CN102660697A - Lead-acid battery grid alloy for power - Google Patents
Lead-acid battery grid alloy for power Download PDFInfo
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- CN102660697A CN102660697A CN2012101295909A CN201210129590A CN102660697A CN 102660697 A CN102660697 A CN 102660697A CN 2012101295909 A CN2012101295909 A CN 2012101295909A CN 201210129590 A CN201210129590 A CN 201210129590A CN 102660697 A CN102660697 A CN 102660697A
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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
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 be 1859 by Fr Pulan special (Plante) invention, the history in existing more than 100 year has 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 safety is arranged in the use, be applicable to heavy-current discharge and 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 main building block of power lead-acid storage battery is: positive plate, negative plate, glass fibre separator, battery container, battery cap, electrolytic solution (dilute sulphuric acid), leading-out terminal and SV etc.
Initial lead acid cell uses two blocks of stereotypes charge and discharge cycles through repeated multiple times in sulphuric acid soln to become positive and negative electrode, it doesn't matter grid.1880, Faure proposed grid type plate, was about to lead plaster and was coated on the sheet lead, and stereotype is as collector.1881, Swan at first proposed the grid notion, used stereotype 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 the negative plate is the chief component of power lead-acid storage battery; In battery, support active substance, serve as the carrier of active substance, conduct and compile electric current; Electric current is evenly distributed on the 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 higher than active substance far away; The grid that conductivity is good can make electric current along the rib uniform distribution, thereby improves the utilization ratio of active substance.
Application number is that 201110106277.9 Chinese invention patent discloses a kind of positive grid of lead-acid accumulator alloy; Form by lead, calcium, tin and REE; Wherein REE is samarium or terbium; Each weight percentages of components is calcium 0.03-0.18%, tin 0.1-2%, and REE 0.005-0.2% and surplus are plumbous.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 the battery charge and discharge process, has prolonged the cycle life of battery.
The power lead-acid storage battery grid of now being produced in use receives because of the sulfuric acid concentration layering easily, and concentration polarization is enlarged, thereby produces polarization impedance; Reduced the utilization ratio of active substance; Under the deep discharge condition,, cell container is descended significantly because the binding ability of grid and active substance reduces; And plate active material takes place easily to come off; Thereby cause the grid corrosion to cause the internal resistance of cell to increase, cycle life shortens, and present employed 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, prolonged store battery work-ing life, 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 in alloy, adds calcium formation is less, near pure lead, is suitable for cold-starting; The overvoltage of hydrogen evolution is higher on calcium, has reduced the self-discharge of battery and the loss of water, has non-maintaining preferably property; Lead-calcium alloy is a precipitation hardenable, promptly in lead base matter, forms Pb
3The close grain deposition of Ca intermetallic compound, being deposited in becomes the sclerosis network in the lead base matter, make alloy have certain mechanical strength.
Described Na is a sodium Metal 99.5, has excellent electroconductibility and good ductility, can conduct and compile electric current effectively; The hardness of sodium is lower; Suitably add, can expand at active substance, when 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 strict control.
Described Sn is a metallic tin, can guarantee separating out of sodium and calcium in the grid alloy, improves opourability and physical strength; Influence the hardness ageing speed of alloy; Improve alloy surface and active substance bonded microtexture, increase the binding ability between grid alloy and the active substance, when active substance expands contraction; 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 the alloy, during the Na too high levels, possibly cause the reduction of pole plate corrosion resistance nature, therefore, the Sn weight percent is preferably 1.4～1.6%, and the Na weight percent is preferably 0.05%～0.10%.
Further preferred, 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 containing mass percent in the grid alloy and be the Na of 1.4% Sn and 0.08%, the lead acid cell that utilizes this grid alloy to make has less relatively internal resistance and relatively long cycle life.
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 containing mass percent in the grid alloy and be the Na of 1.5% Sn and 0.09%, the lead acid cell that utilizes this grid alloy to make has less relatively internal resistance and relatively long cycle life.
The present invention also provides a kind of preparation method of described power lead-acid storage battery grid alloy, may further comprise the steps:
(1) electrolytic lead is added crucible oven, be warming up to 600～660 ℃, successively add Al and Ca, stirred 20～30 minutes, be cooled to 350～400 ℃ with 15～20r/min rotating speed;
(2) add metal Sn, stir, add metal Na in the time of stirring, add the completion continued and stirred 10～30 minutes, can obtain grid alloy with the 15-20r/min rotating speed with the 15-20r/min rotating speed.
The adding of metal Na needs sodium Metal 99.5 is sunk in the alloy liquid.Because sodium Metal 99.5 character is extremely active, therefore,, adds operation and also note safety except the addition of control metal Na.
The add-on of each raw material can obtain through the calculating of the weight percent in the plato grid alloy formulation according to the usage quantity of electrolytic lead.
Metal Na and metal Sn have been added in the power lead-acid storage battery grid alloy of the present invention; Improved the binding ability of grid and active substance effectively; Prolonged the work-ing life of battery, erosion resistance does not have than about-face simultaneously, and the power lead-acid storage battery that the feasible power lead-acid storage battery ohmic resistance of being processed by the present invention is processed than the grid alloy that uses now hangs down about 30%; Simultaneously, the deep discharge performance with recycle the life-span and improved about 15%.
Embodiment
Embodiment 1
(1) the 93.5kg electrolytic lead is added crucible oven, be warming up to 600～660 ℃, successively add 500gAl and 500gCa, stirred 20～30 minutes, be cooled to 350～400 ℃ with the 15-20r/min rotating speed;
(2) add the 5kg metallic tin, stir, add the 500g sodium Metal 99.5 in the time of stirring, add the completion continued and stir 10～30min, can obtain grid alloy with the 15-20r/min rotating speed;
Above-mentioned grid alloy is made lead acid cell (6-DZM-12), and detecting this lead acid cell internal resistance is 12m Ω, and two hourly rate capacity discharge first is 136min; Circulate 50 times, capacity discharge 128min circulates 100 times; Capacity discharge 122min circulates 200 times, capacity discharge 114min.
Embodiment 2
(1) the 98.41kg electrolytic lead is added crucible oven, be warming up to 600～660 ℃, successively add 30gAl and 80gCa, stirred 20～30 minutes, be cooled to 350～400 ℃ with the 15-20r/min rotating speed;
(2) add the 1.4kg metallic tin, stir, add the 80g sodium Metal 99.5 in the time of stirring, add the completion continued and stir 10～30min, can obtain grid alloy with the 15-20r/min rotating speed;
Above-mentioned grid alloy is made lead acid cell (6-DZM-12), and detecting this lead acid cell internal resistance is 6m Ω, and two hourly rate capacity discharge first is 138min; Circulate 50 times, capacity discharge 135min circulates 100 times; Capacity discharge 130min circulates 200 times, capacity discharge 120min.
Embodiment 3
(1) the 98.21kg electrolytic lead is added crucible oven, be warming up to 600～660 ℃, successively add 30gAl and 80gCa, stirred 20～30 minutes, be cooled to 350～400 ℃ with the 15-20r/min rotating speed;
(2) add the 1.6kg metallic tin, stir, add the 80g sodium Metal 99.5 in the time of stirring, add the completion continued and stir 10～30min, can obtain grid alloy with the 15-20r/min rotating speed;
Above-mentioned grid alloy is made store battery (6-DZM-12), and detecting this accumulator internal resistance is 7m Ω, and two hourly rate capacity discharge first is 135min; Circulate 50 times, capacity discharge 125min circulates 100 times; Capacity discharge 120min circulates 200 times, capacity discharge 115min.
Embodiment 4
(1) the 98.24kg electrolytic lead is added crucible oven, be warming up to 600～660 ℃, successively add 30gAl and 80gCa, stirred 20～30 minutes, be cooled to 350～400 ℃ with the 15-20r/min rotating speed;
(2) add the 1.5kg metallic tin, stir, add the 150g sodium Metal 99.5 in the time of stirring, add the completion continued and stir 10～30min, can obtain grid alloy with the 15-20r/min rotating speed;
Above-mentioned grid alloy is made store battery (6-DZM-12), and detecting this accumulator internal resistance is 7m Ω, and two hourly rate capacity discharge first is 135min; Circulate 50 times, capacity discharge 129min circulates 100 times; Capacity discharge 123min circulates 200 times, capacity discharge 114min.
Embodiment 5
(1) the 98.51kg electrolytic lead is added crucible oven, be warming up to 600～660 ℃, successively add 30gAl and 80gCa, stirred 20～30 minutes, be cooled to 350～400 ℃ with the 15-20r/min rotating speed;
(2) add the 1.3kg metallic tin, stir, add the 80g sodium Metal 99.5 in the time of stirring, add the completion continued and stir 10～30min, can obtain grid alloy with the 15-20r/min rotating speed;
Above-mentioned grid alloy is made store battery (6-DZM-12), and detecting this accumulator internal resistance is 7m Ω, and two hourly rate capacity discharge first is 139min; Circulate 50 times, capacity discharge 130min circulates 100 times; Capacity discharge 119min circulates 200 times, capacity discharge 113min.
Embodiment 6
(1) the 98.3kg electrolytic lead is added crucible oven, be warming up to 600～660 ℃, successively add 30gAl and 80gCa, stirred 20～30 minutes, be cooled to 350～400 ℃ with the 15-20r/min rotating speed;
(2) add the 1.5kg metallic tin, stir, add the 90g sodium Metal 99.5 in the time of stirring, add the completion continued and stir 10～30min, can obtain grid alloy with the 15-20r/min rotating speed;
Above-mentioned grid alloy is made store battery (6-DZM-12), and detecting this accumulator internal resistance is 6m Ω, and two hourly rate capacity discharge first is 137min; Circulate 50 times, capacity discharge 134min circulates 100 times; Capacity discharge 128min circulates 200 times, capacity discharge 120min.
Comparative Examples
Grid alloy of the prior art is made store battery (6-DZM-12), detect this accumulator internal resistance 9m Ω, two hourly rate capacity discharge first is 133min; Circulate 50 times, capacity discharge 111min circulates 100 times; Capacity discharge 102min circulates 200 times, capacity discharge 86min.
Compare with Comparative Examples, among the embodiment 1～6, two hourly rate capacity discharging values are slightly higher than Comparative Examples first; After the cycle charge-discharge 200 times, this shows all apparently higher than Comparative Examples capacity discharge time of embodiment 1～6; The adding of metal Na and metal Sn can effectively increase the conductive capability of grid, improves 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, keep the capacity discharge capability.
Among embodiment 1 and the embodiment 4, through after 200 cycle charge-discharges, the power lead-acid storage battery capacity is approaching discharge time; But the Ca among the embodiment 1, Al, the addition of Sn and Na are far away more than embodiment 3; And accumulator internal resistance is 12m Ω among the embodiment 1, greater than the 9m Ω of Comparative Examples, therefore; The ratio of additive is not high more good more, in suitable proportional range, just can reach best effect.
Among embodiment 2 and the embodiment 6; Through after 200 cycle charge-discharges, the power lead-acid storage battery capacity is the longest discharge time, and embodiment 3 compares with embodiment 2; Difference is that the addition of Sn brings up to 1.6kg by 1.4kg; This shows that the addition of Sn is not The more the better, 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, this shows that the addition of Na is not The more the better, and too much Na possibly influence 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 (6)
1. a power lead-acid storage battery grid alloy is characterized in that, 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％。
2. power lead-acid storage battery grid alloy as claimed in claim 1 is characterized in that, 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％。
3. power lead-acid storage battery grid alloy as claimed in claim 2 is characterized in that, 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％。
4. power lead-acid storage battery grid alloy as claimed in claim 1 is characterized in that, raw material weight per-cent consists of:
Ca?0.08％，
Sn?1.4％，
Na?0.08％，
Al?0.03％，
Pb?98.41％。
5. power lead-acid storage battery grid alloy as claimed in claim 1 is characterized in that, raw material weight per-cent consists of:
Ca?0.08％，
Sn?1.5％，
Na?0.09％，
Al?0.03％，
Pb?98.3％。
6. like the preparation method of the arbitrary described power lead-acid storage battery grid alloy of claim 1～5, it is characterized in that, may further comprise the steps:
(1) electrolytic lead is added crucible oven, be warming up to 600～660 ℃, successively add Al and Ca, stirred 20～30 minutes, be cooled to 350～400 ℃ with 15～20r/min rotating speed;
(2) add metal Sn, stir, add metal Na in the time of stirring, add the completion continued and stirred 10～30 minutes, can obtain grid alloy with the 15-20r/min rotating speed with the 15-20r/min rotating speed.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107170990A (en) * | 2017-05-24 | 2017-09-15 | 海志电源技术（赣州）有限公司 | A kind of power lead-acid storage battery and its manufacture 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 |
| CN108396171A (en) * | 2018-02-08 | 2018-08-14 | 天能电池集团有限公司 | A kind of battery grid and preparation method thereof of alloy grain refinement |
| 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 |
| CN111270119A (en) * | 2020-02-26 | 2020-06-12 | 江苏海瑞电源有限公司 | Calcium-aluminum-lanthanum-sodium alloy |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107170990A (en) * | 2017-05-24 | 2017-09-15 | 海志电源技术（赣州）有限公司 | A kind of power lead-acid storage battery and its manufacture 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 |
| 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 |
| US20210040583A1 (en) * | 2018-02-06 | 2021-02-11 | Tianneng Battery Group Co., Ltd. | 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 |
| CN108396171A (en) * | 2018-02-08 | 2018-08-14 | 天能电池集团有限公司 | A kind of battery grid and preparation method thereof of alloy grain refinement |
| CN111270119A (en) * | 2020-02-26 | 2020-06-12 | 江苏海瑞电源有限公司 | Calcium-aluminum-lanthanum-sodium alloy |
| 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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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. |
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