CN103227316B - Positive electrode plate of lead-acid battery and preparation method thereof - Google Patents
Positive electrode plate of lead-acid battery and preparation method thereof Download PDFInfo
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- CN103227316B CN103227316B CN201310115382.8A CN201310115382A CN103227316B CN 103227316 B CN103227316 B CN 103227316B CN 201310115382 A CN201310115382 A CN 201310115382A CN 103227316 B CN103227316 B CN 103227316B
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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 discloses a positive electrode plate of lead-acid battery. The positive electrode plate comprises a positive grid and active substances coated on the positive grid, wherein the active substances comprises the following components by weight parts: 1000 parts of lead dioxide, 5-50 parts of bismuth oxide, 10-50 parts of graphite, 0.1-1 part of composite rare earth, and 0-20 parts of an active additive, and the composite rare earth comprises the following components by mass percent: 52-67 % of Ce, 12-22 % of Y, 10-20 % of Nd and the balance being unavoidable impurities. Compared with traditional lead-tin alloy battery grids, the grid provided by the invention is relatively high in corrosion-resistant deformation properties and high in proportion capacity, still has good battery capacity after several deep charge-discharge cycles, and thus has relatively long service life.
Description
Technical field
The invention belongs to lead accumulator technical field, particularly relate to anode plate technology.
Background technology
At present for environmental protection object, replace conventional petroleum, the contour pollution power sources of coal, electric energy is more and more paid attention to and is applied.And lead acid accumulator is the major impetus source of current electric automobile, bicycle etc.But its reliability.Non-maintaining property, deep cycle battery capacity attenuation and corrosion resistance all have much room for improvement.Especially at present the lead acid accumulator made of terne metal traditional electrode is analysed oxygen and is suppressed not good due to grid corrosion distortion, active material liberation of hydrogen, easily to come off etc. to cause its life-span not long.
Summary of the invention
Goal of the invention: for above-mentioned existing Problems existing and deficiency, the object of this invention is to provide a kind of positive electrode plate of lead-acid battery and preparation method thereof, just actively plate prepared by the method has high corrosion resistance, is concrete dynamic modulus high-specific surface area structure, can significantly improve positive pole charge-discharge performance.
Technical scheme: for achieving the above object, the present invention by the following technical solutions: a kind of positive electrode plate of lead-acid battery, comprise anode plate grid and be coated in active material on this anode plate grid, described active material comprises the component of following parts by weight:
Wherein, following mass fraction component is contained in described compound rare-earth: cerium Ce:52 ~ 67%, yttrium Y:12 ~ 22%, neodymium Nd:10 ~ 20%; And inevitable impurity.
As preferably, described active additive is propenylbenzene ethene or Allyl thiourea.
As preferably, described anode plate grid comprises matrix and top layer, and its mesexine is formed by plating mode, the main component containing following mass percent:
Wherein compound rare-earth contains the component of following mass fraction: cerium Ce:52 ~ 67%, yttrium Y:12 ~ 22%, neodymium Nd:10 ~ 20%; And the inevitable impurity of surplus.
As preferably, described matrix is lead, lead alloy, copper or titanium.
A preparation method for above-mentioned positive electrode plate of lead-acid battery, comprises the following steps:
The preparation of a, anode plate grid: just matrix as in negative electrode immersion plating liquid plating obtain top layer, this plating solution and operating condition as follows:
Wherein, described rare earth addition is the mixture of cerium oxide, yittrium oxide and neodymia; Current density is 1 ~ 5A/dm
2; PH is 4 ~ 6; Temperature is 15 ~ 35 DEG C; Anode is stereotype;
Prepared by b, active material: in snperoxiaized lead powder, add the bismuth oxide of ormal weight, compound rare-earth, graphite and active additive and mix, and make lead plaster;
C, then by lead plaster with smearing machine full-filling on anode plate grid, and through overcuring and drying.
As preferably, the thickness of described anode plate grid mesexine is 5 ~ 10 microns.
Beneficial effect: compared with prior art, the present invention has the following advantages: relatively common lead ashbury metal battery grid have higher anticorrosive deformation nature, high specific gravity capacity, after repeatedly discharge and recharge deeper cavity, still have good battery capacity, therefore the life-span is longer.
Embodiment
Below in conjunction with specific embodiment, illustrate the present invention further, these embodiments should be understood only be not used in for illustration of the present invention and limit the scope of the invention, after having read the present invention, the amendment of those skilled in the art to the various equivalent form of value of the present invention has all fallen within the application's claims limited range.
Embodiment 1
A preparation method for lead acid accumulator, the present embodiment take Titanium as matrix, prepares by the following method:
The preparation of anode plate grid: Titanium base is carried out the alloy surface that plating obtains the Pb-Sb-Sn doped with compound rare-earth element in electroplate liquid, concrete electroplate liquid and running parameter as follows: the stannous chloride of the lead acetate of 40g/L, the potassium antimony tartrate of 2.2g/L, 0.7g/L, the boric acid mixed dissolution of citric acid 120g/L, 35g/L completely after, regulate pH to about 5, add the neodymia of the cerium oxide of 100ppm, the yittrium oxide of 100ppm and 100ppm, under well-beaten condition, after adding the butynol propoxylated compounds BMP of 20ppm, electroplate liquid has configured.Using stereotype as anode, titanium metal substrates as negative electrode and charged lower groove (connect DC power cathode, improve adhesion) electroplate, current density controls at 2 ~ 3A/dm
2in scope, electro-deposition 5 ~ 10 minutes, can obtain the coating of 3 ~ 10 microns, and this coating main component is plumbous, and rare-earth element cerium, yttrium and the neodymium containing the metallic antimony of about 2.8%, the metallic tin of 0.7% and trace.In fact base material can select lead and lead alloy, or copper metal.When selecting copper or titanium, can improve the gravimetric capacity of lead acid accumulator, and Cu and Ti ion pair battery liquid is free from side effects, especially Titanium has high stability, and can improve the corrosion resistance of grid.
Prepared by active material: in snperoxiaized 1000 parts of lead powder, adds 15 parts of bismuth oxides, 24 parts of graphite, the compound rare-earth of 0.5 part, containing cerium Ce:52 ~ 67%, yttrium Y:12 ~ 22%, neodymium Nd:10 ~ 20% in this compound rare-earth; , then add 5 parts of propenylbenzene ethene, after mixing, make lead plaster, and by this lead plaster full-filling on above-mentioned anode plate grid, eventually pass solidification and drying.
In this example, active additive propenylbenzene ethene and graphite have synergy, in grid coating paste solidification dry run, are conducive to the formation of grid in positive active material, improve its porosity.When carrying out discharge and recharge, being conducive to electrolyte permeability mass transfer in active material, thus effectively utilizing active material, improve charge-discharge performance.Graphite can also improve the conductivity of pole plate in addition, reduces internal resistance; The simultaneously introducing of above-mentioned compound rare-earth element and bismuth metal, while raising grid corrosion resistance avoids corrosion-deformation, overpotential for oxygen evolution when effectively improve charging, reduces the loss of electrolyte moisture, improves battery security simultaneously.
Wherein, following mass fraction component is contained in described compound rare-earth: cerium Ce:52 ~ 67%, yttrium Y:12 ~ 22%, neodymium Nd:10 ~ 20%; And inevitable impurity.
Embodiment 2
The present embodiment take metallic copper as base material, and electroplate in following plating solution: after the stannous chloride of the lead acetate of 32g/L, the potassium antimony tartrate of 4.5g/L, 0.5g/L, the boric acid mixed dissolution of citric acid 120g/L, 35g/L are complete, regulate pH to about 5, add the neodymia of the cerium oxide of 200ppm, the yittrium oxide of 100ppm and 50ppm, under well-beaten condition, add the N of 10ppm, after N-diethyl propargylamine DEP, electroplate liquid has configured.Using stereotype as anode, copper metal base as negative electrode and charged lower groove (connection DC power cathode) electroplate, current density controls at 2 ~ 3A/dm
2in scope, electro-deposition 5 ~ 10 minutes, can obtain the coating of 3 ~ 10 microns, and this coating main component is plumbous, and containing the metallic antimony of about 3.5%, the metallic tin of 0.5% and trace be about 0.02% rare-earth element cerium, yttrium and neodymium.
Prepared by active material: in snperoxiaized 1000 parts of lead powder, add 40 parts of bismuth oxides, 40 parts of graphite, 0.2 part of compound rare-earth, wherein comprise cerium Ce:52 ~ 67%, yttrium Y:12 ~ 22%, neodymium Nd:10 ~ 20% in compound rare-earth; And 15 parts of propenylbenzene ethene, mix and make lead plaster.Preferably by this lead plaster full-filling on grid, dry through overcuring.Titanium or copper, as matrix, can reduce pole plate density, improve the gravimetric capacity of battery, and titanium ion are free from side effects to electrolyte.
The grid of embodiment 1 and 2 and common grid are carried out electrolysis in a series arrangement in sulfuric acid solution, takes out sample after a period of time after washing is dried, take the weight before and after electrolysis.Table 1 is comparing result.
Table 1
| Sample | Weight before test, g | Weight after test, g | Corrosion rate, mg/d |
| Embodiment 1 | 21.5255 | 21.4833 | 21.1 |
| Embodiment 2 | 20.3781 | 20.3105 | 33.8 |
| Comparative example | 19.7468 | 19.6237 | 61.5 |
As known from Table 1, the corrosion rate of common grid be the grid of embodiment 1 close to 3 times.In addition, find that liberation of hydrogen of the present invention and oxygen evolution potential are increased significantly by doing cyclic voltammetry curve test to above-mentioned grid, there is higher overpotential, thus water electrolysis formation hydrogen and oxygen can be reduced, improve the stability of battery liquid.
In addition charging performance test is carried out to the battery that the positive pole of embodiment 1 and 2 is made: charge and discharge cycles test is carried out in the degree of depth 8h electric discharge with 85%, 8h charging.The battery of embodiment 1 and 2, through 350 loop tests, still have the battery capacity of more than 86%, and the battery capacity of conventional accumulators has dropped to less than 72%, has needed to scrap.
Adopt the deposited particles refinement more of meticulous dose of BMP alloy plated layer in the present invention, with base material, there is good adhesion simultaneously, also can suppress anodic oxidation.In electroplating process, electrodeposition efficiency is close to 90%, and the distribution of rare earth element in sedimentary deposit is more even relative to forging type.
Claims (4)
1. a positive electrode plate of lead-acid battery, comprises anode plate grid and is coated in the active material on this anode plate grid, it is characterized in that: described active material comprises the component of following parts by weight:
Wherein, following mass fraction component is contained in described compound rare-earth: cerium Ce:52 ~ 67%, yttrium Y:12 ~ 22%, neodymium Nd:10 ~ 20%; And inevitable impurity;
Described active additive is propenylbenzene ethene or Allyl thiourea;
Described anode plate grid comprises matrix and top layer, and its mesexine is formed by plating mode, the main component containing following mass percent, and each component sum is 100%:
Wherein compound rare-earth contains the component of following mass fraction: cerium Ce:52 ~ 67%, yttrium Y:12 ~ 22%, neodymium Nd:10 ~ 20%; And the inevitable impurity of surplus.
2. positive electrode plate of lead-acid battery according to claim 1, is characterized in that: described matrix is lead, lead alloy, copper or titanium.
3. a preparation method for positive electrode plate of lead-acid battery described in claim 2, is characterized in that comprising the following steps:
The preparation of a, anode plate grid: matrix is electroplated in negative electrode immersion plating liquid and obtains top layer, this plating solution and operating condition as follows:
Wherein, described rare earth addition is the mixture of cerium oxide, yittrium oxide and neodymia; Current density is 1 ~ 5A/dm
2; PH is 4 ~ 6; Temperature is 15 ~ 35 DEG C; Anode is stereotype;
Prepared by b, active material: in snperoxiaized lead powder, add the bismuth oxide of ormal weight, compound rare-earth, graphite and active additive and mix, and make lead plaster;
C, then by lead plaster with smearing machine full-filling on anode plate grid, and through overcuring and drying.
4. the preparation method of positive electrode plate of lead-acid battery according to claim 3, is characterized in that: the thickness of described anode plate grid mesexine is 5 ~ 10 microns.
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| US10511022B2 (en) * | 2016-04-27 | 2019-12-17 | Rsr Technologies, Inc. | Lead-based alloy and related processes and products |
| CN107180942A (en) * | 2017-06-08 | 2017-09-19 | 界首市南都华宇电源有限公司 | Start and stop anode lead plaster |
| CN107240686B (en) * | 2017-06-08 | 2020-02-18 | 界首市南都华宇电源有限公司 | High-performance large-current start-stop battery lead paste and start-stop battery |
| CN108075109A (en) * | 2017-11-06 | 2018-05-25 | 超威电源有限公司 | A kind of battery pole plates for improving active material utilization |
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| CN101510610A (en) * | 2009-03-13 | 2009-08-19 | 江苏华富控股集团有限公司 | Positive slab lattice alloy for power lead acid battery and preparation method thereof |
| CN101841031B (en) * | 2010-05-27 | 2012-07-11 | 江苏华富控股集团有限公司 | Method for preparing positive electrode grid of lead storage battery |
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