CN102660697B - Lead-acid battery grid alloy for power - Google Patents
Lead-acid battery grid alloy for power Download PDFInfo
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- CN102660697B CN102660697B CN201210129590.9A CN201210129590A CN102660697B CN 102660697 B CN102660697 B CN 102660697B CN 201210129590 A CN201210129590 A CN 201210129590A CN 102660697 B CN102660697 B CN 102660697B
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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
The invention discloses a lead-acid battery grid alloy for power. The lead-acid battery grid alloy for power comprises the following raw materials by weight percentage: 0.05-0.50% of Ca, 1-5% of Sn, 0.05-0.50% of Na, 0.01-0.50% of Al and 93.5-98.89% of Pb. The invention further discloses a method for preparing the lead-acid battery grid alloy for power. The metal Na and the metal Sn added in the grid alloy improve combination performance of the grid and activate substances, prolong service life of the battery and reduce the ohmic resistance of the prepared lead-acid battery grid alloy for power by about 30% compared with the existing lead-acid battery grid alloy for power prepared by grid alloys, and deep discharging performance and circulation service life are improved by about 15%.
Description
Technical field
The present invention relates to the lead acid cell field, relate in particular to a kind of power lead-acid storage battery grid alloy.
Background technology
Lead acid cell is by Frenchman Pulan special (Plante), to be invented in 1859, and the history of existing more than 100 year, all obtained significant progress at aspects such as lead acid cell theoretical investigation, product category and kind, product electric properties so far.
Lead acid cell is after invention, because it is cheap, starting material are easy to obtain, sufficient reliability is arranged in use, be applicable to heavy-current discharge and the advantage such as ambient temperature range widely, in chemical power source, have overwhelming superiority always, no matter be in traffic, communication, electric power, military affairs or, in navigation, aviation every field, lead acid cell has all played indispensable vital role.
The chief component parts of power lead-acid storage battery are: positive plate, negative plate, glass fibre separator, battery container, battery cap, electrolytic solution (dilute sulphuric acid), leading-out terminal and safety valve etc.
Initial lead acid cell, use two blocks of stereotypes to become positive and negative electrode by repeated multiple times charge and discharge cycles in sulphuric acid soln, it doesn't matter grid.1880, Faure proposed grid type plate, was about to lead plaster and was coated on sheet lead, and stereotype is as collector.1881, at first Swan proposed the grid concept, stereotype used before replacing.After this, Sellon has invented the lead antimony alloy grid, and other various grids also occur in succession.
Grid in positive plate and negative plate is the chief component of power lead-acid storage battery, support active substance in battery, serve as the carrier of active substance, conduct and collect electric current, make balanced current distribution on active substance, to improve the utilization ratio of active substance.Grid is often covered by active substance, less with the electrolytic solution contact area, therefore, it participates in the ability of electrochemical reaction well below active substance, but conductive capability is far away higher than active substance, the grid that conductivity is good can make electric current be uniformly distributed along rib, thereby improves the utilization ratio of active substance.
The Chinese invention patent that application number is 201110106277.9 discloses a kind of positive plate grid alloy, by lead, calcium, tin and rare earth element, formed, its rare earth elements is samarium or terbium, each weight percentages of components is calcium 0.03-0.18%, tin 0.1-2%, rare earth element 0.005-0.2% and surplus lead.This alloy has improved the grid alloy rotproofness, reduces the fracture of grid rib, has improved the float life of battery, in addition, has improved the charge acceptance of battery, prevents the capacity attenuation in battery charge and discharge process, has extended the cycle life of battery.
The power lead-acid storage battery grid of now producing in use easily is subject to because of the sulfuric acid concentration layering, and concentration polarization is enlarged, thereby generation polarization impedance, reduced the utilization ratio of active substance, under the deep discharge condition, binding ability reduction due to grid and active substance, can make cell container significantly descend, and plate active material easily occurs to come off, thereby cause grid corrosion to cause the internal resistance of cell to increase, cycle life shortens, and present used power lead-acid storage battery grid alloy deep discharge scope is shallow.
Summary of the invention
The invention provides a kind of power lead-acid storage battery grid alloy, improved the electroconductibility of grid and the binding ability of grid and active substance, extended service lifetime of accumulator, strengthened the anti-dark charging and discharging capabilities of power lead-acid storage battery.
A kind of power lead-acid storage battery grid alloy, raw material weight per-cent consists of:
Ca?0.05～0.50％，
Sn?1～5％，
Na?0.05～0.50％，
Al?0.01～0.50％，
Pb?93.5～98.89％。
The lead-calcium alloy resistance that adds calcium to form in alloy is less, approaches pure lead, is suitable for cold-starting, on calcium, the overvoltage of hydrogen evolution is higher, has reduced the self-discharge of battery and the loss of water, has non-maintaining property preferably, lead-calcium alloy is precipitation hardenable, in lead base matter, forms Pb
3the close grain precipitation of Ca intermetallic compound, be deposited in lead base matter and become the sclerosis network, makes alloy have certain physical strength.
Described Na is sodium Metal 99.5, there is excellent electroconductibility and good ductility, can effectively conduct and collect electric current, the hardness of sodium is lower, suitably add, can expand at active substance, while shrinking, grid is not easy to be out of shape, and then prevent that active substance from coming off or the warpage that chaps, make the electroconductibility of power lead-acid storage battery and erosion resistance improve 10～15%.Because sodium Metal 99.5 character is extremely active, so addition should strictly be controlled.
Described Sn is metallic tin, can guarantee separating out of sodium and calcium in grid alloy, improve opourability and physical strength, affect the hardness ageing speed of alloy, improve the microtexture that alloy surface is combined with active substance, increase the binding ability between grid alloy and active substance, when the active substance dilation, grid is not yielding, reduces coming off of active substance.
As preferably, grid alloy raw material weight per-cent consists of:
Ca?0.07％～0.08％，
Sn?1.4～1.6％，
Na?0.05％～0.10％，
Al?0.015％～0.03％，
Pb?98.19％～98.465％。
During the too high levels of Sn, may cause the self-discharge of battery in alloy, during the Na too high levels, may cause the reduction of pole plate corrosion resistance nature, therefore, the Sn weight percent is preferably 1.4～1.6%, Na weight percent and is preferably 0.05%～0.10%.
Further preferably, grid alloy raw material weight per-cent consists of:
Ca?0.07％～0.08％，
Sn?1.4％～1.5％，
Na?0.08％～0.09％，
Al?0.025％～0.03％，
Pb?98.3％～98.425％。
As preferably, grid alloy raw material weight per-cent consists of:
Ca?0.08％，
Sn?1.4％，
Na?0.08％，
Al?0.03％，
Pb?98.41％。
When the Sn that to contain mass percent in grid alloy be 1.4% and 0.08% Na, the lead acid cell that utilizes this grid alloy to make has internal resistance and the relatively long cycle life of less.
As preferably, grid alloy raw material weight per-cent consists of:
Ca?0.08％，
Sn?1.5％，
Na?0.09％，
Al?0.03％，
Pb?98.3％。
When the Sn that to contain mass percent in grid alloy be 1.5% and 0.09% Na, the lead acid cell that utilizes this grid alloy to make has internal resistance and the relatively long cycle life of less.
The present invention also provides a kind of preparation method of described power lead-acid storage battery grid alloy, comprises the following steps:
(1) electrolytic lead is added to crucible oven, be warming up to 600～660 ℃, successively add Al and Ca, stir 20～30 minutes with 15～20r/min rotating speed, be cooled to 350～400 ℃;
(2) add metal Sn, stir with the 15-20r/min rotating speed, add metal Na in the time of stirring, added rear continuation and stirred 10～30 minutes with the 15-20r/min rotating speed, can obtain grid alloy.
Adding of metal Na need be sunk to sodium Metal 99.5 in aluminium alloy.Because sodium Metal 99.5 character is extremely active, therefore, except controlling the addition of metal Na, add operation also to should be noted safety.
The add-on of each raw material can, according to the usage quantity of electrolytic lead, be calculated and obtain by the weight percent in plato grid alloy formulation.
Metal Na and metal Sn have been added in power lead-acid storage battery grid alloy of the present invention, effectively improved the binding ability of grid and active substance, extended the work-ing life of battery, not larger change of erosion resistance simultaneously, make low 30% left and right of the power lead-acid storage battery ohmic resistance ratio power lead-acid storage battery that the grid alloy of use is made now of being made by the present invention, simultaneously, deep discharge performance and service life cycle have improved 15% left and right.
Embodiment
Embodiment 1
(1) the 93.5kg electrolytic lead is added to crucible oven, be warming up to 600～660 ℃, successively add 500gAl and 500gCa, stir 20～30 minutes with the 15-20r/min rotating speed, be cooled to 350～400 ℃;
(2) add the 5kg metallic tin, stir with the 15-20r/min rotating speed, add the 500g sodium Metal 99.5 in the time of stirring, added rear continuation and stirred 10～30min, can obtain grid alloy;
Above-mentioned grid alloy is made to lead acid cell (6-DZM-12), and this lead acid cell internal resistance being detected is 12m Ω, and two hourly rate capacity electric discharges first are 136min, circulate 50 times, capacity electric discharge 128min, circulate 100 times, capacity electric discharge 122min, circulate 200 times, capacity electric discharge 114min.
Embodiment 2
(1) the 98.41kg electrolytic lead is added to crucible oven, be warming up to 600～660 ℃, successively add 30gAl and 80gCa, stir 20～30 minutes with the 15-20r/min rotating speed, be cooled to 350～400 ℃;
(2) add the 1.4kg metallic tin, stir with the 15-20r/min rotating speed, add the 80g sodium Metal 99.5 in the time of stirring, added rear continuation and stirred 10～30min, can obtain grid alloy;
Above-mentioned grid alloy is made to lead acid cell (6-DZM-12), and this lead acid cell internal resistance being detected is 6m Ω, and two hourly rate capacity electric discharges first are 138min, circulate 50 times, capacity electric discharge 135min, circulate 100 times, capacity electric discharge 130min, circulate 200 times, capacity electric discharge 120min.
Embodiment 3
(1) the 98.21kg electrolytic lead is added to crucible oven, be warming up to 600～660 ℃, successively add 30gAl and 80gCa, stir 20～30 minutes with the 15-20r/min rotating speed, be cooled to 350～400 ℃;
(2) add the 1.6kg metallic tin, stir with the 15-20r/min rotating speed, add the 80g sodium Metal 99.5 in the time of stirring, added rear continuation and stirred 10～30min, can obtain grid alloy;
Above-mentioned grid alloy is made to store battery (6-DZM-12), and this accumulator internal resistance being detected is 7m Ω, and two hourly rate capacity electric discharges first are 135min, circulate 50 times, capacity electric discharge 125min, circulate 100 times, capacity electric discharge 120min, circulate 200 times, capacity electric discharge 115min.
Embodiment 4
(1) the 98.24kg electrolytic lead is added to crucible oven, be warming up to 600～660 ℃, successively add 30gAl and 80gCa, stir 20～30 minutes with the 15-20r/min rotating speed, be cooled to 350～400 ℃;
(2) add the 1.5kg metallic tin, stir with the 15-20r/min rotating speed, add the 150g sodium Metal 99.5 in the time of stirring, added rear continuation and stirred 10～30min, can obtain grid alloy;
Above-mentioned grid alloy is made to store battery (6-DZM-12), and this accumulator internal resistance being detected is 7m Ω, and two hourly rate capacity electric discharges first are 135min, circulate 50 times, capacity electric discharge 129min, circulate 100 times, capacity electric discharge 123min, circulate 200 times, capacity electric discharge 114min.
Embodiment 5
(1) the 98.51kg electrolytic lead is added to crucible oven, be warming up to 600～660 ℃, successively add 30gAl and 80gCa, stir 20～30 minutes with the 15-20r/min rotating speed, be cooled to 350～400 ℃;
(2) add the 1.3kg metallic tin, stir with the 15-20r/min rotating speed, add the 80g sodium Metal 99.5 in the time of stirring, added rear continuation and stirred 10～30min, can obtain grid alloy;
Above-mentioned grid alloy is made to store battery (6-DZM-12), and this accumulator internal resistance being detected is 7m Ω, and two hourly rate capacity electric discharges first are 139min, circulate 50 times, capacity electric discharge 130min, circulate 100 times, capacity electric discharge 119min, circulate 200 times, capacity electric discharge 113min.
Embodiment 6
(1) the 98.3kg electrolytic lead is added to crucible oven, be warming up to 600～660 ℃, successively add 30gAl and 80gCa, stir 20～30 minutes with the 15-20r/min rotating speed, be cooled to 350～400 ℃;
(2) add the 1.5kg metallic tin, stir with the 15-20r/min rotating speed, add the 90g sodium Metal 99.5 in the time of stirring, added rear continuation and stirred 10～30min, can obtain grid alloy;
Above-mentioned grid alloy is made to store battery (6-DZM-12), and this accumulator internal resistance being detected is 6m Ω, and two hourly rate capacity electric discharges first are 137min, circulate 50 times, capacity electric discharge 134min, circulate 100 times, capacity electric discharge 128min, circulate 200 times, capacity electric discharge 120min.
Comparative Examples
Grid alloy of the prior art is made to store battery (6-DZM-12), this accumulator internal resistance 9m Ω detected, two hourly rate capacity electric discharges first are 133min, circulate 50 times, capacity electric discharge 111min, circulate 100 times, capacity electric discharge 102min, circulate 200 times, capacity electric discharge 86min.
With Comparative Examples, compare, in embodiment 1～6, two hourly rate capacity discharging values are slightly higher than Comparative Examples first, after cycle charge-discharge 200 times, capacity discharge time of embodiment 1～6 is all apparently higher than Comparative Examples, as can be seen here, adding of metal Na and metal Sn, can effectively increase the conductive capability of grid, improve the demixing phenomenon of sulfuric acid electrolyte, reduce polarization impedance, reduce the ohmic resistance of power lead-acid storage battery, increase the binding ability of grid and active substance simultaneously, make battery in the cycle charge discharge electric process, reduce the loss of active substance, maintenance capacity discharge capability.
In embodiment 1 and embodiment 4, through after 200 cycle charge-discharges, the power lead-acid storage battery capacity approaches discharge time, but the Ca in embodiment 1, Al, the addition of Sn and Na is far away more than embodiment 3, and in embodiment 1, accumulator internal resistance is 12m Ω, is greater than the 9m Ω of Comparative Examples, therefore, the ratio of additive is not more high better, in suitable proportional range, just can reach best effect.
In embodiment 2 and embodiment 6, through after 200 cycle charge-discharges, the power lead-acid storage battery capacity is the longest discharge time, embodiment 3 compares with embodiment 2, difference is that the addition of Sn brings up to 1.6kg by 1.4kg, as can be seen here, the addition of Sn is not The more the better, and too high Sn content may cause the self-discharge of battery; Embodiment 4 compares with embodiment 6, and difference is that the addition of Na brings up to 150g by 90g, and as can be seen here, the addition of Na is not The more the better, and too much Na may affect the physical strength of grid alloy; Embodiment 5 compares with embodiment 2, and difference is that the addition of Sn is reduced to 1.3kg by 1.4kg, and the addition of Sn need reach certain proportion, could improve the performance of lead acid cell.
Claims (5)
1. a power lead-acid storage battery grid alloy, is characterized in that, raw material weight per-cent consists of:
Ca0.07%～0.08%，
Sn1.4～1.6%，
Na0.05%～0.10%，
Al0.015%～0.03%，
Pb98.19%～98.465%。
2. power lead-acid storage battery grid alloy as claimed in claim 1, is characterized in that, raw material weight per-cent consists of:
Ca0.07%～0.08%，
Sn1.4%～1.5%，
Na0.08%～0.09%，
Al0.025%～0.03%，
Pb98.3%～98.425%。
3. power lead-acid storage battery grid alloy as claimed in claim 1, is characterized in that, raw material weight per-cent consists of:
Ca0.08%，
Sn1.4%，
Na0.08%，
Al0.03%，
Pb98.41%。
4. power lead-acid storage battery grid alloy as claimed in claim 1, is characterized in that, raw material weight per-cent consists of:
Ca0.08%，
Sn1.5%，
Na0.09%，
Al0.03%，
Pb98.3%。
5. the preparation method of described power lead-acid storage battery grid alloy as arbitrary as claim 1～4, is characterized in that, comprises the following steps:
(1) electrolytic lead is added to crucible oven, be warming up to 600～660 ℃, successively add Al and Ca, stir 20～30 minutes with 15～20r/min rotating speed, be cooled to 350～400 ℃;
(2) add metal Sn, stir with the 15-20r/min rotating speed, add metal Na in the time of stirring, added rear continuation and stirred 10～30 minutes with the 15-20r/min rotating speed, can obtain grid alloy.
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| CN102903934A (en) * | 2012-11-14 | 2013-01-30 | 徐永生 | Lead-acid battery negative plate grid alloy |
| CN105845898A (en) * | 2016-04-01 | 2016-08-10 | 中国电力科学研究院 | Lead-carbon battery negative plate and preparation method therefor |
| CN107170990B (en) * | 2017-05-24 | 2019-11-05 | 海志电源技术（赣州）有限公司 | A kind of power lead-acid storage battery and its manufacturing method |
| CN107760922A (en) * | 2017-09-28 | 2018-03-06 | 河北超威电源有限公司 | A kind of high-energy power slab lattice alloy of lead-acid battery and preparation method thereof |
| CN108467968B (en) * | 2018-02-06 | 2019-07-23 | 天能电池集团股份有限公司 | A kind of preparation method of lead storage battery grid alloy |
| CN108396171B (en) * | 2018-02-08 | 2019-12-17 | 天能电池集团股份有限公司 | Alloy grain refined storage battery grid and preparation method thereof |
| CN111270119B (en) * | 2020-02-26 | 2021-08-06 | 江苏海瑞电源有限公司 | Calcium-aluminum-lanthanum-sodium alloy |
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| CN1076058A (en) * | 1992-02-29 | 1993-09-08 | 山东省文登市密闭蓄电池厂 | Positive and negative plate grid alloy material for sealed lead-acid accumulator |
| CN1294418A (en) * | 1999-10-23 | 2001-05-09 | 杭州南都电源有限公司 | Alloy material for lattice plate of deeply cyclic battery |
| CN1917257A (en) * | 2005-08-16 | 2007-02-21 | 深圳市雄韬电源科技有限公司 | Oxidation resistant protection method for ears of pole plate of accumulator |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1076058A (en) * | 1992-02-29 | 1993-09-08 | 山东省文登市密闭蓄电池厂 | Positive and negative plate grid alloy material for sealed lead-acid accumulator |
| CN1294418A (en) * | 1999-10-23 | 2001-05-09 | 杭州南都电源有限公司 | Alloy material for lattice plate of deeply cyclic battery |
| CN1917257A (en) * | 2005-08-16 | 2007-02-21 | 深圳市雄韬电源科技有限公司 | Oxidation resistant protection method for ears of pole plate of accumulator |
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Address after: 313117 Meishan Industrial Park, Changxing County, Huzhou City, Zhejiang Province Patentee after: Tianneng Battery Group Co., Ltd. Address before: 313117 Meishan Industrial Park, Changxing County, Huzhou City, Zhejiang Province Patentee before: Tianneng Battery Group Co., Ltd. |