01% ~ 0.03%, all the other are plumbous.
2. process for positive slab lattice of lead-acid accumulator alloy according to claim 1, is characterized in that: described lanthanide series rare-earth elements is rhenium (Re).
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CN201410668368.5A CN104377365A (en) | 2014-11-20 | 2014-11-20 | Positive-electrode plate alloy for lead-acid storage battery |
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CN201410668368.5A CN104377365A (en) | 2014-11-20 | 2014-11-20 | Positive-electrode plate alloy for lead-acid storage battery |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111063894A (en) * | 2019-11-30 | 2020-04-24 | 河南超威电源有限公司 | Rare earth grid alloy for lead-acid storage battery |
CN111118337A (en) * | 2019-12-17 | 2020-05-08 | 双登集团股份有限公司 | High-performance corrosion-resistant positive grid alloy of lead-acid storage battery |
CN111682166A (en) * | 2020-05-14 | 2020-09-18 | 天能电池集团股份有限公司 | Positive plate for high-capacity battery, preparation method and high-capacity battery |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101106197A (en) * | 2007-08-06 | 2008-01-16 | 回静 | Accumulated plate bar alloy material and its making method |
CN101510609A (en) * | 2009-03-31 | 2009-08-19 | 赵恒祥 | Alloy material for accumulator positive slab lattice and preparation method thereof |
CN102694180A (en) * | 2012-06-11 | 2012-09-26 | 泉州市东日电器发展有限公司 | Lead-lanthanum storage battery and manufacturing method thereof |
-
2014
- 2014-11-20 CN CN201410668368.5A patent/CN104377365A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101106197A (en) * | 2007-08-06 | 2008-01-16 | 回静 | Accumulated plate bar alloy material and its making method |
CN101510609A (en) * | 2009-03-31 | 2009-08-19 | 赵恒祥 | Alloy material for accumulator positive slab lattice and preparation method thereof |
CN102694180A (en) * | 2012-06-11 | 2012-09-26 | 泉州市东日电器发展有限公司 | Lead-lanthanum storage battery and manufacturing method thereof |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111063894A (en) * | 2019-11-30 | 2020-04-24 | 河南超威电源有限公司 | Rare earth grid alloy for lead-acid storage battery |
CN111118337A (en) * | 2019-12-17 | 2020-05-08 | 双登集团股份有限公司 | High-performance corrosion-resistant positive grid alloy of lead-acid storage battery |
CN111682166A (en) * | 2020-05-14 | 2020-09-18 | 天能电池集团股份有限公司 | Positive plate for high-capacity battery, preparation method and high-capacity battery |
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Application publication date: 20150225 |