CN103219523B - Negative plate of lead-acid storage battery and preparation method of negative plate - Google Patents
Negative plate of lead-acid storage battery and preparation method of negative plate Download PDFInfo
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- CN103219523B CN103219523B CN201310115262.8A CN201310115262A CN103219523B CN 103219523 B CN103219523 B CN 103219523B CN 201310115262 A CN201310115262 A CN 201310115262A CN 103219523 B CN103219523 B CN 103219523B
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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 negative plate of a lead-acid storage battery and a preparation method of the negative plate. The negative pole plate comprises a negative plate grid and an active material coating the negative plate grid. The active material comprises the components of 1000 parts of lead powder, 10-30 parts of bismuth oxide, 5-15 parts of an organic swelling agent and unavoidable impurities in parts by weight. Compared with a common terne metal battery plate grid, the negative plate grid disclosed by the invention has the advantages of higher corrosion and deformation resistance, high proportion volume and high battery capacity after repeated deep charge-discharge cycles. Thus, the service life of the negative plate is longer.
Description
Technical field
The invention belongs to lead accumulator technical field, particularly relate to plate technique.
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 acid accumulator negative pole lead pole plate 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 charge-discharge performance.
Technical scheme: for achieving the above object, the present invention by the following technical solutions: a kind of acid accumulator negative pole lead pole plate, comprise negative electrode grid and the active material of full-filling on this negative electrode grid, described active material comprises the component of following parts by weight:
1000 parts, lead powder;
Bismuth oxide 10 ~ 30 parts;
Organic expander 5 ~ 15 parts;
And inevitable impurity;
Described active material is also containing the compound rare-earth of 0.5 ~ 3 part, and this compound rare-earth contains cerium Ce:52 ~ 67%, yttrium Y:12 ~ 22%, neodymium Nd:10 ~ 20%;
Described negative electrode 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 organic expander is lignin or humic acid.
As preferably, described matrix is lead, lead alloy, copper or titanium.
A preparation method for above-mentioned acid accumulator negative pole lead pole plate, comprises the following steps:
The preparation of a, 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/dm2; PH is 4 ~ 6; Temperature is 15 ~ 35 DEG C; Anode is stereotype;
Prepared by b, active material: in lead powder, add the bismuth oxide of ormal weight, organic expander and compound rare-earth, mix, and make lead plaster;
C, then by lead plaster with smearing machine full-filling on grid, and through overcuring and drying.
As preferably, the thickness of described 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 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 is as negative electrode and charged lower groove (connects DC power cathode, improve adhesion) electroplate, current density controls within the scope of 2 ~ 3A/dm2, electro-deposition 5 ~ 10 minutes, can obtain the coating of 3 ~ 10 microns, 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 1000 parts of lead powder, add 15 parts of bismuth oxides, 7 parts of humic acids, and 0.8 part of compound rare-earth, containing cerium Ce:52 ~ 67%, yttrium Y:12 ~ 22%, neodymium Nd:10 ~ 20% in this compound rare-earth; After mixing, make lead plaster, and by this lead plaster full-filling on above-mentioned negative electrode grid, eventually pass solidification and drying, obtain battery terminal negative pole plate.
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 within the scope of 2 ~ 3A/dm2, electro-deposition 5 ~ 10 minutes, the coating of 3 ~ 10 microns can be obtained, 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 30 parts of bismuth oxides, 10 parts of lignin, 1.2 parts of compound rare-earths, 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.Finally 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.
The present invention passes through lot of experiments, from various material, filter out humic acid and lignin, and inserted in negative electrode active material, can effectively improve its porosity, thus improve the infiltration mass transfer ability of battery electrolyte on active material, improve battery charging and discharging performance; The introducing of compound rare-earth in addition, can improve overpotential of hydrogen evolution, reduces electrolyte moisture loss.
In addition charging performance test is carried out to the battery made of embodiment 1 and 2: 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 (5)
1. an acid accumulator negative pole lead pole plate, comprises negative electrode grid and the active material of full-filling on this negative electrode grid, it is characterized in that: described active material comprises the component of following parts by weight:
1000 parts, lead powder;
Bismuth oxide 10 ~ 30 parts;
Organic expander 5 ~ 15 parts;
And inevitable impurity;
Described active material is also containing the compound rare-earth of 0.5 ~ 3 part, and this compound rare-earth contains cerium Ce:52 ~ 67%, yttrium Y:12 ~ 22%, neodymium Nd:10 ~ 20%;
Described negative electrode grid comprises matrix and top layer, and its mesexine is formed by plating mode, the main component containing following mass percent:
Above component sum is 100%, and 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. acid accumulator negative pole lead pole plate according to claim 1, is characterized in that: described organic expander is lignin or humic acid.
3. acid accumulator negative pole lead pole plate according to claim 2, is characterized in that: described matrix is lead, lead alloy, copper or titanium.
4. a preparation method for acid accumulator negative pole lead pole plate described in claim 3, is characterized in that comprising the following steps:
The preparation of a, negative electrode 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 lead powder, add the bismuth oxide of ormal weight, organic expander and compound rare-earth, mix, and make lead plaster;
C, then by lead plaster with smearing machine full-filling on negative electrode grid, and through overcuring and drying.
5. the preparation method of acid accumulator negative pole lead pole plate according to claim 4, is characterized in that: the thickness of described negative electrode grid mesexine is 5 ~ 10 microns.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104167546B (en) * | 2014-05-21 | 2016-08-24 | 河南超威电源有限公司 | Start and stop battery lead plaster and compound method |
| CN104143640B (en) * | 2014-06-16 | 2016-04-06 | 超威电源有限公司 | A kind of acid accumulator negative pole lead material suppressing liberation of hydrogen |
| CN104979561B (en) * | 2015-05-23 | 2018-06-08 | 保定金阳光能源装备科技有限公司 | A kind of graphene paint and the paint make the preparation method of super lead acid storage battery negative plate |
| WO2017049755A1 (en) * | 2015-09-24 | 2017-03-30 | 陈尚发 | Negative plate of lead-acid battery and manufacturing method thereof |
| CN106099119A (en) * | 2016-07-12 | 2016-11-09 | 河北金星电源有限公司 | A kind of long-life pole plate for lead-acid storage battery and manufacture method thereof |
| CN113394400B (en) * | 2021-05-26 | 2022-03-29 | 天能电池集团股份有限公司 | Negative pole diachylon and negative plate of lead storage battery and lead storage battery |
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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. |