CN103227316A - 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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- CN103227316A CN103227316A CN2013101153828A CN201310115382A CN103227316A CN 103227316 A CN103227316 A CN 103227316A CN 2013101153828 A CN2013101153828 A CN 2013101153828A CN 201310115382 A CN201310115382 A CN 201310115382A CN 103227316 A CN103227316 A CN 103227316A
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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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
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Technical field
The invention belongs to the lead accumulator technical field, relate in particular to the anode plate technology.
Background technology
For the environmental protection purpose, replace traditional oil, the contour pollution power sources of coal at present, electric energy is more and more paid attention to and is used.And lead acid accumulator is the major impetus source of present electric automobile, bicycle etc.But its reliability.Non-maintaining property, dark 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 comes off easily etc. and to cause its life-span not long because grid corrosion-deformation, active material liberation of hydrogen are analysed oxygen and suppressed not good.
Summary of the invention
Goal of the invention: at the problem and shortage of above-mentioned existing existence, the purpose of this invention is to provide a kind of lead acid battery positive electrode pole plate and preparation method thereof, the just actively plate of this method preparation has high corrosion resistance, is porous crack high-specific surface area structure, can obviously improve anodal charge-discharge performance.
Technical scheme: for achieving the above object, the present invention by the following technical solutions: a kind of lead acid battery positive electrode pole plate comprises anode plate grid and is coated in active material on this anode plate grid that described active material comprises the component of following parts by weight:
1000 parts of brown lead oxide;
5～50 parts of bismuth oxides;
10～50 parts in graphite;
0.1～1 part of compound rare-earth;
0～20 part of active additive;
Wherein, contain following mass fraction component in the described compound rare-earth: cerium Ce:52～67%, yttrium Y:12～22%, neodymium Nd:10～20%; And unavoidable impurities.
As preferably, described active additive is propenylbenzene ethene or acrylic thiocarbamide.
As preferably, described anode plate grid comprises matrix and top layer, and its mesexine forms by the plating mode, mainly contains following component by mass percent:
Plumbous Pb:95～98%
Antimony Sb:2～5%;
Tin Sn:0.03～0.1%;
Compound rare-earth: 0.01～0.05%;
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 unavoidable impurities of surplus.
As preferably, described matrix is lead, lead alloy, copper or titanium.
A kind of preparation method of above-mentioned lead acid battery positive electrode pole plate may further comprise the steps:
The preparation of a, anode plate grid: just matrix obtains the top layer as electroplating in the negative electrode immersion plating liquid, and this plating bath and operating condition are as follows:
Lead acetate 30～45g/L;
Potassium antimony tartrate 0.5～5g/L;
Stannous chloride 0.5～1.0g/L;
Citric acid 80～120g/L;
Sulfamic acid 20～50g/L;
Boric acid 20～40g/L;
Rare earth addition 50～500ppm;
Butynediols propoxylation compound BMP 10～100ppm;
Wherein, described rare earth addition is the mixture of cerium oxide, yittrium oxide and neodymia; Current density is 1～5A/dm2; PH is 4～6; Temperature is 15～35 ℃; Anode is a stereotype;
B, active material preparation: in the lead powder of peroxidating, the bismuth oxide, compound rare-earth, graphite and the active additive that add ormal weight mix, and make lead plaster;
C, then with lead plaster with the smearing machine full-filling to 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 discharging and recharging dark circulation, still have battery capacity preferably, so the life-span is longer.
Embodiment
Below in conjunction with specific embodiment, further illustrate the present invention, should understand these embodiment only is used to the present invention is described and is not used in and limit the scope of the invention, after having read the present invention, those skilled in the art all fall within the application's claims institute restricted portion to the modification of the various equivalent form of values of the present invention.
Embodiment 1
A kind of preparation method of lead acid accumulator, present embodiment is matrix with the Titanium, by the following method preparation:
The preparation of anode plate grid: the titanium matrix is carried out the alloy surface that plating obtains being doped with the Pb-Sb-Sn of compound rare-earth element in electroplate liquid, concrete electroplate liquid and running parameter are 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 fully after, regulate about pH to 5, the cerium oxide, the yittrium oxide of 100ppm and the neodymia of 100ppm that add 100ppm, under well-beaten condition, after adding the butynol propoxylation compound BMP of 20ppm, the electroplate liquid configuration is finished.With stereotype as anode, titanium metal substrates (connects dc power cathode as negative electrode and charged groove down, improve adhesion) electroplate, current density is controlled in 2～3A/dm2 scope, electro-deposition 5～10 minutes, can obtain 3～10 microns coating, this coating main component is plumbous, and contains about 2.8% metallic antimony, 0.7% metallic tin and micro-rare-earth element cerium, yttrium and neodymium.In fact base material can be selected lead and lead alloy, or the copper metal.When selecting copper or titanium, can improve the proportion capacity of lead acid accumulator, and Cu and Ti ion pair battery liquid be free from side effects, especially Titanium has high stability, and can improve the corrosion resistance of grid.
Active material preparation: in 1000 parts of lead powder of peroxidating, add 15 parts of bismuth oxides, 24 parts of graphite, 0.5 part compound rare-earth, contain cerium Ce:52～67%, yttrium Y:12～22%, neodymium Nd:10～20% in this compound rare-earth; , add 5 parts of propenylbenzene ethene then, after mixing, make lead plaster, and with this lead plaster full-filling to above-mentioned anode plate grid, at last through overcuring and drying.
In this example, active additive propenylbenzene ethene and graphite have synergy, solidify in the dry run at grid coating paste, help the formation of grid in the positive active material, improve its porosity.When discharging and recharging, help the electrolyte permeability mass transfer in active material, thereby effectively utilize active material, improve charge-discharge performance.Graphite can also improve the conductivity of pole plate in addition, reduces internal resistance; The introducing of above-mentioned compound rare-earth element and bismuth metal simultaneously, when raising grid corrosion resistance was avoided corrosion-deformation, overpotential for oxygen evolution when effectively having improved charging reduced the loss of electrolyte moisture, has improved battery security simultaneously.
1000 parts of brown lead oxide;
5～50 parts of bismuth oxides;
10～50 parts in graphite;
0.1～1 part of compound rare-earth;
0～20 part of active additive;
Wherein, contain following mass fraction component in the described compound rare-earth: cerium Ce:52～67%, yttrium Y:12～22%, neodymium Nd:10～20%; And unavoidable impurities.
Embodiment 2
Present embodiment is base material with the metallic copper, and in following plating bath, electroplate: 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 fully after, regulate about pH to 5, the cerium oxide, the yittrium oxide of 100ppm and the neodymia of 50ppm that add 200ppm, under well-beaten condition, the N that adds 10ppm, behind the N-diethyl propargylamine DEP, the electroplate liquid configuration is finished.With stereotype as anode, the copper metal base is electroplated as the also charged groove (connection dc power cathode) down of negative electrode, current density is controlled in 2～3A/dm2 scope, electro-deposition 5～10 minutes, can obtain 3～10 microns coating, this coating main component is plumbous, and contains 0.02% rare-earth element cerium, yttrium and the neodymium of being about of about 3.5% metallic antimony, 0.5% metallic tin and trace.
The active material preparation: in 1000 parts of lead powder of peroxidating, 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 the compound rare-earth; And 15 parts of propenylbenzene ethene, mix and make lead plaster.Preferably with this lead plaster full-filling on grid, through the overcuring drying.Titanium or copper can reduce pole plate density as matrix, improve the proportion capacity of battery, and titanium ion are free from side effects to electrolyte.
The grid and the common grid of embodiment 1 and 2 are carried out electrolysis with series system in sulfuric acid solution, take out sample after a period of time after washing is dried, take by weighing the weight of electrolysis front and back.Table 1 is a comparing result.
Table 1
| Sample | Weight before the test, g | Test back weight, g | Corrosion rate, mg/d |
| Embodiment 1 | 21.5255 | 21.4833 | 21.1 |
| Embodiment 2 | 20.3781 | 20.3105 | 33.8 |
| Comparative Examples | 19.7468 | 19.6237 | 61.5 |
As known from Table 1, the corrosion rate of common grid be embodiment 1 grid near 3 times.In addition, find that by above-mentioned grid being done the cyclic voltammetry curve test liberation of hydrogen of the present invention and oxygen evolution potential have obvious rising, have higher overpotential, form hydrogen and oxygen, improved the stability of battery liquid thereby can reduce water electrolysis.
The battery that the positive pole of embodiment 1 and 2 is made carries out the charging performance test in addition: the charge and discharge cycles test is carried out in degree of depth 8h discharge, 8h charging with 85%.Embodiment 1 and 2 battery still have the battery capacity more than 86%, and the battery capacity of conventional accumulators have dropped to below 72% through 350 loop tests, need scrap.
Adopt the deposited particles refinement more of meticulous dose of BMP alloy plated layer among the present invention, have good bonding force with base material simultaneously, also can suppress anodic oxidation.In electroplating process, electrodeposition efficiency is near 90%, and the relative forging type of the distribution of rare earth element in sedimentary deposit is more even.
Claims (6)
1. a lead acid battery positive electrode pole plate comprises anode plate grid and the active material that is coated on this anode plate grid, and it is characterized in that: described active material comprises the component of following parts by weight:
1000 parts of brown lead oxide;
5～50 parts of bismuth oxides;
10～50 parts in graphite;
0.1～1 part of compound rare-earth;
0～20 part of active additive;
Wherein, contain following mass fraction component in the described compound rare-earth: cerium Ce:52～67%, yttrium Y:12～22%, neodymium Nd:10～20%; And unavoidable impurities.
2. according to the described lead acid battery positive electrode pole plate of claim 1, it is characterized in that: described active additive is propenylbenzene ethene or acrylic thiocarbamide.
3. according to claim 1 or 2 described lead acid battery positive electrode pole plates, it is characterized in that: described anode plate grid comprises matrix and top layer, and its mesexine forms by the plating mode, mainly contains following component by mass percent:
Plumbous Pb:95～98%
Antimony Sb:2～5%;
Tin Sn:0.03～0.1%;
Compound rare-earth: 0.01～0.05%;
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 unavoidable impurities of surplus.
4. according to the described lead acid battery positive electrode pole plate of claim 3, it is characterized in that: described matrix is lead, lead alloy, copper or titanium.
5. the preparation method of the described lead acid battery positive electrode pole plate of claim 4 is characterized in that may further comprise the steps:
The preparation of a, anode plate grid: just matrix obtains the top layer as electroplating in the negative electrode immersion plating liquid, and this plating bath and operating condition are as follows:
Lead acetate 30～45g/L;
Potassium antimony tartrate 0.5～5g/L;
Stannous chloride 0.5～1.0g/L;
Citric acid 80～120g/L;
Sulfamic acid 20～50g/L;
Boric acid 20～40g/L;
Rare earth addition 50～500ppm;
Butynediols propoxylation compound BMP 10～100ppm;
Wherein, described rare earth addition is the mixture of cerium oxide, yittrium oxide and neodymia; Current density is 1～5A/dm2; PH is 4～6; Temperature is 15～35 ℃; Anode is a stereotype;
B, active material preparation: in the lead powder of peroxidating, the bismuth oxide, compound rare-earth, graphite and the active additive that add ormal weight mix, and make lead plaster;
C, then with lead plaster with the smearing machine full-filling to anode plate grid, and through overcuring and drying.
6. according to the preparation method of the described lead acid battery positive electrode pole plate of claim 5, it is characterized in that: the thickness of described anode plate grid mesexine is 5～10 microns.
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| CN201310115382.8A CN103227316B (en) | 2013-04-03 | 2013-04-03 | Positive electrode plate of lead-acid battery and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107240686A (en) * | 2017-06-08 | 2017-10-10 | 界首市南都华宇电源有限公司 | High-performance high current start and stop battery lead plaster and start and 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 |
| CN109196688A (en) * | 2016-04-27 | 2019-01-11 | Rsr技术公司 | Lead-containing alloy and correlation technique and product |
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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 |
| CN101841031A (en) * | 2010-05-27 | 2010-09-22 | 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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| 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 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109196688A (en) * | 2016-04-27 | 2019-01-11 | Rsr技术公司 | Lead-containing alloy and correlation technique and product |
| 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 |
| CN107240686A (en) * | 2017-06-08 | 2017-10-10 | 界首市南都华宇电源有限公司 | High-performance high current start and stop battery lead plaster and start and stop battery |
| 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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| CN103227316B (en) | 2015-07-01 |
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Effective date of registration: 20211117 Address after: 225600 No.88 Bosideng Avenue, Gaoyou Economic Development Zone, Yangzhou City, Jiangsu Province Patentee after: JIANGSU OLITER ENERGY TECHNOLOGY Co.,Ltd. Address before: 225600 No. 8 Bosten Avenue, Gaoyou Economic Development Zone, Yangzhou City, Jiangsu Province Patentee before: JIANGSU HAIDESEN ENERGY Co.,Ltd. |
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