CN105177354B - A kind of maintenance-free lead accumulator positive grid alloy - Google Patents
A kind of maintenance-free lead accumulator positive grid alloy Download PDFInfo
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Abstract
The present invention provides a kind of maintenance-free lead accumulator positive grid alloy and preparation method thereof, described alloy is made up of lead, barium, silver, calcium, stannum, rare earth element, its percentage by weight is 0.02 0.15% barium, 0.002 0.01% silver medal, 0.04 0.15% calcium, 0.25 1.80% stannum, 0.02 0.20% rare earth element and surplus lead.This alloy improves the intensity of alloy, enhances the corrosion resistance of alloy, thus improves the high-temperature floating-charge life-span of battery, deeper cavity life-span.
Description
Technical field
The invention belongs to lead-acid accumulator field, be specifically related to a kind of maintenance-free lead accumulator positive grid alloy.
Background technology
Since French G.Plante invention lead-acid accumulator in 1859, the history of existing more than 100 year, experience during this
Major transformation and development.Along with going from bad to worse of environment, improving constantly of people's environmental consciousness, maintenance-free lead accumulator exists
In the life of people, proportion is increasing.Thus improve and promote maintenance-free lead accumulator performance further and become scientific research
Worker and the focal point of manufacturer, wherein by improving grid alloy composition, reducing the loss of maintenance-free lead-acid battery water is
Wherein one of research emphasis.
Lead acid accumulator plate grid material is initially to use pure lead as both positive and negative polarity, but its intensity is low, yielding, causes battery
Shock resistance poor.Sellon(Zhu Song is right, Zhang Boran. lead battery technology. and Beijing: China Machine Press,
1988.) antimony is added in grid alloy, using lead-antimony alloy as the positive and negative electrode grid of battery, the mechanical performance of gained grid,
Casting quality etc. is all greatly improved.But the hydrogen-separating quantity of lead-antimony alloy is big, cause water loss the most serious, it is impossible to as non-maintaining
The grid alloy of battery uses, thus, people start low antimony or study without antimony alloy.At present, maintenance-free lead acid electric power storage
The anode plate grid material in pond is mainly lead-calcium-tin alloy.The maintenance-free performance of lead-calcium alloy is excellent, and hydrogen-evolution overpotential is high, and water is lost
Few, but it is easily caused " premature capacity loss ", and grid non-deformability is poor.Along with people are to the high temperature of battery and deep discharge
Can require that increasingly stringent, tradition lead-calcium-tin alloy are difficult to meet the demand of battery performance.Patent CN103050710A discloses one
Plant the preparation method of lead-acid battery lead-antimony alloy grid: melted by pure lead, add pure gadolinium, form lead-gadolinium foundry alloy；By pure lead
Fusing, adds pure yttrium, forms lead-yttrium foundry alloy；After melted for pure lead, add star antimony, be continuously heating to 800-900 DEG C of holding
20-30min, then heats to 1200-1300 DEG C and keeps 20-30min, be down to 600-700 DEG C of holding the most under nitrogen protection
30-40min；Above-mentioned lead-gadolinium, lead-yttrium foundry alloy are joined in above-mentioned melted lead antimony liquid mixing, is incubated 1-2h, form lead
Antimony gadolinium yittrium alloy grid.Lead-antimony alloy grid prepared by this invention, has higher electric conductivity and decay resistance so that lead
Acid battery has longer service life.The open a kind of slab lattice alloy of lead-acid battery additive of knowing clearly of patent CN103805809A
And preparation method thereof, slab lattice alloy of lead-acid battery additive includes the raw material of following weight: 940 ~ 960 parts of lead, antimony
20 ~ 40 parts, 5 ~ 12 parts of stannum, 0.55 ~ 0.65 part of selenium, copper 0.7 ~ 0.9 part, sulfur 0.1 ~ 0.2 part.Its preparation method be by containing selenium, copper,
It is standby that the alloy of element sulphur and lead are configured to lead selenium copper-sulphur alloy, then takes lead and puts into fusing of heating in high temperature furnace, then adds in batches
Enter whole additive, by scarfing cinder after stir process, ingot casting, obtain slab lattice alloy of lead-acid battery, i.e. obtain plumbic acid after fusing and store
Battery slab lattice alloy additive.The battery grid using alloy casting prepared by this invention have good decay resistance and
Tensile strength, extend grid accumulator cell charging and discharging circulate in service life.Although the alloy prepared by above-mentioned document
Respectively have advantage, but need to improve at alloy corrosion, high intensity, the uniform aspect of Elemental redistribution.
Accordingly, it would be desirable to a kind of anticorrosive, high intensity, Elemental redistribution uniform high performance alloys material of exploitation, it is used for improving
The use high temperature deeper cavity life-span of lead-acid accumulator.
Summary of the invention
It is an object of the invention to provide one and there is preferable corrosion resistance, non-deformability, be not easily formed passivating film
High performance positive plate alloy material for lattice.
A kind of maintenance-free lead accumulator positive grid alloy, including the composition of following percetage by weight:
Barium 0.02-0.15%,
Silver 0.002-0.01%,
Calcium 0.04-0.15%,
Stannum 0.25-1.80%,
Rare earth element 0.02-0.20%,
Lead surplus.
Described rare earth element is one or more in lanthanum, cerium, praseodymium and neodymium.
As preferentially, the percentage by weight of barium is 0.02-0.08%.
As preferentially, the percentage by weight of silver is 0.002-0.004%.
As preferentially, the percentage by weight of rare earth element is 0.02-0.1%.
A kind of maintenance-free lead accumulator positive grid alloy, including the composition of following percetage by weight:
Barium 0.05%,
Silver 0.003%,
Calcium 0.08%,
Stannum 0.95%,
Praseodymium 0.02%,
Neodymium 0.04%,
Lead surplus.
The preparation method of a kind of maintenance-free lead accumulator positive grid alloy, comprises the following steps:
(1) lead being divided into two parts, a part of lead melts at 410-440 DEG C, and another part is stand-by；After lead melts,
Add stannum；After being completely melt, it is warming up to 1500-1600 DEG C, adds calcium；After it is completely melt, stir；It is down to 500-
When 550 DEG C, come out of the stove, obtain slicker solder calcium alloy；
(2) in the high-temperature smelting pot of 950 DEG C, found rare earth element, after being completely melt, be warming up to 1000-1100 DEG C, then add
Enter silver, after it is completely melt, stir；When being down to 400-450 DEG C, come out of the stove, obtain silver rare-earth alloy；
(3) putting in lead pan by another part lead, temperature melts at rising to 410-440 DEG C；It is warming up to 600-650 DEG C, depends on
Secondary addition silver rare-earth alloy and slicker solder calcium alloy, mixed smelting also stirs；It is warming up to 760-800 DEG C, adds barium, after fusing
Stirring 5-10min；Fused solution is incubated 20min at 760-800 DEG C, grid alloy of coming out of the stove to obtain of lowering the temperature.
As preferably, the 25-30wt% that consumption is total lead of lead in described step (1), the consumption of lead in described step (3)
70-75wt% for total lead.
As preferably, described step (3) is carried out under nitrogen protection.
As preferably, it is 400-500 r/min that described step (3) adds the mixing speed after barium fusing.
The effect of the present invention: first, adds barium and can form Pb3Ba intermetallic precipitates forms hardening in lead base
Network, increases the intensity of grid, simultaneously can reduce the addition of Ca in alloy, effectively inhibits in passivating film the oxidations such as PbO
The generation of thing.
Secondly, add silver-colored so that rare earth element the most more disperses, stop rare earth element to float so that rare earth
Element is distributed more uniform in the alloy.
Again, the interpolation of rare earth element is so that crystal grain is tiny, regular.The interpolation of rare earth element changes metal
Structure, forms thinner corrosion product, fine and close corrosion layer, and effective prevention electrolyte corrodes grid alloy substrate further,
Alleviate the intercrystalline corrosion of grid alloy, prevent the outbreak-crash of grid so that it is there is preferable decay resistance.
Use the positive grid alloy prepared by the present invention, the charge acceptance of lead-acid accumulator can be improved, on an equal basis
Under the conditions of, accumulator charge acceptance 20-30% can be improved.Increase the resistance to corrosion of alloy, use constant current weight-loss method
Testing, experiment condition is 0.3A/cm2Electric current carry out constant current charge 100 hours, find the corrosion-resistant of alloy of the present invention
The alloy that energy force rate is traditional improves 15%-30%.Increase the anti-ability of growing up of grid, due to the existence of hardening element so that this
The tensile strength of bright alloy is higher than conventional alloys, uses GB/T228-2002 to test, test result indicate that tensile strength carries
High 20-25%.
Detailed description of the invention
Embodiment 1
A kind of maintenance-free lead accumulator positive grid alloy, including the composition of following percetage by weight:
Barium 0.02%,
Silver 0.002%,
Calcium 0.04%,
Stannum 0.25%,
Lanthanum 0.02%,
Lead surplus；
According to the proportioning of above-mentioned grid alloy, make to prepare as follows:
(1) lead being divided into two parts, a part of lead melts at 410-440 DEG C, and another part is stand-by；After lead melts,
Add stannum；After being completely melt, it is warming up to 1500-1600 DEG C, adds calcium；After it is completely melt, stir；It is down to 500-
When 550 DEG C, come out of the stove, obtain slicker solder calcium alloy；
(2) in the high-temperature smelting pot of 950 DEG C, found rare earth element, after being completely melt, be warming up to 1000-1100 DEG C, then add
Enter silver, after it is completely melt, stir；When being down to 400-450 DEG C, come out of the stove, obtain silver rare-earth alloy；
(3) putting in lead pan by another part lead, temperature melts at rising to 410-440 DEG C；It is warming up to 600-650 DEG C, depends on
Secondary addition silver rare-earth alloy and slicker solder calcium alloy, mixed smelting also stirs；It is warming up to 760-800 DEG C, adds barium, after fusing
Stirring 5-10min；Fused solution is incubated 20min at 760-800 DEG C, grid alloy of coming out of the stove to obtain of lowering the temperature；
Wherein, the 25wt% that consumption is total lead of lead in step (1), the 75wt% that consumption is total lead of lead in step (3)；Institute
State step (3) to carry out under nitrogen protection；It is 400-500 r/min that described step (3) adds the mixing speed after barium fusing.
Embodiment 2
A kind of maintenance-free lead accumulator positive grid alloy, including the composition of following percetage by weight:
Barium 0.05%,
Silver 0.003%,
Calcium 0.08%,
Stannum 0.95%,
Praseodymium 0.02%,
Neodymium 0.04%,
Lead surplus；
According to the proportioning of above-mentioned grid alloy, make to prepare as follows:
(1) lead being divided into two parts, a part of lead melts at 410-440 DEG C, and another part is stand-by；After lead melts,
Add stannum；After being completely melt, it is warming up to 1500-1600 DEG C, adds calcium；After it is completely melt, stir；It is down to 500-
When 550 DEG C, come out of the stove, obtain slicker solder calcium alloy；
(2) in the high-temperature smelting pot of 950 DEG C, found rare earth element, after being completely melt, be warming up to 1000-1100 DEG C, then add
Enter silver, after it is completely melt, stir；When being down to 400-450 DEG C, come out of the stove, obtain silver rare-earth alloy；
(3) putting in lead pan by another part lead, temperature melts at rising to 410-440 DEG C；It is warming up to 600-650 DEG C, depends on
Secondary addition silver rare-earth alloy and slicker solder calcium alloy, mixed smelting also stirs；It is warming up to 760-800 DEG C, adds barium, after fusing
Stirring 5-10min；Fused solution is incubated 20min at 760-800 DEG C, grid alloy of coming out of the stove to obtain of lowering the temperature；
Wherein, the 27wt% that consumption is total lead of lead in step (1), the 73wt% that consumption is total lead of lead in step (3)；Institute
State step (3) to carry out under nitrogen protection；It is 400-500 r/min that described step (3) adds the mixing speed after barium fusing.
Embodiment 3
A kind of maintenance-free lead accumulator positive grid alloy, including the composition of following percetage by weight:
Barium 0.05%,
Silver 0.003%,
Calcium 0.08%,
Stannum 0.95%,
Praseodymium 0.04%,
Neodymium 0.02%,
Lead surplus；
According to the proportioning of above-mentioned grid alloy, make to prepare as follows:
(1) lead being divided into two parts, a part of lead melts at 410-440 DEG C, and another part is stand-by；After lead melts,
Add stannum；After being completely melt, it is warming up to 1500-1600 DEG C, adds calcium；After it is completely melt, stir；It is down to 500-
When 550 DEG C, come out of the stove, obtain slicker solder calcium alloy；
(2) in the high-temperature smelting pot of 950 DEG C, found rare earth element, after being completely melt, be warming up to 1000-1100 DEG C, then add
Enter silver, after it is completely melt, stir；When being down to 400-450 DEG C, come out of the stove, obtain silver rare-earth alloy；
(3) putting in lead pan by another part lead, temperature melts at rising to 410-440 DEG C；It is warming up to 600-650 DEG C, depends on
Secondary addition silver rare-earth alloy and slicker solder calcium alloy, mixed smelting also stirs；It is warming up to 760-800 DEG C, adds barium, after fusing
Stirring 5-10min；Fused solution is incubated 20min at 760-800 DEG C, grid alloy of coming out of the stove to obtain of lowering the temperature；
Wherein, the 27wt% that consumption is total lead of lead in step (1), the 73wt% that consumption is total lead of lead in step (3)；Institute
State step (3) to carry out under nitrogen protection；It is 400-500 r/min that described step (3) adds the mixing speed after barium fusing.
Embodiment 4
A kind of maintenance-free lead accumulator positive grid alloy, including the composition of following percetage by weight:
Barium 0.08%,
Silver 0.004%,
Calcium 0.12%,
Stannum 1.3%,
Praseodymium 0.1%,
Lead surplus；
According to the proportioning of above-mentioned grid alloy, make to prepare as follows:
(1) lead being divided into two parts, a part of lead melts at 410-440 DEG C, and another part is stand-by；After lead melts,
Add stannum；After being completely melt, it is warming up to 1500-1600 DEG C, adds calcium；After it is completely melt, stir；It is down to 500-
When 550 DEG C, come out of the stove, obtain slicker solder calcium alloy；
(2) in the high-temperature smelting pot of 950 DEG C, found rare earth element, after being completely melt, be warming up to 1000-1100 DEG C, then add
Enter silver, after it is completely melt, stir；When being down to 400-450 DEG C, come out of the stove, obtain silver rare-earth alloy；
(3) putting in lead pan by another part lead, temperature melts at rising to 410-440 DEG C；It is warming up to 600-650 DEG C, depends on
Secondary addition silver rare-earth alloy and slicker solder calcium alloy, mixed smelting also stirs；It is warming up to 760-800 DEG C, adds barium, after fusing
Stirring 5-10min；Fused solution is incubated 20min at 760-800 DEG C, grid alloy of coming out of the stove to obtain of lowering the temperature；
Wherein, the 28wt% that consumption is total lead of lead in step (1), the 72wt% that consumption is total lead of lead in step (3)；Institute
State step (3) to carry out under nitrogen protection；It is 400-500 r/min that described step (3) adds the mixing speed after barium fusing.
Embodiment 5
A kind of maintenance-free lead accumulator positive grid alloy, including the composition of following percetage by weight:
Barium 0.15%,
Silver 0.01%,
Calcium 0.15%,
Stannum 1.80%,
Cerium 0.20%,
Lead surplus；
According to the proportioning of above-mentioned grid alloy, make to prepare as follows:
(1) lead being divided into two parts, a part of lead melts at 410-440 DEG C, and another part is stand-by；After lead melts,
Add stannum；After being completely melt, it is warming up to 1500-1600 DEG C, adds calcium；After it is completely melt, stir；It is down to 500-
When 550 DEG C, come out of the stove, obtain slicker solder calcium alloy；
(2) in the high-temperature smelting pot of 950 DEG C, found rare earth element, after being completely melt, be warming up to 1000-1100 DEG C, then add
Enter silver, after it is completely melt, stir；When being down to 400-450 DEG C, come out of the stove, obtain silver rare-earth alloy；
(3) putting in lead pan by another part lead, temperature melts at rising to 410-440 DEG C；It is warming up to 600-650 DEG C, depends on
Secondary addition silver rare-earth alloy and slicker solder calcium alloy, mixed smelting also stirs；It is warming up to 760-800 DEG C, adds barium, after fusing
Stirring 5-10min；Fused solution is incubated 20min at 760-800 DEG C, grid alloy of coming out of the stove to obtain of lowering the temperature；
Wherein, the 30wt% that consumption is total lead of lead in step (1), the 70wt% that consumption is total lead of lead in step (3)；Institute
State step (3) to carry out under nitrogen protection；It is 400-500 r/min that described step (3) adds the mixing speed after barium fusing.
Embodiment 6
A kind of maintenance-free lead accumulator positive grid alloy, including the composition of following percetage by weight:
Barium 0.05%,
Silver 0.003%,
Calcium 0.08%,
Stannum 0.95%,
Praseodymium 0.02%,
Neodymium 0.04%,
Lead surplus；
According to the proportioning of above-mentioned grid alloy, make to prepare as follows:
(1) stannum is melted at 410-440 DEG C, after being completely melt, be warming up to 1500-1600 DEG C, add calcium；Treat that it is complete
After fusing, stir；When being down to 500-550 DEG C, come out of the stove, obtain slicker solder calcium alloy；
(2) in the high-temperature smelting pot of 950 DEG C, found rare earth element, after being completely melt, be warming up to 1000-1100 DEG C, then add
Enter silver, after it is completely melt, stir；When being down to 400-450 DEG C, come out of the stove, obtain silver rare-earth alloy；
(3) putting in lead pan by lead, temperature melts at rising to 410-440 DEG C；It is warming up to 600-650 DEG C, is sequentially added into silver
Rare earth alloy and stannum calcium alloy, mixed smelting also stirs；It is warming up to 760-800 DEG C, adds barium, after fusing, stir 5-
10min；Fused solution is incubated 20min at 760-800 DEG C, grid alloy of coming out of the stove to obtain of lowering the temperature；
Wherein, the 27wt% that consumption is total lead of lead in step (1), the 73wt% that consumption is total lead of lead in step (3)；Institute
State step (3) to carry out under nitrogen protection；It is 400-500 r/min that described step (3) adds the mixing speed after barium fusing.
Grid alloy prepared by embodiment 1-6 is carried out performance test, and test result is shown in Table 1.
Wherein, the resistance to corrosion of alloy, use constant current corrosion weight loss method to test, experiment condition is: at 75 DEG C
Water environment under, 0.3A/cm2Electric current carry out constant current charge 100 hours, then use weight-loss method compare.
Tensile strength is tested, and tests with reference to GB/T228-2002.
The performance test results of table 1. grid alloy
By table 1 data it can be seen that the corrosion rate of grid alloy obtained by embodiment 2-3 than embodiment 1 and is implemented
The corrosion rate of example 4-5 is lower, and the tensile strength of the grid alloy obtained by embodiment 2-3 than embodiment 1 and is implemented
The tensile strength of example 4-5 wants height, illustrates that employing rare earth element uses the performance of the grid alloy obtained by praseodymium and neodymium more preferably simultaneously.
And the corrosion rate of the grid alloy that the corrosion rate of the grid alloy prepared by embodiment 6 compares embodiment 1-5 to exceed perhaps
Many, and low than embodiment 1-5 of tensile strength, illustrate that alloy proportion of the present invention and lead divide two parts to be prepared
The grid alloy obtained by method, it is possible to drop low-alloyed relatively corrosive speed, improve the intensity of grid alloy.
A kind of maintenance-free lead accumulator positive grid alloy provided the embodiment of the present invention above, has been carried out in detail
Thin introducing, principle and the embodiment of the present invention are set forth by specific case used herein, saying of above example
Bright method and the core concept thereof being only intended to help to understand the present invention；Simultaneously for one of ordinary skill in the art, foundation
The thought of the present invention, the most all will change, and in sum, this specification content is not
It is interpreted as limitation of the present invention.
Claims (7)
1. a maintenance-free lead accumulator positive grid alloy, it is characterised in that be grouped by the one-tenth of following percetage by weight
Become:
Barium 0.02-0.08%,
Silver 0.002-0.004%,
Calcium 0.04-0.15%,
Stannum 0.25-1.80%,
Rare earth element 0.02-0.20%,
Lead surplus.
Grid alloy the most according to claim 1, it is characterised in that described rare earth element is in lanthanum, cerium, praseodymium and neodymium
Plant or multiple.
Grid alloy the most according to claim 1, it is characterised in that the percentage by weight of described rare earth element is further
0.02-0.1%。
4. a maintenance-free lead accumulator positive grid alloy, it is characterised in that be grouped by the one-tenth of following percetage by weight
Become:
Barium 0.05%,
Silver 0.003%,
Calcium 0.08%,
Stannum 0.95%,
Praseodymium 0.02%,
Neodymium 0.04%,
Lead surplus.
5. a preparation method for the maintenance-free lead accumulator positive grid alloy as described in any one of claim 1-4,
It is characterized in that, comprise the following steps:
(1) lead being divided into two parts, a part of lead melts at 410-440 DEG C, and another part is stand-by；After lead melts, add
Stannum；After being completely melt, it is warming up to 1500-1600 DEG C, adds calcium；After it is completely melt, stir；It is down to 500-550 DEG C
Time, come out of the stove, obtain slicker solder calcium alloy；
(2) in the high-temperature smelting pot of 950 DEG C, found rare earth element, after being completely melt, be warming up to 1000-1100 DEG C, add silver,
After it is completely melt, stir；When being down to 400-450 DEG C, come out of the stove, obtain silver rare-earth alloy；
(3) putting in lead pan by another part lead, temperature melts at rising to 410-440 DEG C；It is warming up to 600-650 DEG C, adds successively
Entering silver rare-earth alloy and slicker solder calcium alloy, mixed smelting also stirs；It is warming up to 760-800 DEG C, adds barium, stir after fusing
5-10min；Fused solution is incubated 20min at 760-800 DEG C, grid alloy of coming out of the stove to obtain of lowering the temperature.
The preparation method of positive grid alloy the most according to claim 5, it is characterised in that lead in described step (1)
Consumption is the 25-30wt% of total lead, the 70-75wt% that consumption is total lead of lead in described step (3).
The preparation method of positive grid alloy the most according to claim 5, it is characterised in that described step (3) is at nitrogen
Carry out under protection.
The preparation method of positive grid alloy the most according to claim 5, it is characterised in that described step (3) adds barium
Mixing speed after fusing is 400-500 r/min.
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| CN102623753B (en) * | 2012-04-11 | 2014-08-06 | 淄博明泰电器科技有限公司 | Plate-type polar plate lead acid storage battery |
| CN103762369B (en) * | 2014-01-10 | 2016-08-17 | 江苏海宝电池科技有限公司 | A kind of rare-earth lead alloy for lead-acid storage battery positive grid |
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2015
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108808010A (en) * | 2018-06-12 | 2018-11-13 | 河北超威电源有限公司 | A kind of Moped Scooter positive electrode grid of lead storage battery alloy and preparation method thereof |
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