CN101685863A - Rare-earth alloy lead plate grid material for accumulator - Google Patents
Rare-earth alloy lead plate grid material for accumulator Download PDFInfo
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- CN101685863A CN101685863A CN200810200752A CN200810200752A CN101685863A CN 101685863 A CN101685863 A CN 101685863A CN 200810200752 A CN200810200752 A CN 200810200752A CN 200810200752 A CN200810200752 A CN 200810200752A CN 101685863 A CN101685863 A CN 101685863A
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- accumulator
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- 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
Abstract
The invention provides a rare-earth alloy lead plate grid material for an accumulator. The plate grid material comprises the following chemical components: 0.06-0.08wt% of Ca, 0.01-0.02wt% of Al, 0.1-1.3wt% of Sn, 0.04-0.06wt% of Bi, 0.002-0.25wt% of RE and the balance Pb, wherein the RE can be selected from one to three of La, Ce and Sm. The plate grid material has superior corrosion-resisting properties and can be widely used for the batteries of an electrically-operated car, an automobile, a UPS, solar energy, wind energy, energy storage and the like, the accumulator manufactured by the plate grid material is environment-friendly, green and pollution-free and is suitable for deep circulation charge and discharge, and the service life of the accumulator is greatly prolonged.
Description
Technical field
The present invention relates to field of alloy material, specifically, the present invention relates to a kind of rare-earth alloy lead plate grid material that is used for storage battery.
Background technology
The development of the reform of industrial structure, environmental protection, utilization of resources and resource regeneration etc.; lead acid accumulator many new requirements have been proposed; to this; countries in the world are all at the high performance battery of research and development; solve the reliability of lead acid accumulator, non-maintaining property, dark circulation, problem such as corrosion-resistant; grid more plays an important role in the research process of storage battery as the main part of storage battery.
Grid is the nonactive parts of lead acid accumulator most critical, and it has two big functions in storage battery: the one, support positive negative active material, and the 2nd, between discharge and charge period, serve as collector, this alloy that just requires to make grid must have good performance.At present, the anode plate for lead acid accumulator grid material adopts plumbous antimony or lead-calcium alloy mostly.
Lead-antimony alloy mechanical strength height, casting character are good, with its storage battery of making, using, especially when charging, antimony will be dissolved into the solution from positive plate, deposits on the negative electrode active material, along with the increase of antimony content in the anode plate grid and cycle-index, the antimony amount that accumulates on the negative electrode active material increases, and H
+Discharge has a lower overpotential on antimony, the existence of antimony can make storage battery overcharge, hydrogen-separating quantity increases when storing.In addition, a part of antimony is adsorbed on the positive active material, has reduced the overpotential that oxygen is separated out at positive pole, and the decomposition voltage of water is descended, and the water capacity is easily decomposed during charging, has quickened self discharge when depositing.Use the storage battery of lead-antimony alloy grid can't make sealed type, need often in electrolyte, add water, to replenish the moisture that loses because of charging and self discharge.When overcharging, toxic gas SbH also can overflow
3, and the anode plate grid corrosion rate can increase with the increase of antimony content.
The main advantage of lead-calcium alloy is exactly that its overpotential of hydrogen evolution is approximately than the high about 200mV of lead-antimony alloy, thereby suppressed effectively battery self discharge and when charging negative pole hydrogen-separating quantity, has maintenance-free performance preferably, and the conductive capability of lead-calcium alloy is better than lead-antimony alloy, its cryogenic property also obviously is better than lead-antimony alloy, but in charging process, very easily the grow high-resistance anodic attack layer of one deck and serious intercrystalline corrosion takes place of its anode plate grid surface, greatly having influenced battery thus fills deeply, put performance, shortened the useful life of battery, as according to the Shanghai provincial standard, the cycle life of lead-acid accumulator for electric bicycle will reach 350 times, the shortcoming of lead-calcium alloy just seems particularly outstanding like this, mainly show the anode plate grid material of uncomfortable cooperation deep discharge circulating storage battery, it is relatively poor to fill ability to accept again, and early stage capacitance loss easily takes place, promptly so-called no antimony effect.
For overcoming this shortcoming, add the tin of high-load usually in the alloy simultaneously, this alloy has obtained using widely on maintenance-free lead accumulator at valve-control sealed lead acid battery and automobile.Add the volume ratio that tin can increase by the second phase particle a little in lead-calcium alloy, calcium, tin are with (PbSn)
3Ca or Sn
3The form of Ca precipitation is distributed in the lead base body, because it compares Pb
3The stability of Ca is high, thereby lead alloy is strengthened.The corrosion rate of alloy reduces with the increase of tin content, but tin content can increase alloy grain size and the unnecessary tin grain boundary of can emanating when high, makes alloy be subjected to serious intercrystalline corrosion.
Shortcoming at above-mentioned alloy material existence, domestic researcher begins to study to the rare earth lead acid accumulator, find that the adding of rare earth helps improving tensile strength, hardness, decay resistance and the overpotential of hydrogen evolution of battery lead plate lead-containing alloy, add rare earth in the active component and can reduce the anodal hydrogen amount of separating out, improve the utilance of positive active material, thus the performance and the useful life of improving storage battery.Chinese patent CN1221991 has reported a kind of preparation method of high specific energy lead-acid battery for electric vehicle, and its anode plate grid adopts the lead-containing alloy material that contains 0.01～1.0%Ag or Ce or La.The extended life seal lead acid accumulator that CN1309434 introduces, plate railings of anode and cathode all adopts the lead-calcium alloy material, and has comprised 0.005～0.12%RE, and employed RE kind is more, has increased cost of material.The disclosed a kind of Deep Cycle Grid Alloy Used for Lead-Acid Battery Positive prescription of CN1476118, it is characterized in that adding in the Pb-Ca-Sn-Al alloy rare earth metals such as metallic yttrium and metallic cerium, yttrium content 0.06%～1.2%, cerium content 0.06%～0.15%, by in Pb-Ca-Sn-Al alloy, adding the crystal structure that rare earth metals such as yttrium and cerium change grid alloy, corrosion resistance, conductivity and the electrochemical stability of electrode plate grid have been strengthened, thereby the dark cycle life of lead acid accumulator is obviously improved, but the content of rare earth of its adding is also more, has increased cost of material.Also there is patent to relate to the research of rare earth lead acid accumulator abroad, the disclosed lead acid accumulator plate grid of JP2003221633, by in the Pb-Ca-Sn-Al alloy, adding a certain amount of Ce, obtain decay resistance and mechanical strength preferably, the lead acid accumulator that US6180286 and US5874186 introduce, add norium in its preferred positive plate lead-containing alloy, contain 50%Ce in the mishmetal, 15～30%La, all the other are other various rare earth elements, but their preparation technology is comparatively complicated, has increased production cost.
Consider that storage battery not only should have long useful life, and should be easy to produce, with low cost, the inventor is by studying for a long period of time, designed a kind of novel grid material---rare earth alloy lead, functional with the accumulator cell charging and discharging that this grid material is made, prolong the useful life of storage battery, thereby finished the present invention.
The object of the present invention is to provide a kind of storage battery rare-earth alloy lead plate grid material.
Summary of the invention
The invention provides a kind of storage battery rare-earth alloy lead plate grid material, the chemical composition of described grid material comprises: Ca (calcium): 0.06～0.08wt%, Al (aluminium): 0.01～0.02wt%, Sn (tin): 0.1～1.3wt%, Bi (bismuth): 0.04～0.06wt%, RE (rare earth element): 0.002～0.25wt%, surplus is Pb (lead).
According to storage battery rare-earth alloy lead plate grid material of the present invention, described Pb is the lead bullion of purity more than 99.97%.
According to storage battery rare-earth alloy lead plate grid material of the present invention, described RE is selected from a kind of among La (lanthanum), Ce (cerium) and the Sm (samarium).
According to storage battery rare-earth alloy lead plate grid material of the present invention, described RE is selected from any two kinds among La (lanthanum), Ce (cerium) and the Sm (samarium).
According to storage battery rare-earth alloy lead plate grid material of the present invention, described RE is La (lanthanum), Ce (cerium) and Sm (samarium).
At first, rare earth and calcium have close overpotential of hydrogen evolution, can reduce moisture content and run off, and improve the mechanical performance of grid material.
Secondly, rare earth element and lead can form the high-melting point metal compound, improve the intergranular of lead alloy and tear phenomenon, improve the hot-workability of alloy, increase the toughness and the creep-resistant property of grid alloy.The adding of rare earth also can increase the age-hardening effect of grid alloy, improves mechanical performance, chemical property and the decay resistance of lead acid accumulator plate grid material.
After rare earth joins in the lead alloy, can make alloy grain careful, structure is tight, thereby makes the anticorrosive chemical property that waits of grid alloy obtain very big improvement.Among the crystal boundary and phase boundary that is generating when rare earth element is easy to be deposited on alloy graining, hinder growing up of crystal grain, make grain refinement.High-melting-point rare earth metal and the compound thereof of dispersing and dissolving in alloy then is the nucleus that particle in suspension has served as heterogeneous forming core, played the effect of alterant (nucleating agent), thereby refinement alloy grain, elongate crystal boundary, the intensity of alloy and decay resistance are significantly improved.Aspect electrochemistry, the formation of lead oxide in the corrosive film has effectively been controlled in the adding of rare earth, reduce the thickness of corrosive film, it is even to make the particle of corrosive film be tending towards refinement, and obviously reduce in the hole in the corrosive film, the corrosive film of this structure can alleviate preferably because the stress that change in volume produces, the phenomenon that can cause corrosive film to break and peel off not, active material is closely contacted with grid, thereby can improve the conductivity between anode plate grid and the active material, help prolonging the deep discharge cycle life of battery.And lead-calcium alloy tends to form passivating film because more lead oxide is arranged corrosion product, causes the too early termination of the life of storage battery.
Once more, rare earth also can purify impurity such as sulphur in the alloy, oxygen, reduces harmful element, has improved the plasticity of alloy, and elongation is high 2 times, and the timeliness cycle of alloy is shortened, to the following process of grid and shorten the manufacturing cycle and all be beneficial to.
Simultaneously, add bismuth Bi in the rare earth alloy lead, can improve the initial capacity of battery and the hardness and the castability of grid, reduced separating out of gas in the gas replenishment process, helped deep discharge and dark circulation; The adding of rare earth metal has changed crystal structure of alloy, ohmic internal resistance reduces obviously, stability is strong in sulfuric acid solution, can make active substance solution that electrochemical reaction takes place easily, and then the discharge performance of grid decay resistance and active material is increased, thereby reduced the phenomenon of lead acid accumulator premature capacity loss and life-span premature termination.
Beneficial effect of the present invention is: with rare earth alloy lead of the present invention as the battery positive voltage grid, lead-calcium alloy is as negative plate, discharge and recharge every day twice, has the cycle life that charges and discharge more than 800 times, be applicable to dark cycle charge-discharge, prolong the useful life of storage battery greatly, can be widely used in batteries such as electric motor car, automobile, UPS (UPS), solar energy, wind energy and energy storage.
Embodiment
Below for a more detailed description with embodiment to the present invention.These embodiment only are the descriptions to best mode for carrying out the invention, scope of the present invention are not had any restriction.
Embodiment 1
Carry out the preparation of grid material by the chemical composition shown in the table 1, wherein RE is Ce: (purity is that L.M.E is more than 99.97% with lead bullion earlier, wherein L.M.E is a London Metal Exchange) be heated to 350～600 ℃, form plumbous liquid, more plumbous liquid is poured into the crucible of vacuum furnace, put into RE in this crucible in advance, heat under the vacuum state to 600～820 ℃, after treating the RE fusing, the cooling mold forms the Pb-RE foundry alloy; In addition, in crucible, add quantitative plumbous liquid, add Ca and Al again, form the Pb-CaAl foundry alloy 600～620 ℃ of fusings; In the plumbous liquid of melting pot, add a certain proportion of Pb-RE foundry alloy and Pb-CaAl foundry alloy at last, add a certain proportion of Sn and Bi again, in 500 ℃ of mixing and stirring, the cooling mold.
Embodiment 2
Except RE is Ce, La and Sm, the Pb-RE vacuum state is heated to 880～1100 ℃, and all the other execution modes are with embodiment 1.
Embodiment 3
Except RE is Sm, the Pb-RE vacuum state is heated to 880～1100 ℃, and all the other execution modes are with embodiment 1.
Embodiment 4
Except RE is La, the Pb-RE vacuum state is heated to 720～940 ℃, and all the other execution modes are with embodiment 1.
Embodiment 5
Except RE is Ce and Sm, all the other execution modes are with embodiment 1.
Embodiment 6
Except RE is La and Sm, all the other execution modes are with embodiment 1.
Embodiment 7-8
Execution mode is with embodiment 1.
Embodiment 9-10
Except RE is Ce, La and Sm, all the other execution modes are with embodiment 1.
The chemical composition (wt%) of table 1 embodiment of the invention 1-10 grid material
| Sequence number | ??Ca | ??Al | ??Sn | ??Bi | ??RE | ??Pb |
| Embodiment 1 | ??0.062 | ??0.015 | ??1.25 | ??0.04 | ??0.052 | Surplus |
| Embodiment 2 | ??0.074 | ??0.019 | ??1.30 | ??0.05 | ??0.13 | Surplus |
| Embodiment 3 | ??0.079 | ??0.010 | ??1.12 | ??0.057 | ??0.22 | Surplus |
| Embodiment 4 | ??0.070 | ??0.015 | ??1.22 | ??0.046 | ??0.18 | Surplus |
| Embodiment 5 | ??0.065 | ??0.012 | ??1.20 | ??0.06 | ??0.07 | Surplus |
| Embodiment 6 | ??0.080 | ??0.018 | ??1.15 | ??0.055 | ??0.09 | Surplus |
| Embodiment 7 | ??0.073 | ??0.020 | ??0.55 | ??0.048 | ??0.002 | Surplus |
| Embodiment 8 | ??0.063 | ??0.018 | ??0.6 | ??0.043 | ??0.0042 | Surplus |
| Embodiment 9 | ??0.068 | ??0.012 | ??0.73 | ??0.06 | ??0.008 | Surplus |
| Embodiment 10 | ??0.060 | ??00.020 | ??0.42 | ??0.058 | ??0.003 | Surplus |
Claims (5)
1, a kind of storage battery rare-earth alloy lead plate grid material, it is characterized in that, the chemical composition of described grid material comprises: Ca:0.06～0.08wt%, Al:0.01～0.02wt%, Sn:0.1～1.3wt%, Bi:0.04～0.06wt%, RE:0.002～0.25wt%, surplus is Pb.
2, grid material according to claim 1 is characterized in that, described Pb is the lead bullion of purity more than 99.97%.
3, grid material according to claim 1 is characterized in that, described RE is selected from a kind of among La, Ce and the Sm.
4, grid material according to claim 1 is characterized in that, described RE is selected from any two kinds among La, Ce and the Sm.
5, grid material according to claim 1 is characterized in that, described RE is La, Ce and Sm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810200752A CN101685863A (en) | 2008-09-28 | 2008-09-28 | Rare-earth alloy lead plate grid material for accumulator |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810200752A CN101685863A (en) | 2008-09-28 | 2008-09-28 | Rare-earth alloy lead plate grid material for accumulator |
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| CN101685863A true CN101685863A (en) | 2010-03-31 |
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| CN200810200752A Pending CN101685863A (en) | 2008-09-28 | 2008-09-28 | Rare-earth alloy lead plate grid material for accumulator |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103219523A (en) * | 2013-04-03 | 2013-07-24 | 江苏海德森能源有限公司 | Negative plate of lead-acid storage battery and preparation method of negative plate |
| CN103762369A (en) * | 2014-01-10 | 2014-04-30 | 江苏苏中电池科技发展有限公司 | Rare-earth lead alloy for lead-acid storage battery positive grid |
| CN106684391A (en) * | 2016-12-21 | 2017-05-17 | 河南超威电源有限公司 | Rare earth grid alloy for lead-acid storage batteries and production method thereof |
| CN108754229A (en) * | 2018-08-02 | 2018-11-06 | 江苏科耐尔新能源科技有限公司 | A kind of accumulator plate grid alloy and its production method |
| CN110423917A (en) * | 2018-07-31 | 2019-11-08 | 荷贝克电池有限责任及两合公司 | Metal, electrode and battery |
| CN111063894A (en) * | 2019-11-30 | 2020-04-24 | 河南超威电源有限公司 | Rare earth grid alloy for lead-acid storage battery |
| CN112786884A (en) * | 2021-01-05 | 2021-05-11 | 浙江南都电源动力股份有限公司 | High-performance graphene storage battery for starting and stopping automobile |
| CN113097573A (en) * | 2021-03-25 | 2021-07-09 | 北京阳光鸿志电气工程技术有限公司 | Quick-charging full-sealed maintenance-free lead-acid storage battery |
-
2008
- 2008-09-28 CN CN200810200752A patent/CN101685863A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103219523A (en) * | 2013-04-03 | 2013-07-24 | 江苏海德森能源有限公司 | Negative plate of lead-acid storage battery and preparation method of negative plate |
| CN103219523B (en) * | 2013-04-03 | 2015-07-01 | 江苏海德森能源有限公司 | Negative plate of lead-acid storage battery and preparation method of negative plate |
| CN103762369A (en) * | 2014-01-10 | 2014-04-30 | 江苏苏中电池科技发展有限公司 | Rare-earth lead alloy for lead-acid storage battery positive grid |
| CN103762369B (en) * | 2014-01-10 | 2016-08-17 | 江苏海宝电池科技有限公司 | A kind of rare-earth lead alloy for lead-acid storage battery positive grid |
| CN106684391A (en) * | 2016-12-21 | 2017-05-17 | 河南超威电源有限公司 | Rare earth grid alloy for lead-acid storage batteries and production method thereof |
| CN110423917A (en) * | 2018-07-31 | 2019-11-08 | 荷贝克电池有限责任及两合公司 | Metal, electrode and battery |
| CN108754229A (en) * | 2018-08-02 | 2018-11-06 | 江苏科耐尔新能源科技有限公司 | A kind of accumulator plate grid alloy and its production method |
| CN111063894A (en) * | 2019-11-30 | 2020-04-24 | 河南超威电源有限公司 | Rare earth grid alloy for lead-acid storage battery |
| CN112786884A (en) * | 2021-01-05 | 2021-05-11 | 浙江南都电源动力股份有限公司 | High-performance graphene storage battery for starting and stopping automobile |
| CN113097573A (en) * | 2021-03-25 | 2021-07-09 | 北京阳光鸿志电气工程技术有限公司 | Quick-charging full-sealed maintenance-free lead-acid storage battery |
| CN113097573B (en) * | 2021-03-25 | 2022-08-12 | 北京阳光鸿志电气工程技术有限公司 | Quick-charging full-sealed maintenance-free lead-acid storage battery |
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