CN101237045A - Multi-element alloy for making lead acid accumulator plate grid - Google Patents
Multi-element alloy for making lead acid accumulator plate grid Download PDFInfo
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- CN101237045A CN101237045A CNA2007100199886A CN200710019988A CN101237045A CN 101237045 A CN101237045 A CN 101237045A CN A2007100199886 A CNA2007100199886 A CN A2007100199886A CN 200710019988 A CN200710019988 A CN 200710019988A CN 101237045 A CN101237045 A CN 101237045A
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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
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- Y02E60/10—Energy storage using batteries
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Abstract
The present invention discloses a multi-component alloy for manufacturing lead-acid battery grids. The alloy contains elements of lead, calcium, tin, aluminum and bismuth, and the mass percentages of the components in the total amount of the alloy are that: calcium accounts for 0.06-0.12 percent, tin accounts for 0.08-1.5 percent, aluminum accounts for 0.017-0.034 percent, bismuth accounts for 0.084-0.13 percent; the rest is electrolytic lead. The alloy is high in hydrogen evolution potential and high in corrosion resistance. When the alloy is used for manufacturing lead-acid battery grids, the recombination efficiency of a cathode to oxygen inside batteries can be improved; the charge acceptance and overdischarge resistance of an anode in the process of deep discharge recycling use can be increased; the cycle life span of made-up lead-acid batteries is remarkably increased, and the increase rate is about 20 percent.
Description
Technical field
The present invention relates to a kind of material of making lead acid accumulator plate grid, particularly contain the multicomponent alloy of plumbous calcium tin aluminium, belong to the lead acid accumulator field.
Background technology
In recent years, to the pollution of environment generation and the reason of energy growing tension, many countries are all in the research that steps up the high-performance electric motor car for motor vehicle.Can electric motor car obtain business success, and key is its core---electrical source of power, considers from fail safe, performance and price and technology maturity, and valve controlled sealed lead-acid accumulator remains the most economical and the most practical electrical source of power of Moped Scooter.Electric boosted Vehicular battery is mainly with the medium current continuous discharge, based on dark circulation.Press the actual instructions for use of power battery, higher to the specific energy and the dark cycle life index of Vehicular battery than fixed battery request.With the most frequently used 12V10Ah of existing market (2hr capacity) battery is example, the general requirement of its 100%DOD cycle life (that is: to 36V or 48V battery were with the single lattice of constant voltage 2.45V/, current limliting 1.8-2.0A charging 8-10 hour on the same group, it is a complete cycle that constant current 5A is discharged to single battery average voltage 10.5V) reaches more than 250-300 time.Because the plumbous calcium series alloy grid material of former use is applicable to the floating charge state and uses, not anti-deep discharge circulation, in order to improve the dark cycle life of battery, most battery manufacturing enterprise tends to adopt plumbous antimony series alloy.But because the etching problem of common low antimony alloy in the battery cyclic process, and antimony moves the thermal runaway bulging problem that produces after the caused battery dehydration from positive pole dissolving to negative pole, and a lot of electrokinetic cell manufactories have adopted the method for adding cadmium in the lead-antimony alloy in manufacture process.Cadmium exists organism can not the injury of reparation property, as a kind of product for civilian use, Pb-Sb-Cd alloy make and use, in the discarded process, cadmium will cause great injury to environment, this influence to environment has caused a lot of knowledgeable people's worry.
People were studying the composition of grid alloy always in recent years, many scholar's research other element that in the Pb-Ca-Sn-Al alloy, mixes, expectation makes lead-calcium alloy keep that existing processing technology is good, on the basis of gassing overpotential height, low cost and other advantages, possess the performance that better anti-deep discharge recycles.Bismuth is present in once in plumbous and the secondary lead as a kind of difficult impurity of removing usually, and remaining bismuth causes that to the influence of battery performance people pay close attention to greatly.A lot of to the research of adding bismuth in the alloy, but do not realize satisfactory results so far.
Summary of the invention
The technical problem to be solved in the present invention is to overcome weak point of the prior art, a kind of multicomponent alloy of making lead acid accumulator plate grid is provided, and this alloy is made simple and easy, and cost is low, environment is not produced injury, and the lead acid accumulator of making can obviously improve charge acceptance and cycle life.
Technical scheme of the present invention is: the multicomponent alloy of making the lead-acid battery grid contains element lead, calcium, tin, aluminium, improvements are to contain in the alloy bismuth that mass percent is 0.084%-0.13%, and the mass percent of each component in the alloy total amount is calcium 0.06%-0.12%; Tin 0.08%-1.5%; Aluminium 0.017%-0.034%; Bismuth 0.084%-0.13%; All the other are electrolytic lead.
The gold that contains of the present invention is used in the Pb-Ca-Sn-Al quaternary quantitatively to drop on the basis of alloy and is analyzed pure bismuth granule and smelt and form, and prepares simple and easyly, and cost is low; Make grid by this alloy, and then make lead acid accumulator, show to have following advantage after tested with development test:
1, the sealed reaction efficient of battery is better than the low antimony alloy of plumbous antimony series, and is suitable with the sealed reaction efficient of common lead calcium alloy battery, can reach more than 98.5%; Simultaneously, alloy is carried out the electrokinetic potential sweep test to be proved, has suppressed in the battery hydrogen and separates out thereby this alloy has improved the overpotential of hydrogen evolution of grid, not obvious to the acceleration that oxygen on the positive pole is separated out.
2, good corrosion resistance.Alloy is carried out cyclic voltammetric test and corrosion back electron microscope scanning, found that when the Bi content that adds in the alloy is lower than certain level, the corrosion of alloy is accelerated on the contrary, but when the content of Bi in the alloy was in 0.084%～0.130% level, the decay resistance that adds the alloy ratio normal alloy of bismuth improved.
3, corrosion layer conductivity increases.With AC impedence method alloy is tested, find to add 0.034%～0.130% Bi in the alloy, the conductivity of the corrosion layer of alloy obviously improves, and degree maximum when 0.034% left and right sides of improving, but consider the influence that the alloy corrosion rate is accelerated by low content Bi, the present invention has determined that finally the addition of Bi is 0.084%～0.130%.
4, detect by the special-purpose 6-DZM-10 lead acid accumulator of the electric motor car that drops into this multicomponent alloy material grid, find that the charge acceptance of battery in cyclic process increases (20～30) % with respect to the battery of common lead calcium alloy under the same process conditions; Battery shows in the 100%DOD loop test, the battery that common relatively alloy is made, the battery that this alloy is made becomes gently at the middle and later periods of cycle life capacity attenuation, thereby has prolonged 100%DOD cycle life (15～25) % of battery under equal process conditions.
Description of drawings
Fig. 1 is the 100%DOD cycle life curve that contains the battery pack II of 0.094% bismuth in the battery pack I of common lead calcium alloy and the grid for grid, wherein
Represent battery pack I,
Represent battery pack II;
Fig. 2 is the charge acceptance curve of battery pack II in the life-span cyclic process that contains 0.094% bismuth in the battery pack I of common lead calcium alloy and the grid for grid, wherein
Represent battery pack I,---represent battery pack II.
Embodiment
Multicomponent alloy of the present invention can be used as the grid material of lead acid accumulator positive and negative electrode individually or simultaneously.
Below in conjunction with accompanying drawing, the 6-DZM-10 battery the most frequently used with Moped Scooter is example, introduces the composition, use of multicomponent alloy and to the influence of the charge acceptance in cell sealing reaction efficiency, the cyclic process, dark cycle life aspect.
Embodiment 1:
1, cell preparation
With Pb-Ca-Sn-Al quaternary foundry alloy, quantitatively put in No. 1 electrolytic lead of strain smelting of fusion, make the Pb-Ca-Sn-Al quaternary and use alloy, the mass percentage content of each composition of alloy is respectively: Ca 0.064%; Sn 1.224%; Al 0.018%, and all the other are No. 1 electrolytic lead.Utilize this alloy casting to go out grid A.
On the basis of above-mentioned alloy, quantitatively drop into and analyze pure bismuth granule, be mixed with the Pb-Ca-Sn-Al-Bi quinary alloy, the mass percentage content of each composition of alloy is respectively: Ca 0.064%; Sn 1.224%; Al 0.018%, and Bi 0.094%; All the other are No. 1 electrolytic lead.Utilize this alloy casting to go out bismuth-containing grid B.
Continuous three samples of alloy that above-mentioned alloying component is after the preparation produce the mean value of actual analysis result on the atom direct reading emission spectrometer in ARL4460-433 type Switzerland Arl Inc..After the grid casting,, change over to then in 65 ℃ ± 2 ℃ the hothouse and carry out age-hardening in 1 day through room temperature ageing sclerosis 5 days.
The used lead plaster of battery smear is Tianjin, island formula lead powder of 1.64g/mL by oxidizability 72.5%, apparent density, adds positive and negative electrode prescription and system respectively and forms.With above-mentioned grid all according to manufacturing process respectively through smear, solidify dryly, after strict utmost point group weight combo, be assembled into 32 of the electric boosted automobile-used electrokinetic cells of 6-DZM-10 respectively.With the 2hr calculation of capacity, prepared cell positive active material dry weight is 14.4g/Ah, and the negative electrode active material dry weight is 12.9g/Ah.The Weight control tolerance of preparation process is ± 1g, and design capacity tolerance span is 1.6min.With the sulfuric acid (having added 0.03% analytical pure sulfuric acid sodium) of 1.255g/ml (25 ℃) battery is annotated acidifying and becomes, change into and adopt three two systems of putting of filling to be internalized into standard, detailed standard such as the table 1 of changing into:
Table 1 Experimental cell changes into mode
After battery rolls off the production line, left standstill 72 hours, then according to the discharge final pressure difference of control during capacity check less than 30mV, battery terminal voltage difference is less than 20mV simultaneously, make the battery pack I and the battery pack II of 36V series respectively, wherein battery pack I is the battery of bismuth-containing not, and battery pack II is the battery that grid has added 0.094% bismuth.
Respectively battery pack I and II are carried out air seal reaction efficiency, cycling life test with reference to " JB/T10262-2001 sealing lead acid storage battery for electric vehicle " standard, and the difference of test battery charge acceptance in cyclic process.
2, multicomponent alloy of the present invention is to the influence of cell sealing reaction efficiency
From battery pack I and II, extract 6 batteries respectively at random out, behind the complete full charge of battery, under the environment of temperature (25 ± 2) ℃, with 0.2I
2(A) electric current trickle charge 48h is then with 0.1I
2(A) electric current trickle charge 29h begins to collect gas from the 25h that changes electric current, measures the sealed reaction efficient of each battery respectively.
The sealed reaction efficient of each battery sees Table 2.
The sealed reaction efficient of table 2 battery I and battery II
Test result in the table 2 shows, adds in lead-calcium alloy after 0.094% the bismuth, and the cell sealing reaction efficiency is compared with the battery of bismuth-containing not, and the sealed reaction efficient of gas is improved generally.
3, alloy of the present invention is to the influence of battery cycle life
Extract among above-mentioned battery pack I and the battery pack II each four respectively, in 25 ℃ ± 2 ℃ environment, carry out the test of 100%DOD (100% depth of discharge) cycle life simultaneously.
Testing equipment is that Zhangjiagang Jin Fan Electrosource, Inc. produces 48v50A type small-sized sealing battery circulating inspector.
The circulation standard is: constant voltage 44.4v, current limliting 1.8A are to every Battery pack charging 10h, after leaving standstill 2h, being discharged to battery voltage 31.5v with constant current 6A is a circulation, the discharge time of each circulation of record battery pack, when being lower than 70min, judge that battery cycle life stops to the discharge time of putting in order Battery pack.
With the discharge time and the cycle-index of battery pack, draw out battery pack 100%DOD cycle life curve in the experiment, see accompanying drawing 1.
Accompanying drawing 1 shows, observes from cycle life, adds 0.094% bismuth in lead-calcium alloy, and the cycle life of battery pack is improved, and the raising rate is about about 20%; Battery pack is at 100% depth of discharge circulation time, add 0.094% bismuth, the discharge curve fluctuation is less, the capacity attenuation speed that is battery pack becomes mild generally, this early stage that acts on battery cycle life is not clearly, at later stage of battery cycle life significant difference as can be seen, this is the reason that improves of battery pack cycle life just also.Relatively about the interpolation of bismuth the influence of battery cycle life is reported not really significantly in the pertinent literature, discovery cyclic test is in the past generally only carried out in 20 times, infer thus, contain an amount of bismuth in the grid, it is to the influence of battery life, more show the later stage aspect of performance that the degree of depth discharges and recharges, circulates for a long time, the interfacial conductive performance between grid and the active material forms high impedance layer along with the carrying out of circulation further worsens at this moment.Do not enter active material after also not getting rid of in the anode plate grid bismuth dissolving, the structure of active material is played the possibility of improvement, a large amount of tests was explored after this needed.
4, alloy of the present invention is to the influence of charge acceptance in the dark cyclic process of battery
Each one of the battery pack of sampling respectively I and II carry out 100%DOD acceleration cycle test, and the test standard is: with 10A with battery power discharge behind 31.5v, constant voltage 44.4v current limliting 3A charging 5h is a complete cycle.In process of the test, the variation of the electric current in 3 hours moment of batteries charging with cycle-index worked as in observation, and the charge acceptance of battery pack in cyclic process is described.Result of the test is seen accompanying drawing 2.
From accompanying drawing 2 as can be seen, after adding 0.094% bismuth in the Pb-Ca-Sn-Al alloy of battery at grid, the charge acceptance of battery in the deep discharge cyclic process, during the initial stage with the battery difference of bismuth-containing not and not obvious, deep discharge circulation along with battery, battery pack II shows the charge acceptance of becoming better and better than battery pack I, and the charging current decling phase that its cyclic process middle finger is regularly carved is to gently.The test explanation, the alloy among the present invention has improved the charge acceptance of lead-acid battery in dark cyclic process.
Embodiment 2:
Each composition quality degree of grid A is changed into Ca 0.096%; Sn 0.084%; Al 0.032%; All the other are No. 1 electrolytic lead, and each composition quality degree of grid B is changed into Ca 0.096%; Sn 0.084%; Al 0.032%; Bi 0.085%; All the other are No. 1 electrolytic lead, and cell preparation and test effect comparison are consistent with embodiment 1.
Embodiment 3:
Each composition quality degree of grid A is changed into Ca 0.11%; Sn 1.4%; Al 0.022%; All the other are No. 1 electrolytic lead, and each composition quality degree of grid B is changed into Ca 0.11%; Sn 1.4%; Al 0.022%; Bi 0.12%; All the other are No. 1 electrolytic lead, and the preparation of battery and test effect comparison are consistent with embodiment 1.
Claims (1)
1. multicomponent alloy of making lead acid accumulator plate grid, contain element lead, calcium, tin, aluminium, it is characterized in that containing in this alloy the bismuth that mass percent is 0.084%-0.13%, the mass percent of each component in the alloy total amount is: calcium 0.06%-0.12%; Tin 0.08%-1.5%; Aluminium 0.017%-0.034%; Bismuth 0.084%-0.13%; All the other are electrolytic lead.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNA2007100199886A CN101237045A (en) | 2007-02-03 | 2007-02-03 | Multi-element alloy for making lead acid accumulator plate grid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100199886A CN101237045A (en) | 2007-02-03 | 2007-02-03 | Multi-element alloy for making lead acid accumulator plate grid |
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| CN101237045A true CN101237045A (en) | 2008-08-06 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875104A (en) * | 2010-06-30 | 2010-11-03 | 长兴诺力电源有限公司 | Grid plate preparation method |
| WO2013062694A2 (en) * | 2011-09-21 | 2013-05-02 | Hollingsworth & Vose Company | Battery components with leachable metal ions and uses thereof |
| CN103779580A (en) * | 2012-10-25 | 2014-05-07 | 天能电池(芜湖)有限公司 | Novel storage battery grid |
| CN105304883A (en) * | 2015-02-15 | 2016-02-03 | 济源市万洋绿色能源有限公司 | Storage battery negative electrode corrosion-resistant alloy |
| CN107275645A (en) * | 2017-08-02 | 2017-10-20 | 双登集团股份有限公司 | Make the alloy of lead acid accumulator plate grid |
| US10535853B2 (en) | 2010-09-21 | 2020-01-14 | Hollingsworth & Vose Company | Glass compositions with leachable metal oxides and ions |
| 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 |
| CN111370776A (en) * | 2020-02-20 | 2020-07-03 | 天能电池集团股份有限公司 | Container formation process for valve-controlled storage battery |
| CN115418527A (en) * | 2022-08-22 | 2022-12-02 | 铅锂智行(北京)科技有限公司 | Grid alloy of lead-acid storage battery |
-
2007
- 2007-02-03 CN CNA2007100199886A patent/CN101237045A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875104A (en) * | 2010-06-30 | 2010-11-03 | 长兴诺力电源有限公司 | Grid plate preparation method |
| CN101875104B (en) * | 2010-06-30 | 2012-01-25 | 长兴诺力电源有限公司 | Grid plate preparation method |
| US10535853B2 (en) | 2010-09-21 | 2020-01-14 | Hollingsworth & Vose Company | Glass compositions with leachable metal oxides and ions |
| WO2013062694A2 (en) * | 2011-09-21 | 2013-05-02 | Hollingsworth & Vose Company | Battery components with leachable metal ions and uses thereof |
| WO2013062694A3 (en) * | 2011-09-21 | 2014-05-08 | Hollingsworth & Vose Company | Battery components with leachable metal ions and uses thereof |
| CN103779580A (en) * | 2012-10-25 | 2014-05-07 | 天能电池(芜湖)有限公司 | Novel storage battery grid |
| CN105304883A (en) * | 2015-02-15 | 2016-02-03 | 济源市万洋绿色能源有限公司 | Storage battery negative electrode corrosion-resistant alloy |
| CN105304883B (en) * | 2015-02-15 | 2017-12-22 | 济源市万洋绿色能源有限公司 | A kind of accumulator negative plate corrosion-resisant alloy |
| CN107275645A (en) * | 2017-08-02 | 2017-10-20 | 双登集团股份有限公司 | Make the alloy of lead acid accumulator plate grid |
| 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 |
| CN111370776A (en) * | 2020-02-20 | 2020-07-03 | 天能电池集团股份有限公司 | Container formation process for valve-controlled storage battery |
| CN115418527A (en) * | 2022-08-22 | 2022-12-02 | 铅锂智行(北京)科技有限公司 | Grid alloy of lead-acid storage battery |
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Open date: 20080806 |