CN108754228A - A kind of accumulator plate grid alloy and its production method with rare earth element - Google Patents
A kind of accumulator plate grid alloy and its production method with rare earth element Download PDFInfo
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- CN108754228A CN108754228A CN201810870610.5A CN201810870610A CN108754228A CN 108754228 A CN108754228 A CN 108754228A CN 201810870610 A CN201810870610 A CN 201810870610A CN 108754228 A CN108754228 A CN 108754228A
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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
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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
-
- 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
-
- 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 discloses a kind of accumulator plate grid alloys with rare earth element, include following components by weight percentage：Ca0.05-0.25%, La0.001-0.002%, Yb0.001-0.015%, Ce0.018-0.036%, Sm0.001-0.002%, Nd0.02-0.05%, Al0.035-0.055%, Ag0.015-0.025%, Zn0.1-0.2%, S0.01-0.05%, surplus Pb.Present invention improves lead-acid battery grid alloy performances, reduce battery dehydration, improve the maintenance-free performance of battery, while enhancing alloy corrosion resistance energy.The fault of construction caused by impurity is also reduced, to enhance the plasticity and toughness of alloy, while improving the creep-resistant property and corrosion resistance of alloy.
Description
Technical field
The present invention specifically a kind of accumulator plate grid alloy and its production method with rare earth element, belong to lead accumulator
Technical field.
Background technology
With the development of science and technology and the continuous development of New Energy Industry, Environmental protection and resource rational utilization
Continuous attention, the requirement to accumulator is also higher and higher, pursues the high-performance of accumulator, improve accumulator corrosion resistance,
Deeper cavity and charge acceptance etc., wherein grid alloy play critically important effect in accumulator.
Grid is the important component of lead-acid accumulator, mainly plays support active material, conducts electric current and uniformly
The effect of distributed current chemically reacts at stream although not participating in battery, has for battery charging and discharging performance and cycle life
Highly important influence.Currently, lead acid accumulator plate grid material is mainly lead-antimony alloy and lead-calcium alloy two major classes, but this two class
Deficiency is individually present in alloy.Lead-antimony alloy overpotential of hydrogen evolution is relatively low, and battery gassing and dehydration are serious, and maintenance-free performance is poor.
And lead-calcium alloy then has that creep-resistant property and deep discharge cycle performance are poor.So, a kind of tool how is developed
There is the technical issues of good non-maintaining, deep discharge and the strong grid alloy of corrosion resistance become current urgent need to resolve.
Invention content
For above-mentioned background technology there are the problem of, the present invention provides a kind of accumulator plate grid alloy and its production method,
Accumulator corrosion resistance, deep discharge cyclicity, maintenance-free and charge acceptance etc. can be improved, making for accumulator is extended
Use the service life.
To achieve the goals above, a kind of accumulator plate grid alloy with rare earth element of the present invention, is wrapped in parts by weight
Include following components：Ca 0.05-0.25%, La 0.001-0.002%, Yb 0.001-0.015%, Ce 0.018-0.036%,
Sm 0.001-0.002%, Nd 0.02-0.05%, Al 0.035-0.055%, Ag 0.015-0.025%, Zn 0.1-
0.2%, S 0.01-0.05%, surplus Pb.
A kind of accumulator plate grid alloy with rare earth element includes following components in parts by weight：Ca 0.15%, La
0.015%, Yb 0.008%, Ce 0.027%, Sm 0.015%, Nd 0.035%, Ag 0.02%, Zn 0.15%, S
0.035%, surplus Pb.
A kind of production method of the accumulator plate grid alloy with rare earth element, includes the following steps：
1) raw material is weighed according to aforementioned proportion；
2) lead is put into vacuum high-pressure smelting furnace and is heated to 1300-1350 DEG C, be fused into lead night, vacuum degree 0.1-
0.3Pa, heating time 20-25min；
3) metal Zn is added in the lead liquid of 70%-80%, continues to be heated to 800-900 DEG C, stirs evenly, be made and close
Golden liquid Zn-Pb；
4) residual lead liquid 30-40% is transferred to lead melting furnace and continues to heat up, and when temperature rises to 1000-1200 DEG C, sequentially adds
La, Yb, Ce, and stir evenly, so that metal is completely melt, rare earth element alloy liquid is made；
5) the remaining lead liquid of residual lead liquid transfers to another lead melting furnace in step (4), and temperature is controlled in 1200-1300
DEG C, Sm, Nd are sequentially added, and stir evenly, metal is made all to melt, another rare earth element alloy liquid is made；
6) aluminium alloy made from step (3), (4), (5) is mixed into high pressure smelting furnace, makes temperature control in 1200-
It 1250 DEG C, is stirred, Al, Ag is added in whipping process, until stirring evenly, casting is cooled and shaped；
Preferably, La is first added in the step (4), and after stirring 15-20min, Yb is added, is stirred for 5-6min, Ce is added,
Continue to stir 20-25min.
Preferably, Sm is first added in the step (5), after stirring 10-20min, Nd is added, is stirred for 5-9min.
Preferably, Al is first added in the step (6), adds Ag after stirring 5-6min, is then stirred for 10-15min.
Compared with prior art, present invention improves lead-acid battery grid alloy performances, improve alloy synthesis mechanical property
Energy and alloy liberation of hydrogen and overpotential for oxygen evolution, reduce hydrogen and oxygen evolution reaction rate, to reduce battery dehydration,
Improve the maintenance-free performance of battery, while enhancing alloy corrosion resistance energy, reduces alloy anodized film resistance.Another party
Face, La, Yb, Ce element have very strong chemism, can generate high melting compound with the element reactions such as carbon, hydrogen, oxygen, sulphur,
Play the role of eliminating impurity, purification alloy structure, reduces the fault of construction caused by impurity, to enhance alloy
Plasticity and toughness improve the creep-resistant property of alloy.Rare earth element addition is it is also possible that lead alloy surface forms one layer of cause
Close protective oxide layer enhances alloy corrosion resistance energy.
Specific implementation mode
With reference to embodiment, the invention will be further described.
Embodiment 1：
A kind of accumulator plate grid alloy with rare earth element of the present invention, total weight 100kg, concrete component are as follows：
Ca 5kg, La 0.1kg, Yb 0.1kg, Ce 1.8kg, Sm 0.1kg, Nd 2kg, Al 3.5kg, Ag 1.5kg,
Zn 10kg, S 1kg, surplus Pb.
A kind of production method of the accumulator plate grid alloy with rare earth element, includes the following steps：
1) raw material is weighed according to aforementioned proportion；
2) lead is put into vacuum high-pressure smelting furnace and is heated to 1300 DEG C, be fused into lead night, vacuum degree 0.3Pa, heating
Time is 20-25min；
3) metal Zn is added in 70% lead liquid, continues to be heated to 900 DEG C, stirs evenly, aluminium alloy Zn- is made
Pb；
4) residual lead liquid 30% is transferred to lead melting furnace and continues to heat up, and when 1200 DEG C of temperature liter, La is first added, stirs 15min
Afterwards, Yb is added, is stirred for 5min, Ce is added, continues to stir 20min, rare earth element alloy liquid is made；
5) the remaining lead liquid of residual lead liquid transfers to another lead melting furnace in step (4), temperature is controlled at 1300 DEG C, first
Sm is added, after stirring 10min, Nd is added, is stirred for 5min.Another rare earth element alloy liquid is made；
6) aluminium alloy made from step (3), (4), (5) is mixed into high pressure smelting furnace, temperature is made to control 1250 DEG C, into
Row stirs, and Al, Ag are added in whipping process, and Al is first added, and Ag is added after stirring 6min, is then stirred for 10-min until stirring
It mixes uniformly, casting is cooled and shaped；
Embodiment 2：
A kind of accumulator plate grid alloy with rare earth element of the present invention, total weight 100kg, concrete component are as follows：
Ca 15kg, La 1.5kg, Yb 0.8kg, Ce 2.7kg, Sm 1.5kg, Nd 3.5kg, Al 4.5kg, Ag 2kg,
Zn 15kg, S 3.5kg, surplus Pb.
A kind of production method of the accumulator plate grid alloy with rare earth element, includes the following steps：
1) raw material is weighed according to aforementioned proportion；
2) lead is put into vacuum high-pressure smelting furnace and is heated to 1325 DEG C, be fused into lead night, vacuum degree 0.2Pa, heating
Time is 23min；
3) metal Zn is added in 75% lead liquid, continues to be heated to 850 DEG C, stirs evenly, aluminium alloy Zn- is made
Pb；
4) residual lead liquid 35% is transferred to lead melting furnace and continues to heat up, and when temperature rises to 1150 DEG C, La is first added, and stirs
After 17min, Yb is added, is stirred for 5.5min, Ce is added, continues to stir 23min.And stir evenly, so that metal is completely melt, makes
Obtain rare earth element alloy liquid；
5) the remaining lead liquid of residual lead liquid transfers to another lead melting furnace in step (4), temperature is controlled at 1250 DEG C, first
Sm is added, after stirring 15min, Nd is added, is stirred for 7min and another rare earth element alloy liquid is made；
6) aluminium alloy made from step (3), (4), (5) is mixed into high pressure smelting furnace, makes temperature control at 1225 DEG C,
It is stirred, Al, Ag is added in whipping process, Al is first added, add Ag after stirring 5.5min, be then stirred for 13min.Directly
To stirring evenly, casting is cooled and shaped.
Embodiment 3：
A kind of accumulator plate grid alloy with rare earth element of the present invention, total weight 100kg, concrete component are as follows：
Ca 25kg, La 0.2kg, Yb 1.5kg, Ce 3.6kg, Sm 0.2kg, Nd 5kg, Al 5.5kg, Ag 2.5kg,
Zn 20kg, S 5k surpluses are Pb.
A kind of production method of the accumulator plate grid alloy with rare earth element, includes the following steps：
1) raw material is weighed according to aforementioned proportion；
2) lead is put into vacuum high-pressure smelting furnace and is heated to 1350 DEG C, be fused into lead night, vacuum degree 0.1Pa, heating
Time is 20min；
3) metal Zn is added in 80% lead liquid, continues to be heated to 900 DEG C, stirs evenly, aluminium alloy Zn- is made
Pb；
4) residual lead liquid 40% is transferred to lead melting furnace and continues to heat up, and when temperature rises to 1200 DEG C, La is first added, and stirs
After 15min, Yb is added, is stirred for 6min, Ce is added, continues to stir 25min, rare earth element alloy liquid is made；
5) the remaining lead liquid of residual lead liquid transfers to another lead melting furnace in step (4), temperature is controlled at 1300 DEG C, first
Sm is added, after stirring 10min, Nd is added, is stirred for 5min, another rare earth element alloy liquid is made；
6) aluminium alloy made from step (3), (4), (5) is mixed into high pressure smelting furnace, temperature is made to control 1250 DEG C, into
Row stirs, and Al, Ag are added in whipping process, and Al is first added, and adds Ag after stirring 5min, is then stirred for 10min.Until stirring
It mixes uniformly, casting is cooled and shaped；
Lead accumulator grid of the present invention is tested as follows：
1. corrosion resistance：The anode of external power is connected with Electrode, abdominal muscle is using two conventional lead-calcium alloy positive plates
Grid are used as to electrode, and the corrosion resistance of alloy grid is detected after continuing 300h using 2.5A constant-current charges；
2. creep resistance：With alloy anode, platinum electrode is abdominal muscle, carries out three-electrode system lower linear electric potential scanning, works as electricity
When electrode potential is 1.50V (vs.Hg/Hg2S04), the analysis oxygen current density of alloy is detected：
3. hardness test：After 5 days timeliness of alloy, using the test force of 0.01kg, retention time 30S or more detects Vickers
Hardness number.
The results are shown in Table 1, and alloy made from above-described embodiment is in terms of timeliness hardness, creep-resistant property, corrosion resistance
Data.
It can be obtained by table 1, the grid alloy that embodiment 1 is prepared to embodiment 3, corrosion resistance, resists maintenance-free performance
Croop property and service life are significantly improved.
Claims (6)
1. a kind of accumulator plate grid alloy with rare earth element, which is characterized in that include following components in parts by weight：Ca
0.05-0.25%, La 0.001-0.002%, Yb 0.001-0.015%, Ce 0.018-0.036%, Sm 0.001-
0.002%, Nd 0.02-0.05%, Al 0.035-0.055%, Ag 0.015-0.025%, Zn 0.1-0.2%, S 0.01-
0.05%, surplus Pb.
2. a kind of accumulator plate grid alloy with rare earth element according to claim 1, which is characterized in that by weight
Number includes following components：Ca 0.15%, La 0.015%, Yb 0.008%, Ce 0.027%, Sm 0.015%, Nd
0.035%, Ag 0.02%, Zn 0.15%, S 0.035%, surplus Pb.
3. a kind of production method of the accumulator plate grid alloy with rare earth element as described in claim 1, which is characterized in that
Include the following steps：
1) raw material is weighed according to aforementioned proportion；
2) lead is put into vacuum high-pressure smelting furnace and is heated to 1300-1350 DEG C, be fused into lead night, vacuum degree 0.1-0.3Pa,
Heating time is 20-25min；
3) metal Zn is added in the lead liquid of 70%-80%, continues to be heated to 800-900 DEG C, stirs evenly, aluminium alloy is made
Zn-Pb；
4) residual lead liquid 30-40% is transferred to lead melting furnace and continues to heat up, when temperature rises to 1000-1200 DEG C, sequentially add La,
Yb, Ce, and stir evenly, so that metal is completely melt, rare earth element alloy liquid is made；
5) the remaining lead liquid of residual lead liquid transfers to another lead melting furnace in step (4), and temperature is controlled at 1200-1300 DEG C,
Sm, Nd are sequentially added, and is stirred evenly, metal is made all to melt, another rare earth element alloy liquid is made；
6) aluminium alloy made from step (3), (4), (5) is mixed into high pressure smelting furnace, makes temperature control in 1200-1250
DEG C, it is stirred, Al, Ag is added in whipping process, until stirring evenly, casting is cooled and shaped.
4. a kind of accumulator plate grid alloy production method with rare earth element according to claim 3, which is characterized in that
La is first added in the step (4), and after stirring 15-20min, Yb is added, is stirred for 5-6min, Ce is added, and continues to stir 20-
25min。
5. a kind of production method of accumulator plate grid alloy with rare earth element according to claim 3, feature exist
In Sm is first added in the step (5), after stirring 10-20min, Nd is added, is stirred for 5-9min.
6. a kind of production method of accumulator plate grid alloy with rare earth element according to claim 3, feature exist
In being first added Al in the step (6), add Ag after stirring 5-6min, be then stirred for 10-15min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076058A (en) * | 1992-02-29 | 1993-09-08 | 山东省文登市密闭蓄电池厂 | Positive and negative plate grid alloy material for sealed lead-acid accumulator |
| CN1393948A (en) * | 2001-06-22 | 2003-01-29 | 浙江南都电源动力股份有限公司 | Alloy material used to make plate lattice of accumulator |
| CN101656312A (en) * | 2009-07-08 | 2010-02-24 | 张天任 | Alloy material for high-energy accumulator grid and preparation method thereof |
| US20140376352A1 (en) * | 2013-06-24 | 2014-12-25 | Seagate Technology Llc | Materials for near field transducers, near field tranducers containing same, and methods of forming |
-
2018
- 2018-08-02 CN CN201810870610.5A patent/CN108754228A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076058A (en) * | 1992-02-29 | 1993-09-08 | 山东省文登市密闭蓄电池厂 | Positive and negative plate grid alloy material for sealed lead-acid accumulator |
| CN1393948A (en) * | 2001-06-22 | 2003-01-29 | 浙江南都电源动力股份有限公司 | Alloy material used to make plate lattice of accumulator |
| CN101656312A (en) * | 2009-07-08 | 2010-02-24 | 张天任 | Alloy material for high-energy accumulator grid and preparation method thereof |
| US20140376352A1 (en) * | 2013-06-24 | 2014-12-25 | Seagate Technology Llc | Materials for near field transducers, near field tranducers containing same, and methods of forming |
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Application publication date: 20181106 |