CN104073683A - Low-temperature deep-cycle positive grid alloy and preparation method thereof - Google Patents
Low-temperature deep-cycle positive grid alloy and preparation method thereof Download PDFInfo
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- CN104073683A CN104073683A CN201410298050.2A CN201410298050A CN104073683A CN 104073683 A CN104073683 A CN 104073683A CN 201410298050 A CN201410298050 A CN 201410298050A CN 104073683 A CN104073683 A CN 104073683A
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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 low-temperature deep-cycle positive grid alloy which consists of the following materials in percentage by weight: 0.05-0.12% of calcium, 0.2-2.0% of tin, 0.01%-0.1% of aluminum, 0.01-0.2 of zinc and the balance of lead. The alloy disclosed by the invention has good low temperature performance, and reduces impedance for forming an anode corrosion membrane at a low temperature. The zinc element can improve deep-cycle performances of the battery very obviously even under a low temperature condition due to good conductivity of PbZnO oxides.
Description
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Technical field
The invention belongs to lead acid cell field, relate to dark circulation process for positive slab lattice of lead-acid accumulator Alloy And Preparation Method for a kind of low temperature.
Background technology
In lead-acid cell field, the low-temperature performance of battery is always unsatisfactory.It has been generally acknowledged that what affect low-temperature performance is mainly that negative plate determines, yet find that positive plate also limits the low-temperature performance of battery in reality test, further find simultaneously, the resistance of conventional anode plate grid Pb-Ca-Sn-Al alloy formed anodic corrosion film under low temperature condition is relatively large, has limited thus battery deep-circulating performance at low temperatures.
Summary of the invention
The object of the invention is to, not enough for the alloy low-temperature performance of the plumbous calcium tin of existing routine aluminium, dark circulation positive grid alloy for a kind low temperature is provided, to battery performance under low temperature, can approach performance under normal temperature.The technical problem that simultaneously will solve is that the index method of this positive grid alloy is provided.
For reaching above-mentioned technical purpose, technical scheme of the present invention is as follows:
A dark circulation positive grid alloy for low temperature, is comprised 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 a kind of preferred alloying element mass percent, be: calcium: 0.09%, tin: 1.8%, aluminium: 0.05%, zinc: 0.08%, plumbous is surplus.
A preparation method for dark circulation positive grid alloy for low temperature, comprises the following steps: by the mass percent of above-mentioned raw materials,
(1) lead button that accounts 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 ℃, lead button is fully melted, with the sheet lead that accounts for leady raw materials total mass 0.5 ~ 1%, calcium bits and aluminium foil that parcel mixes, and be pressed into together in the plumbous liquid of melting, then stir 2 ~ 3min calcium aluminium element is mixed in plumbous liquid, in this process, keep the temperature of melt between 670 ~ 680 ℃;
(3) stop stirring and heating, add remaining lead button, melt is stirred, when temperature is down to 520 ~ 540 ℃, to melt, add tin and zinc, then stir 2 ~ 3min and make tin melt completely and mix with zinc;
(4) slag-cleaning agent is spread to bath surface, stir 1 ~ 2min, then scum silica frost is removed;
(5) when being down to 480 ~ 500 ℃, melt temperature casts.
The bits of calcium described in step (1), aluminium foil are all that diameter is the flap of 3 ~ 4mm.
By aspect of sheet lead parcel, be convenient reinforced, prevent that in addition calcium bits from contacting with oxygen, reduce calcium bits and be oxidized in air.
Described graphite market pot has vertical long semielliptical shape inner chamber.Conventionally market pot is square, calrod heating; Square lead pan has stirring dead angle, and intermediate frequency heating speed is fast simultaneously, efficiency is high, and heating has from agitating function simultaneously, like this can be so that the alloying constituent of allotting is more even.
Adopted after 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, has reduced to form under low temperature the impedance of anodic corrosion film.Zinc element can clearly improve the deep-circulating performance of battery, even under cold condition, because the cause of the good conductivity of PbZnO type oxide.
2, the present invention, in process for preparation, joins the calcium bits that mix in plumbous liquid with aluminium foil simultaneously, has removed the process of traditional preparation calcium aluminium mother alloy, so not only avoids a large amount of scaling loss of calcium, and enhances productivity, and has saved production cost.
3, the graphite market pot of the present invention's long semielliptical shape inner chamber used and the intermediate frequency furnace with automatic stirring function, these can make to allot the alloying constituent uniformity that comes, and have improved production efficiency.
Accompanying drawing explanation
Fig. 1 is example one and the impedance spectrum schematic diagram of example two alloys under 0.8V.By impedance spectrum, contrast discovery, the anonite membrane impedance that example two forms is much smaller than example one.
Embodiment
The applicant has submitted plumbous calcium tin aluminium positive grid alloy and preparation method thereof patent application on the same day to, 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, for the impact of convenient relatively zinc alloy low-temperature performance, therefore, the alloying element proportioning outside the embodiment of the present application 1-3 zinc remains unchanged.
Embodiment mono-
A dark circulation positive grid alloy preparation method for low temperature, is characterized in that comprising the following steps:
(1) raw material is prepared: 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 that accounts for leady raw materials total mass 85% is added in the graphite market pot of intermediate frequency furnace and be heated to 670 ~ 680 ℃, lead button is fully melted, with the sheet lead that accounts for leady raw materials total mass 0.5%, calcium bits and aluminium foil that parcel mixes, and be pressed into together in the plumbous liquid of melting, then stir 2 ~ 3min calcium aluminium element is mixed in plumbous liquid, in this process, keep the temperature of melt between 670 ~ 680 ℃;
(3) stop stirring and heating, add remaining lead button, melt is stirred, when temperature is down to 520 ~ 540 ℃, to melt, add tin and zinc, then stir 2 ~ 3min and make tin melt completely and mix with zinc;
(4) slag-cleaning agent is spread to bath surface, stir 1 ~ 2min, then scum silica frost is removed;
(5) when being down to 480 ~ 500 ℃, melt temperature casts.
Embodiment bis-
A dark circulation positive grid alloy preparation method for low temperature, is characterized in that comprising the following steps:
(1) raw material is prepared: 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 that accounts for leady raw materials total mass 85% is added in the graphite market pot of intermediate frequency furnace and be heated to 670 ~ 680 ℃, lead button is fully melted, with the sheet lead that accounts for leady raw materials total mass 0.5%, calcium bits and aluminium foil that parcel mixes, and be pressed into together in the plumbous liquid of melting, then stir 2 ~ 3min calcium aluminium element is mixed in plumbous liquid, in this process, keep the temperature of melt between 670 ~ 680 ℃;
(3) stop stirring and heating, add remaining lead button, melt is stirred, when temperature is down to 520 ~ 540 ℃, to melt, add tin and zinc, then stir 2 ~ 3min and make tin melt completely and mix with zinc;
(4) slag-cleaning agent is spread to bath surface, stir 1 ~ 2min, then scum silica frost is removed;
(5) when being down to 480 ~ 500 ℃, melt temperature casts.
Embodiment tri-
A dark circulation positive grid alloy preparation method for low temperature, is characterized in that comprising the following steps:
(1) raw material is prepared: 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 that accounts for leady raw materials total mass 85% is added in the graphite market pot of intermediate frequency furnace and be heated to 670 ~ 680 ℃, lead button is fully melted, with the sheet lead that accounts for leady raw materials total mass 0.5%, calcium bits and aluminium foil that parcel mixes, and be pressed into together in the plumbous liquid of melting, then stir 2 ~ 3min calcium aluminium element is mixed in plumbous liquid, in this process, keep the temperature of melt between 670 ~ 680 ℃;
(3) stop stirring and heating, add remaining lead button, melt is stirred, when temperature is down to 520 ~ 540 ℃, to melt, add tin and zinc, then stir 2 ~ 3min and make tin melt completely and mix with zinc;
(4) slag-cleaning agent is spread to bath surface, stir 1 ~ 2min, then scum silica frost is removed;
(5) when being down to 480 ~ 500 ℃, melt temperature casts.
Above-mentioned example one, example two alloy smears are assembled into the test of 12V12Ah experimental cell, the dark loop test system of low temperature is: the charging stage, store battery is in temperature is the environment of-15 ℃ ± 1 ℃, take single store battery average voltage as 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, is full of after electricity at store battery, in the environment of-15 ℃ ± 1 ℃, with 6A, discharges into when accumulator voltage reaches 10.50V and stops.Through dark loop test, find that the dark at low temperatures circulation volume of example one alloy cell is in 6Ah left and right, the dark at low temperatures circulation volume of example two alloy cell is in 10Ah left and right,
The interpolation of zinc has improved the low temperature deep-circulating performance of battery well.
Claims (5)
1. a dark circulation positive grid alloy for low temperature, is characterized in that being comprised 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.
2. dark circulation positive grid alloy for a kind of low temperature 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 dark circulation positive grid alloy for a kind of low temperature described in preparation claim 1 or 2, comprises the following steps: by the mass percent of above-mentioned raw materials,
(1) lead button that accounts 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 ℃, lead button is fully melted, with the sheet lead that accounts for leady raw materials total mass 0.5 ~ 1%, calcium bits and aluminium foil that parcel mixes, and be pressed into together in the plumbous liquid of melting, then stir 2 ~ 3min calcium aluminium element is mixed in plumbous liquid, in this process, keep the temperature of melt between 670 ~ 680 ℃;
(3) stop stirring and heating, add remaining lead button, melt is stirred, when temperature is down to 520 ~ 540 ℃, to melt, add tin and zinc, then stir 2 ~ 3min and make tin melt completely and mix with zinc;
(4) slag-cleaning agent is spread to bath surface, stir 1 ~ 2min, then scum silica frost is removed;
(5) when being down to 480 ~ 500 ℃, melt temperature casts.
4. the preparation method of dark circulation positive grid alloy for a kind of low temperature as claimed in claim 3, is characterized in that: the bits of calcium described in step (1), aluminium foil are all that diameter is the flap of 3 ~ 4mm.
5. the preparation method of dark circulation positive grid alloy for a kind of low temperature as claimed in claim 3, 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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| CN104073683A true CN104073683A (en) | 2014-10-01 |
| CN104073683B CN104073683B (en) | 2016-02-10 |
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| CN201410298050.2A Active 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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| WO (1) | WO2015196624A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015196624A1 (en) * | 2014-06-27 | 2015-12-30 | 天能集团江苏科技有限公司 | Gate alloy for low-temperature deep-cycle positive electrode plate, and preparation method therefor |
| CN107287470A (en) * | 2017-05-25 | 2017-10-24 | 天能电池集团有限公司 | A kind of lead accumulator grid alloy comprising nanometer tungsten carbide material and preparation method |
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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 |
| 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 |
| CN101656312A (en) * | 2009-07-08 | 2010-02-24 | 张天任 | Alloy material for high-energy accumulator grid and preparation method thereof |
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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 |
| 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 |
| 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 |
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- 2014-06-27 CN CN201410298050.2A patent/CN104073683B/en active Active
- 2014-10-11 WO PCT/CN2014/088342 patent/WO2015196624A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| US6210837B1 (en) * | 1998-05-23 | 2001-04-03 | Varta Batterie Aktiengesellschaft | Electrode grid for lead storage batteries |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2015196624A1 (en) * | 2014-06-27 | 2015-12-30 | 天能集团江苏科技有限公司 | Gate alloy for low-temperature deep-cycle positive electrode plate, and preparation method therefor |
| CN107287470A (en) * | 2017-05-25 | 2017-10-24 | 天能电池集团有限公司 | A kind of lead accumulator grid alloy comprising nanometer tungsten carbide material 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 |
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| Publication number | Publication date |
|---|---|
| WO2015196624A1 (en) | 2015-12-30 |
| CN104073683B (en) | 2016-02-10 |
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