CN106532063A - Multi-element lead-based grid alloy and production method thereof - Google Patents
Multi-element lead-based grid alloy and production method thereof Download PDFInfo
- Publication number
- CN106532063A CN106532063A CN201610806944.7A CN201610806944A CN106532063A CN 106532063 A CN106532063 A CN 106532063A CN 201610806944 A CN201610806944 A CN 201610806944A CN 106532063 A CN106532063 A CN 106532063A
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- Prior art keywords
- lead
- alloy
- strontium
- indium
- sodium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/68—Selection of materials for use in lead-acid accumulators
- H01M4/685—Lead alloys
-
- 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
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/73—Grids for lead-acid accumulators, e.g. frame plates
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention relates to a multi-element lead-based grid alloy and a production method thereof. The multi-element lead-based grid alloy comprises the following components: 0.01%-0.05% of sodium, 0.02%-0.05% of aluminum, 0.6%-0.9% of tin, 0.02%-0.05% of indium, 0.02%-0.05% of strontium and the balance of lead and inevitable impurities. The multi-element lead-based grid alloy provided by the invention does not contain a calcium element, a traditional lead-calcium alloy is replaced and the problem that a passivation film with poor conductivity in an anode is generated by the combined surface of a positive grid of a lead-acid storage battery produced by the lead-calcium alloy and lead paste in a chemical reaction process is solved. Meanwhile, the content of the tin is reduced and the production cost is directly reduced. The corrosion resistance of the grid alloy is effectively improved through addition of multiple elements of the sodium, the aluminum, the tin, the indium, the strontium and the like, generation of the passivation film with poor conductivity in a pole plate is suppressed, the ductility and the casting property of the alloy are effectively improved, the initial capacity cycle performance of the storage battery is greatly improved and the service life of the storage battery is prolonged.
Description
Technical field
A kind of the present invention relates to polynary lead base grid alloy that with the addition of sodium aluminium, tin and indium strontium, and its production method.
Background technology
At present lead-containing alloy is had been widely used in maintenance-free lead accumulator industrial production, several conventional non-maintaining
Metal has a common ground, all contains mostly metal calcium constituent, due to the presence of calcium, when making lead series alloy anodic oxidation
The anodic attack layer of high impedance is easily formed, that is, defines the passivating film of one layer of poorly conductive, affect the cycle charge-discharge of battery
Ability.In order to improve the conductivity problems of passivating film, many people introduce the additives such as rare earth, silver in grid alloy in recent years, it
Can reduce passivating film impedance and improve grid alloy rotproofness, but production cost is higher.
The content of the invention
The invention aims to provide a kind of generation of the passivating film for suppressing poorly conductive in pole plate, effectively increase
The polynary lead base grid alloy of the elongation percentage and casting properties of alloy.
The present invention also aims to provide the production method of above-mentioned polynary lead base grid alloy.
Technical program of the present invention lies in：Polynary lead base grid alloy, its composition include (wt%)：Sodium 0.01-0.05%,
Aluminium 0.02-0.05%, tin 0.6-0.9%, indium 0.02-0.05%, strontium 0.02-0.05%, lead surplus and inevitable impurity.
Production method of the present invention is：Load weighted lead pig is put into into testing furnace, 350～380 DEG C are warming up to, melts lead
Change, allocate reducing agent slag making into, after dragging for surface reduction slag, after being warmed up to 450-500 DEG C, the air-breather opened on Electric furnace casing is past
Nitrogen is passed through in stove, while adding metering sodium, is stirred 5-10min, is continuously heating to 650-700 DEG C, then stirs 3-5min, casts
Ingot, obtains sodium foundry alloy；
Load weighted lead pig is put into into testing furnace, 350～380 DEG C is warming up to, is melted lead, allocate reducing agent slag making into, drag for
After surface reduction slag is warmed up to 450-500 DEG C after weighing, the air-breather opened on testing furnace cover is passed through nitrogen toward in stove, together
When add metering indium, stir 5-10min, be continuously heating to 650-700 DEG C, then stir 3-5min, ingot casting obtains that indium is female to be closed
Gold；
Load weighted lead pig is put into into testing furnace, 350～380 DEG C is warming up to, is melted lead, allocate reducing agent slag making into, drag for
After surface reduction slag is warmed up to 600-650 DEG C after weighing, the air-breather opened on testing furnace cover is passed through nitrogen toward in stove, together
When add metering strontium, stir 5-10min, be continuously heating to 800-850 DEG C, then stir 3-5min, ingot casting obtains that strontium is female to be closed
Gold；
Load weighted lead pig is all added in lead pan and is warmed up to 350～380 DEG C, melted lead, allocate reducing agent slag making into, drag for
Surface reduction slag is warmed up to 650-700 DEG C after weighing, and sequentially adds aluminium, the tin of weighing, stirs 5-10min, is cooled to 520-550
Configured good sodium foundry alloy is sequentially added after DEG C, and indium foundry alloy, strontium foundry alloy, stirring 10-15min are allowed to be sufficiently mixed
It is even, quantitative coverture is eventually adding, sample examination detection reaches ingot casting after standard is required.
Reducing agent of the present invention is rosin, caustic soda or carbon, and consumption is 60T lead 5-10Kg reducing agents.
Coverture of the present invention is carbon dust, compares carbon dust according to weight:Lead=0.25：1000 ratio is added.
It is 2 tons of lead 10-15L nitrogen that the present invention is passed through the amount of nitrogen into stove, and the time is 15-20min.Present invention step
Nitrogen is passed through in testing furnace in rapid, in order to prevent element oxide scaling loss, improves element utilization rate；
The formula of the present invention adds aluminium form a kind of diaphragm, protects other elements not oxidized；The sodium of addition is effectively carried
The elongation percentage and casting properties of high alloy；The generation of the indium of addition, strontium to the passivating film of poorly conductive in suppression positive plate, makes
The initial capacity cycle performance of battery is very significantly improved, and strengthens the service life of battery, while reduce producing into
This.
The polynary lead base grid alloy of the present invention does not contain calcium constituent, instead of traditional lead-calcium alloy, solves and is closed with lead calcium
The positive grid of lead-acid accumulator and lead plaster faying face of gold production produces the poor conductive passivating film of anode in chemical reaction process
Problem.The content of tin is reduced simultaneously, directly reduces production cost.The addition of the multiple elements such as sodium, aluminium, tin, indium, strontium is effectively carried
The high corrosion resistance of grid alloy, suppresses the generation of the passivating film of poorly conductive in pole plate, effectively increases the extension of alloy
Rate and casting properties, are very significantly improved the initial capacity cycle performance of battery, strengthen the service life of battery.
" calcium effect " that the present invention will be solved or reduction is now occurred using process in battery with lead-calcium alloy, extending battery makes
Use the life-span.And manufacturing cost will not increase or even can also reduce on original cost basis.It will become the main flow of metal --
Without antimony without calcium composite alloy, with wide market scene and huge Social benefit and economic benefit.
Specific embodiment
Embodiment：3 tons of 1# lead pigs are weighed first（Divide three parts, 1 ton per part）, 10Kg sodium, 10Kg indiums, 10Kg strontium metals it is stand-by,
1 ton of 1# lead pig is put into into testing furnace, is had refractory lining inside the testing furnace, is electric furnace between liner and outer furnace wall
Silk.380 DEG C are warming up to, melt lead, allocate reducing agent slag making into, dragged for after 480 DEG C being warmed up to after surface reduction slag is weighed, open
Air-breather on testing furnace cover is passed through nitrogen toward in stove, while adding the sodium of 20Kg, stirs 10min, is continuously heating to 680
DEG C, 5min is then stirred, sampling detection, the content of sodium reach ingot casting after 1.5-2%, obtain can be used for the sodium of next step test
Foundry alloy.
By another 1 ton of 1# lead pigs input testing furnace, 380 DEG C are warming up to, melt lead, allocated reducing agent slag making into, drag for
Surface reduction slag is warmed up to 480 DEG C after weighing after, the air-breather opened on testing furnace cover is passed through nitrogen toward in stove, while plus
Enter the indium of 20Kg, stir 10min, be continuously heating to 680 DEG C, then stir 5min, sampling detection, the content of indium reach 1.5-2%
Ingot casting, obtains can be used for the indium foundry alloy of next step test afterwards.
By last 1 ton of 1# lead pigs input testing furnace, 380 DEG C are warming up to, melt lead, allocated reducing agent slag making into, drag for
After going surface reduction slag to be warmed up to 630 DEG C after weighing, the air-breather opened on testing furnace cover is passed through nitrogen toward in stove, while
The strontium of 20Kg is added, 10min is stirred, is continuously heating to 830 DEG C, then stir 5min, sampling detection, the content of strontium reach 1.5-
Ingot casting after 2%, obtains can be used for the strontium foundry alloy of next step test.
Then 30 tons of 1# lead pigs are weighed, load weighted 1# lead pigs is all added in lead pan and is warmed up to 370 DEG C, melted lead, match somebody with somebody
Enter reducing agent slag making, drag for after surface reduction slag is weighed and be warmed up to 680 DEG C, sequentially add aluminium, the 240Kg tin of 12Kg, stir
10min, sequentially adds configured good sodium foundry alloy 450Kg, indium foundry alloy 600Kg, strontium foundry alloy after being cooled to 530 DEG C
600Kg, stirring 15min are allowed to be sufficiently mixed uniformly, are eventually adding 7.5Kg covertures, and sample examination detection reaches standard formula
Ingot casting after content requirement.
Claims (5)
1. a kind of polynary lead base grid alloy, it is characterised in that its composition includes (wt%)：Sodium 0.01-0.05%, aluminium 0.02-
0.05%, tin 0.6-0.9%, indium 0.02-0.05%, strontium 0.02-0.05%, lead surplus and inevitable impurity.
2. the production method of polynary lead base grid alloy described in a kind of claim 1, it is characterised in that：According to claim 1 institute
Alloying component dispensing is stated, load weighted lead pig is put into into testing furnace, 350～380 DEG C is warming up to, is melted lead, allocate reduction into
Agent slag making, after dragging for surface reduction slag, after being warmed up to 450-500 DEG C, the air-breather opened on Electric furnace casing is passed through nitrogen toward in stove
Gas, while adding metering sodium, stirs 5-10min, is continuously heating to 650-700 DEG C, then stirs 3-5min, and ingot casting obtains sodium
Foundry alloy；
Load weighted lead pig is put into into testing furnace, 350～380 DEG C is warming up to, is melted lead, allocate reducing agent slag making into, drag for
After surface reduction slag is warmed up to 450-500 DEG C after weighing, the air-breather opened on testing furnace cover is passed through nitrogen toward in stove, together
When add metering indium, stir 5-10min, be continuously heating to 650-700 DEG C, then stir 3-5min, ingot casting obtains that indium is female to be closed
Gold；
Load weighted lead pig is put into into testing furnace, 350～380 DEG C is warming up to, is melted lead, allocate reducing agent slag making into, drag for
After surface reduction slag is warmed up to 600-650 DEG C after weighing, the air-breather opened on testing furnace cover is passed through nitrogen toward in stove, together
When add metering strontium, stir 5-10min, be continuously heating to 800-850 DEG C, then stir 3-5min, ingot casting obtains that strontium is female to be closed
Gold；
Load weighted lead pig is all added in lead pan and is warmed up to 350～380 DEG C, melted lead, allocate reducing agent slag making into, drag for
Surface reduction slag is warmed up to 650-700 DEG C after weighing, and sequentially adds aluminium, the tin of weighing, stirs 5-10min, is cooled to 520-550
Configured good sodium foundry alloy is sequentially added after DEG C, and indium foundry alloy, strontium foundry alloy, stirring 10-15min are allowed to be sufficiently mixed
It is even, quantitative coverture is eventually adding, sample examination detection reaches ingot casting after standard is required.
3. the production method of polynary lead base grid alloy according to claim 2, it is characterised in that：The reducing agent is pine
Fragrant, caustic soda or carbon, consumption are 60T lead 5-10Kg reducing agents.
4. the production method of polynary lead base grid alloy according to claim 1, it is characterised in that：The coverture is carbon
Powder, compares carbon dust according to weight:Lead=0.25：1000 ratio is added.
5. the production method of polynary lead base grid alloy according to claim 1, it is characterised in that：Nitrogen is passed through into stove
Measure as 2 tons of lead 10-15L nitrogen, the time is 15-20min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610806944.7A CN106532063A (en) | 2016-09-07 | 2016-09-07 | Multi-element lead-based grid alloy and production method thereof |
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|---|---|---|---|
| CN201610806944.7A CN106532063A (en) | 2016-09-07 | 2016-09-07 | Multi-element lead-based grid alloy and production method thereof |
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| CN106532063A true CN106532063A (en) | 2017-03-22 |
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| CN201610806944.7A Pending CN106532063A (en) | 2016-09-07 | 2016-09-07 | Multi-element lead-based grid alloy and production method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109913687A (en) * | 2019-02-24 | 2019-06-21 | 贵州省过程工业技术研究中心 | A kind of application of carbon dust in the preparation of quaternary alloy anode plate |
| CN116287858A (en) * | 2023-03-30 | 2023-06-23 | 巨江电源科技有限公司 | Lead-based barium sodium aluminum alloy for negative grid of lead-acid storage battery, and preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109913687A (en) * | 2019-02-24 | 2019-06-21 | 贵州省过程工业技术研究中心 | A kind of application of carbon dust in the preparation of quaternary alloy anode plate |
| CN116287858A (en) * | 2023-03-30 | 2023-06-23 | 巨江电源科技有限公司 | Lead-based barium sodium aluminum alloy for negative grid of lead-acid storage battery, and preparation method and application thereof |
| CN116287858B (en) * | 2023-03-30 | 2023-11-28 | 巨江电源科技有限公司 | Lead-based barium sodium aluminum alloy for negative grid of lead-acid storage battery, and preparation method and application thereof |
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Application publication date: 20170322 |