CN104073682B - A kind of long lifetime deeper cavity positive grid alloy and preparation method thereof - Google Patents
A kind of long lifetime deeper cavity positive grid alloy and preparation method thereof Download PDFInfo
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- CN104073682B CN104073682B CN201410298073.3A CN201410298073A CN104073682B CN 104073682 B CN104073682 B CN 104073682B CN 201410298073 A CN201410298073 A CN 201410298073A CN 104073682 B CN104073682 B CN 104073682B
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Abstract
The invention discloses a kind of long lifetime deeper cavity process for positive slab lattice of lead-acid accumulator alloy, be made up of the raw material of following mass percent, calcium: 0.05 ~ 0.12%, tin: 0.1 ~ 2.0%, aluminium: 0.01 ~ 0.1%, zinc: 0.01 ~ 0.2%, silver: 0.01 ~ 0.2%, lead is surplus.The corrosion resistant performance that the alloy that the present invention provides has had, does not affect the deep-circulating performance of battery simultaneously.The interpolation of zinc can improve deep-circulating performance and the low-temperature performance of battery well; The interpolation of silver can improve the erosion resistance of grid alloy, in contrasting as can be seen from accompanying drawing 1 and accompanying drawing 2, the silver added can be enriched in subgrain boundary and grain boundaries with tin, and the silver being enriched in crystal boundary can improve the erosion resistance of crystal boundary, thus improves the work-ing life of alloy grid.
Description
Technical field
The invention belongs to lead acid cell field, relate to a kind of long lifetime deeper cavity process for positive slab lattice of lead-acid accumulator Alloy And Preparation Method.
Background technology
Grid is an important integral part in lead-acid cell, although it does not have direct castering action to capacity, but play as conducting in the skeletal support effect of active substance and battery charge and discharge process, evenly distributing electric current effect, these performances directly limit capacity and the cycle life of battery, and whether these performances are superior depends primarily on grid alloy used.
The main Pb-Sb-Cd alloy of grid material of traditional lead acid batteries, the castability of this alloy and mechanical property all can meet the production of battery and use needs, and its corrosion layer formed has good electroconductibility, substantially can suppress PCL phenomenon.But the overpotential of hydrogen evolution of antimony and cadmium is lower, the especially dissolving of antimony and transfer in alloy, makes positive and negative electrode analyse oxygen overpotential of hydrogen evolution and reduces, cause battery dehydration to be accelerated like this, self-discharge increase.And cadmium is hypertoxic metal, battery preparation and reclaim all can cause larger pollution to environment, harm operator healthy.
Prohibit the use already abroad containing cadmium alloy, domestic explicit stipulation will prohibit the use to the end of the year 2013 containing cadmium alloy, so Pb-Sb-Cd alloy has exited the arena of history, lead-calcium alloy just becomes the study hotspot of lead-acid cell thereupon.Lead-calcium alloy resistance is less, close to pure lead; And overpotential of hydrogen evolution is high, so water decomposition is few; Calcium is negative potential simultaneously, can not cause self-discharge and toxic gas SbH by solution transfer to negative pole
3precipitation.But find the corrosive film poorly conductive that calcium is formed, and calcium also makes alloy rotproofness decline, and the non-antimony effect of generation easily makes lead-acid cell occur premature capacity loss and life-span premature termination etc.So Pb-Ca-Sn-Al alloy arises, but find that the life-span is than Pb-Sb-Cd alloy battery decreased average nearly 1/3, find after deliberation, the coarse grains of conventional Pb-Ca-Sn-Al alloy, easily cause intergranular corrosion, thus making alloy monolithic rotproofness not good, this is the principal element that battery life terminates in advance.
Summary of the invention
The object of the invention is to, rotproofness for existing conventional Pb-Ca-Sn-Al alloy is not enough, a kind of long lifetime deeper cavity process for positive slab lattice of lead-acid accumulator alloy is provided, makes battery have longer cycle life, Pb-Sb-Cd alloy battery performance can be exceeded to battery performance.Meanwhile, the present invention will provide the preparation method of this positive grid alloy.
For reaching above-mentioned technical purpose, technical scheme of the present invention is as follows:
A kind of long lifetime deeper cavity process for positive slab lattice of lead-acid accumulator alloy, to be made up of the raw material of following mass percent, calcium: 0.05 ~ 0.12%, tin: 0.1 ~ 2.0%, aluminium: 0.01 ~ 0.1%, zinc: 0.01 ~ 0.2%, silver: 0.01 ~ 0.2%, lead is surplus.
Further preferred version is, calcium: 0.09%, tin: 0.18%, aluminium: 0.05%, zinc: 0.08%, silver: 0.05%, lead is surplus.
A preparation method for long lifetime deeper cavity process for positive slab lattice of lead-acid accumulator alloy, comprises the following steps:
(1) lead button accounting for leady raw materials total mass 80 ~ 85% is added in the graphite market pot of intermediate frequency furnace and be heated to 670 ~ 680 DEG C, lead button is fully melted, with the sheet lead accounting for leady raw materials total mass 0.5 ~ 1%, wrap up the calcium bits and aluminium foil that mix, and be pressed in the plumbous liquid of melting together, then stirring 2 ~ 3min makes calcium aluminium element mix in plumbous liquid, in the process, keeps the temperature of melt between 670 ~ 680 DEG C;
(3) stop stirring and heating, add remaining lead button, melt is stirred, add tin, zinc, silver when temperature is down to 520 ~ 540 DEG C to melt, then stir 2 ~ 3min and make tin, zinc, silver melt completely and mix;
(4) slag-cleaning agent is spread to bath surface, stir 1 ~ 2min, then scum silica frost is removed;
(5) cast when melt temperature is down to 480 ~ 500 DEG C.
The flap of the bits of calcium described in step (1), aluminium foil to be all diameters be 3 ~ 4mm.
It is convenient reinforced for wrapping up an aspect with sheet lead, prevents calcium from considering to be worth doing in addition and contacts with oxygen, reduces calcium bits and is oxidized in atmosphere.
Described graphite market pot has vertical long semielliptical shape inner chamber.Usual market pot is square, and calrod heats; Square lead pan has stirring dead angle, and simultaneously intermediate frequency heating speed is fast, efficiency is high, and heating has from agitating function simultaneously, the alloying constituent allotted can be made like this evenly.
After have employed technique scheme, the invention has the beneficial effects as follows:
1, the corrosion resistant performance that the alloy that the present invention provides has had, does not affect the deep-circulating performance of battery simultaneously.The interpolation of zinc can improve deep-circulating performance and the low-temperature performance of battery well; The interpolation of silver can improve the erosion resistance of grid alloy, in contrasting as can be seen from accompanying drawing 1 and accompanying drawing 2, the silver added can be enriched in subgrain boundary and grain boundaries with tin, and the silver being enriched in crystal boundary can improve the erosion resistance of crystal boundary, thus improves the work-ing life of alloy grid.
2, the effect of zinc: the zone of oxidation of zinc in anodic corrosion film can form PbSnZnO type oxide, this oxide compound has better conduction property semi-conductor, even if electroconductibility is still superior under cryogenic.So the interpolation of zinc to improve grid electroconductibility at low temperatures, reduce low-temperature resistance, improve the low temperature capacity of battery.
3, the present invention is in process for preparation, and the calcium bits mixed are joined in plumbous liquid with aluminium foil simultaneously, eliminates the process of tradition preparation calcium aluminium mother alloy, so not only avoids a large amount of scaling loss of calcium, and enhance productivity, saved production cost.
4, the long semielliptical shape inner chamber that the present invention is used graphite market pot with there is the intermediate frequency furnace of automatic stirring function, these can make to allot the alloying constituent uniformity come, and improve production efficiency.
Accompanying drawing explanation
Fig. 1 is the metallograph of the embodiment of the present invention two alloy.
Fig. 2 example one and the impedance spectrum schematic diagram of example two alloy under 0.8V.Found by impedance spectrum contrast, the anonite membrane impedance that example two is formed is much smaller than example one.
Embodiment
Embodiment one
A kind of low temperature deeper cavity positive grid alloy preparation method, is characterized in that comprising the following steps:
(1) raw material prepares: lead, calcium, tin and aluminium, and the mass percent that each raw material accounts for total raw material is: calcium: 0.09%, tin: 0.2%, aluminium: 0.05%, zinc: 0.02%, silver: 0.01%, plumbous is surplus;
(2) lead button accounting for leady raw materials total mass 85% is added in intermediate frequency furnace graphite market pot be heated to 670 ~ 680 DEG C, lead button is fully melted, with the sheet lead accounting for leady raw materials total mass 0.5%, wrap up the calcium bits and aluminium foil that mix, and be pressed in the plumbous liquid of melting together, then stirring 2 ~ 3min makes calcium aluminium element mix in plumbous liquid, in the process, keeps the temperature of melt between 670 ~ 680 DEG C;
(3) stop stirring and heating, add remaining lead button, melt is stirred, add tin, zinc, silver when temperature is down to 520 ~ 540 DEG C to melt, then stir 2 ~ 3min and make tin, zinc, silver melt completely and mix;
(4) slag-cleaning agent is spread to bath surface, stir 1 ~ 2min, then scum silica frost is removed;
(5) cast when melt temperature is down to 480 ~ 500 DEG C.
Embodiment two
A kind of low temperature deeper cavity positive grid alloy preparation method, is characterized in that comprising the following steps:
(1) raw material prepares: lead, calcium, tin and aluminium, and the mass percent that each raw material accounts for total raw material is: calcium: 0.09%, tin: 0.18%, aluminium: 0.05%, zinc: 0.08%, silver: 0.05%, plumbous is surplus;
(2) lead button accounting for leady raw materials total mass 85% is added in intermediate frequency furnace be heated to 670 ~ 680 DEG C, lead button is fully melted, with the sheet lead accounting for leady raw materials total mass 0.5%, wrap up the calcium bits and aluminium foil that mix, and be pressed in the plumbous liquid of melting together, then stirring 2 ~ 3min makes calcium aluminium element mix in plumbous liquid, in the process, keeps the temperature of melt between 670 ~ 680 DEG C;
(3) stop stirring and heating, add remaining lead button, melt is stirred, add tin, zinc, silver when temperature is down to 520 ~ 540 DEG C to melt, then stir 2 ~ 3min and make tin, zinc, silver melt completely and mix;
(4) slag-cleaning agent is spread to bath surface, stir 1 ~ 2min, then scum silica frost is removed;
(5) cast when melt temperature is down to 480 ~ 500 DEG C.
Embodiment three
A kind of low temperature deeper cavity positive grid alloy preparation method, is characterized in that comprising the following steps:
(1) raw material prepares: lead, calcium, tin and aluminium, and the mass percent that each raw material accounts for total raw material is: calcium: 0.09%, tin: 0.2%, aluminium: 0.05%, zinc: 0.15%, silver: 0.15%, plumbous is surplus;
(2) lead button accounting for leady raw materials total mass 80 ~ 85% is added in intermediate frequency furnace be heated to 670 ~ 680 DEG C, lead button is fully melted, the calcium bits and aluminium foil that mix are wrapped up with sheet lead, and be pressed in the plumbous liquid of melting together, then stirring 2 ~ 3min makes calcium aluminium element mix in plumbous liquid, in the process, keep the temperature of melt between 670 ~ 680 DEG C;
(3) stop stirring and heating, add remaining lead button, melt is stirred, add tin, zinc, silver when temperature is down to 520 ~ 540 DEG C to melt, then stir 2 ~ 3min and make tin, zinc, silver melt completely and mix;
(4) slag-cleaning agent is spread to bath surface, stir 1 ~ 2min, then scum silica frost is removed;
(5) cast when melt temperature is down to 480 ~ 500 DEG C.
By above-mentioned three embodiment alloys respectively smear be assembled into 12V12Ah experimental cell test, deeper cavity work system is: the charging stage, store battery is in the environment of 25 DEG C ± 5 DEG C in temperature, with single store battery average voltage for 15V(current limliting 3A) constant voltage trickle charge 8h maybe when charging latter stage current stabilization 3h constant, be now and be full of electricity; Discharge regime, adopts GB GB/T22199-20086.12.1 electric discharge, namely after store battery is full of electricity, in the environment of 25 DEG C ± 5 DEG C, discharges into when accumulator voltage reaches 10.50V stop with 6A.Find that the cycle life of each embodiment alloy cell is as table 1 through deeper cavity test, can find out that embodiment two has higher cycle life, embodiment three is because cause grid corrosion rete too fine and close excessive the adding of silver, thus cause active substance and grid to cause bulk to come off, therefore the life-span does not obviously promote.
Above-mentioned example one, example two alloy smear are assembled into the test of 12V12Ah experimental cell, low temperature deeper cavity work system is: the charging stage, store battery is in the environment of-15 DEG C ± 1 DEG C in temperature, with single store battery average voltage for 15V(current limliting 3A) constant voltage trickle charge 8h maybe when charging latter stage current stabilization 3h constant, be now and be full of electricity; Discharge regime, after store battery is full of electricity, in the environment of-15 DEG C ± 1 DEG C, discharges into when accumulator voltage reaches 10.50V with 6A and stops.Deeper cavity capacity is at about 6Ah at low temperatures to find example one alloy cell through deeper cavity test, and example two alloy cell at low temperatures deeper cavity capacity exists
About 10Ah, the interpolation of zinc improves the low temperature deep-circulating performance of battery well.
The each alloy grid battery cycle life of table 1
| Embodiment one | Embodiment two | Embodiment three | ||
| Life-span (week) | 232 | 531 | 276 |
Claims (4)
1. the preparation method of a long lifetime deeper cavity process for positive slab lattice of lead-acid accumulator alloy, its feature exists: be made up of the raw material of following mass percent, calcium: 0.05 ~ 0.12%, tin: 0.1 ~ 2.0%, aluminium: 0.01 ~ 0.1%, zinc: 0.01 ~ 0.2%, silver: 0.01 ~ 0.2%, lead is surplus;
Preparation process is as follows:
(1) lead button accounting for leady raw materials total mass 80 ~ 85% is added in the graphite market pot of intermediate frequency furnace and be heated to 670 ~ 680 DEG C, lead button is fully melted, with the sheet lead accounting for leady raw materials total mass 0.5 ~ 1%, wrap up the calcium bits and aluminium foil that mix, and be pressed in the plumbous liquid of melting together, then stirring 2 ~ 3min makes calcium aluminium element mix in plumbous liquid, in the process, keeps the temperature of melt between 670 ~ 680 DEG C;
(3) stop stirring and heating, add remaining lead button, melt is stirred, add tin, zinc, silver when temperature is down to 520 ~ 540 DEG C to melt, then stir 2 ~ 3min and make tin, zinc, silver melt completely and mix;
(4) slag-cleaning agent is spread to bath surface, stir 1 ~ 2min, then scum silica frost is removed;
(5) cast when melt temperature is down to 480 ~ 500 DEG C.
2. the preparation method of a kind of long lifetime deeper cavity process for positive slab lattice of lead-acid accumulator alloy as claimed in claim 1, it is characterized in that: the mass percent that each raw material accounts for total raw material is, calcium: 0.09%, tin: 0.18%, aluminium: 0.05%, zinc: 0.08%, silver: 0.05%, lead is surplus.
3. the preparation method of a kind of long lifetime deeper cavity process for positive slab lattice of lead-acid accumulator alloy as claimed in claim 1, is characterized in that: the flap of the bits of calcium described in step (1), aluminium foil to be all diameters be 3 ~ 4mm.
4. the preparation method of a kind of long lifetime deeper cavity process for positive slab lattice of lead-acid accumulator alloy as claimed in claim 1, is characterized in that: described graphite market pot has vertical long semielliptical shape inner chamber.
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| CN106636737B (en) * | 2016-12-21 | 2018-11-06 | 河南超威电源有限公司 | A kind of power type positive electrode grid of lead storage battery alloy and preparation method |
| CN107287470B (en) * | 2017-05-25 | 2019-02-15 | 天能电池集团有限公司 | A kind of lead storage battery grid alloy and preparation method comprising nanometer tungsten carbide material |
| CN110129616A (en) * | 2019-04-18 | 2019-08-16 | 肇庆理士电源技术有限公司 | A kind of lead-acid accumulator corrosion-resistant metal and preparation method thereof |
| CN110284026A (en) * | 2019-07-09 | 2019-09-27 | 安徽理士电源技术有限公司 | A kind of grid alloy and preparation method for high-temperature cyclic type AGM battery |
| CN113471447B (en) * | 2021-07-05 | 2023-08-04 | 林章勇 | Grid alloy for lead storage battery and preparation process thereof |
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| CN1198599A (en) * | 1997-05-05 | 1998-11-11 | 陈有孝 | High specific energy fully closed maintenanceless lead acid accumulator |
| US6210837B1 (en) * | 1998-05-23 | 2001-04-03 | Varta Batterie Aktiengesellschaft | Electrode grid for lead storage batteries |
| CN101656312A (en) * | 2009-07-08 | 2010-02-24 | 张天任 | Alloy material for high-energy accumulator grid and preparation method thereof |
| CN101696479A (en) * | 2009-11-03 | 2010-04-21 | 株洲冶炼集团股份有限公司 | Method for producing lead-calcium alloy |
| CN103107310A (en) * | 2012-11-11 | 2013-05-15 | 广西天鹅蓄电池有限责任公司 | Manufacturing method of storage battery green plate |
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Patent Citations (5)
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| CN1198599A (en) * | 1997-05-05 | 1998-11-11 | 陈有孝 | High specific energy fully closed maintenanceless lead acid accumulator |
| US6210837B1 (en) * | 1998-05-23 | 2001-04-03 | Varta Batterie Aktiengesellschaft | Electrode grid for lead storage batteries |
| CN101656312A (en) * | 2009-07-08 | 2010-02-24 | 张天任 | Alloy material for high-energy accumulator grid and preparation method thereof |
| CN101696479A (en) * | 2009-11-03 | 2010-04-21 | 株洲冶炼集团股份有限公司 | Method for producing lead-calcium alloy |
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