CN104073683B - A kind of low temperature deeper cavity positive grid alloy and preparation method thereof - Google Patents
A kind of low temperature deeper cavity positive grid alloy and preparation method thereof Download PDFInfo
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- CN104073683B CN104073683B CN201410298050.2A CN201410298050A CN104073683B CN 104073683 B CN104073683 B CN 104073683B CN 201410298050 A CN201410298050 A CN 201410298050A CN 104073683 B CN104073683 B CN 104073683B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C11/00—Alloys based on lead
- C22C11/06—Alloys based on lead with tin as the next major constituent
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Abstract
The invention discloses a kind of low temperature deeper cavity positive grid alloy, be made up of: calcium 0.05 ~ 0.12%, tin 0.2 ~ 2.0%, aluminium 0.01 ~ 0.1%, zinc 0.01 ~ 0.2% raw material of following mass percent, surplus is plumbous.The low-temperature performance that the alloy that the present invention provides has had, forms the impedance of anodic corrosion film under reducing low temperature.Zinc element clearly can improve the deep-circulating performance of battery, even under cryogenic, because the good conductivity of PbZnO type oxide.
Description
Technical field
The invention belongs to lead acid cell field, relate to a kind of low temperature deeper cavity process for positive slab lattice of lead-acid accumulator Alloy And Preparation Method.
Background technology
In lead-acid cell field, the low-temperature performance of battery is always unsatisfactory.It has been generally acknowledged that what the mainly negative plate affecting low-temperature performance determined, but find that positive plate also limits the low-temperature performance of battery in reality test, find further simultaneously, the resistance of the anodic corrosion film that conventional cathode grid Pb-Ca-Sn-Al alloy is formed at low temperatures is relatively large, thus limit battery deep-circulating performance at low temperatures.
Summary of the invention
The object of the invention is to, the alloy low-temperature performance for existing routine plumbous calcium tin aluminium is not enough, provides a kind low temperature deeper cavity positive grid alloy, can close to performance under normal temperature to battery performance under low temperature.The technical problem that simultaneously will solve is, provides the index method of this positive grid alloy.
For reaching above-mentioned technical purpose, technical scheme of the present invention is as follows:
A kind of low temperature deeper cavity positive grid alloy, is made up of the raw material of following mass percent:
Calcium 0.05 ~ 0.12%
Tin 0.2 ~ 2.0%
Aluminium 0.01 ~ 0.1%
Zinc 0.01 ~ 0.2%
Surplus is plumbous.
As the preferred alloying element mass percent of one be: calcium: 0.09%, tin: 1.8%, aluminium: 0.05%, zinc: 0.08%, plumbous is surplus.
A preparation method for low temperature deeper cavity positive grid alloy, comprises the following steps: by the mass percent of above-mentioned raw materials,
(1) lead button accounting for leady raw materials total mass 80 ~ 85% is added in the graphite market pot of intermediate frequency furnace 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 and zinc when temperature is down to 520 ~ 540 DEG C to melt, then stir 2 ~ 3min and make tin and zinc 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 low-temperature performance that the alloy that the present invention provides has had, forms the impedance of anodic corrosion film under reducing low temperature.Zinc element clearly can improve the deep-circulating performance of battery, even under cryogenic, because the good conductivity of PbZnO type oxide.
2, 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.
3, 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 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
The applicant have submitted plumbous calcium tin aluminium positive grid alloy and preparation method thereof patent application on the same day, and this part of patent application provides, and alloy corrosion resisting alloy element preferred mass is than being calcium: 0.09%, tin: 1.8%, aluminium: 0.05%.In the application, conveniently compare the impact of zinc alloy low-temperature performance, therefore, the alloying element proportioning outside the embodiment of the present application 1-3 zinc remains unchanged.
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: 1.8%, aluminium: 0.05%, zinc: 0.01%, plumbous is surplus;
(2) lead button accounting for leady raw materials total mass 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%, 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 and zinc when temperature is down to 520 ~ 540 DEG C to melt, then stir 2 ~ 3min and make tin and zinc 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: 1.8%, aluminium: 0.05%, zinc: 0.08%, plumbous is surplus;
(2) lead button accounting for leady raw materials total mass 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%, 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 and zinc when temperature is down to 520 ~ 540 DEG C to melt, then stir 2 ~ 3min and make tin and zinc 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: 0.5%, aluminium: 0.05%, zinc: 0.2%, plumbous is surplus;
(2) lead button accounting for leady raw materials total mass 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%, 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 and zinc when temperature is down to 520 ~ 540 DEG C to melt, then stir 2 ~ 3min and make tin and zinc 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.
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.Through deeper cavity test find example one alloy cell at low temperatures deeper cavity capacity at about 6Ah, example two alloy cell at low temperatures deeper cavity capacity at about 10Ah,
The interpolation of zinc improves the low temperature deep-circulating performance of battery well.
Claims (4)
1. a low temperature preparation method for deeper cavity positive grid alloy, is characterized in that being made up of the raw material of following mass percent:
Calcium 0.05 ~ 0.12%
Tin 0.2 ~ 2.0%
Aluminium 0.01 ~ 0.1%
Zinc 0.01 ~ 0.2%
Surplus is plumbous;
Comprise the following steps: by the mass percent of above-mentioned raw materials,
(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 and zinc when temperature is down to 520 ~ 540 DEG C to melt, then stir 2 ~ 3min and make tin and zinc 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 low temperature deeper cavity positive grid alloy as claimed in claim 1, is characterized in that: calcium: 0.09%, tin: 1.8%, aluminium: 0.05%, zinc: 0.08%, plumbous is surplus.
3. the preparation method of a kind of low temperature deeper cavity positive grid 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 low temperature deeper cavity positive grid alloy as claimed in claim 1, is characterized in that: described graphite market pot has vertical long semielliptical shape inner chamber.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410298050.2A CN104073683B (en) | 2014-06-27 | 2014-06-27 | A kind of low temperature deeper cavity positive grid alloy and preparation method thereof |
| PCT/CN2014/088342 WO2015196624A1 (en) | 2014-06-27 | 2014-10-11 | Gate alloy for low-temperature deep-cycle positive electrode plate, and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410298050.2A CN104073683B (en) | 2014-06-27 | 2014-06-27 | A kind of low temperature deeper cavity positive grid alloy and preparation method thereof |
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| Publication Number | Publication Date |
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| CN104073683A CN104073683A (en) | 2014-10-01 |
| CN104073683B true CN104073683B (en) | 2016-02-10 |
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| WO (1) | WO2015196624A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104073683B (en) * | 2014-06-27 | 2016-02-10 | 天能集团江苏科技有限公司 | A kind of low temperature deeper cavity positive grid alloy and preparation method thereof |
| 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 |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO1995015587A1 (en) * | 1993-11-30 | 1995-06-08 | Shi Xue Dou | Improved grid alloy for lead-acid battery |
| BR9505372A (en) * | 1995-12-07 | 1997-10-28 | Microlite S A | Lead alloy - calcium - tin - aluminum - silver for the manufacture of electric battery grids |
| US20040112486A1 (en) * | 1996-03-01 | 2004-06-17 | Aust Karl T. | Thermo-mechanical treated lead and lead alloys especially for current collectors and connectors in lead-acid batteries |
| CN1198599A (en) * | 1997-05-05 | 1998-11-11 | 陈有孝 | High specific energy fully closed maintenanceless lead acid accumulator |
| DE19823147A1 (en) * | 1998-05-23 | 1999-11-25 | Vb Autobatterie Gmbh | Electrode grid for lead accumulators |
| CN101656312B (en) * | 2009-07-08 | 2011-09-21 | 张天任 | Alloy material for high-energy accumulator grid and preparation method thereof |
| CN102517471A (en) * | 2011-12-19 | 2012-06-27 | 河南豫光金铅股份有限公司 | Production method of adding calcium in lead |
| CN102703755B (en) * | 2012-06-21 | 2016-08-31 | 上海锦众信息科技有限公司 | The preparation method of lead-acid accumulator grid alloy material |
| CN102709528A (en) * | 2012-06-21 | 2012-10-03 | 上海锦众信息科技有限公司 | Method for preparing positive plate of lead-acid storage battery |
| CN103107310B (en) * | 2012-11-11 | 2015-07-22 | 广西天鹅蓄电池有限责任公司 | Manufacturing method of storage battery green plate |
| CN102938465B (en) * | 2012-11-11 | 2015-08-19 | 骆驼集团华南蓄电池有限公司 | Lead-acid storage battery grid lead alloy |
| CN104073683B (en) * | 2014-06-27 | 2016-02-10 | 天能集团江苏科技有限公司 | A kind of low temperature deeper cavity positive grid alloy and preparation method thereof |
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- 2014-06-27 CN CN201410298050.2A patent/CN104073683B/en active Active
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| CN104073683A (en) | 2014-10-01 |
| WO2015196624A1 (en) | 2015-12-30 |
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