CN101174692A - Negative plate grid alloy of lead-acid accumulator - Google Patents
Negative plate grid alloy of lead-acid accumulator Download PDFInfo
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- CN101174692A CN101174692A CNA2007101652159A CN200710165215A CN101174692A CN 101174692 A CN101174692 A CN 101174692A CN A2007101652159 A CNA2007101652159 A CN A2007101652159A CN 200710165215 A CN200710165215 A CN 200710165215A CN 101174692 A CN101174692 A CN 101174692A
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Abstract
The present invention relates to a cathode grid alloy of lead-acid storage battery, including lead, calcium, aluminum and tin respectively with the weight percentage of 99.77-99.85 percents, 0.06-0.10 percents, 0.02-0.05 percents and 0.07-0.08 percents. When the tin content in the cathode grid alloy provided by the present invention is reduced to 0.07-0.08 percents, expensive pure tin is unnecessarily added to the alloy furnace in the preparation process of the cathode alloy and the tin recovered from the anode alloy can meet the tin content of 0.07-0.08 percents in cathode. The present invention reduces the production cost of the battery cathode plate by 0.5-1.0 percent, which alone can improve the net profit of the company by 1-1.5 percents.
Description
Technical field
The present invention relates to a kind of lead acid batteries electrode plate grid, relate in particular to a kind of lead-acid battery negative pole plate grid.
Background technology
Grid is an important component part of lead-acid battery electrode, the nonactive parts of most critical, and it has two effects greatly in storage battery: one, support active material, two, the effect of conduction, serve as collector at charging, interdischarge interval.This has good performance with regard to the alloy that requires to make grid.As the negative plate grid alloy of lead acid accumulator, overpotential of hydrogen evolution can not be too low, and will be easy to casting, is convenient to conduction of current etc.In recent years, Pb-Ca-Sn-Al alloy has replaced original lead-antimony alloy, with its good casting character, performance characteristics such as overpotential of hydrogen evolution is high and the self discharge of the battery made is little, always by the first-selection of existing most producers as the casting negative electrode grid.But tin content is about 0.4% of total alloy content in the existing Pb-Ca-Sn-Al alloy, and the price of tin is 6～8 times of plumbous price, thereby makes the cost of raw material of lead-acid battery improve 1-2 doubly.Under so high production cost pressure, enterprise is difficult to stablize sustainable development.
Summary of the invention
The objective of the invention is at the problems referred to above, provide a kind of production cost low negative plate grid alloy of lead-acid accumulator.
Technical scheme of the present invention is: a kind of negative plate grid alloy of lead-acid accumulator, comprise lead, calcium, aluminium and tin, and wherein the each component weight percent content is: calcium 0.06-0.10%, aluminium 0.02-0.05%, tin 0.07-0.08%, plumbous 99.77-99.85%.
Beneficial effect of the present invention is: negative pole Sn content in alloys provided by the invention is reduced to 0.07-0.08%, at this moment, do not need in the process for preparation of negative pole alloy to add expensive pure tin in alloying furnace, the anodal tin that reclaims in the alloy just can reach the tin content of the 0.07-0.08% in the negative pole; Make the accumulator negative plate production cost reduce 0.5-1.0%, only this item can make company's product net profit improve 1-1.5 percentage point.
Description of drawings
Fig. 1 is the timeliness hot strength change curve of alloy A and alloy B;
Fig. 2 is the timeliness firmness change curve chart of alloy A and alloy B;
Fig. 3 is 12V100AH battery capacity attenuation curve figure when adopting alloy A and alloy B respectively;
Fig. 4 is 4V1AH battery capacity attenuation curve figure when adopting alloy A and alloy B respectively;
Fig. 5 is 12V100AH battery capacity attenuation curve figure when adopting alloy C and alloy D respectively
Fig. 6 is 4V1AH battery capacity attenuation curve figure when adopting alloy C and alloy D respectively
The invention will be further described below in conjunction with embodiment and accompanying drawing.
Embodiment
1, take by weighing each composition of alloy by weight percent content shown in the table 1, alloyage in lead pan, this alloy is numbered B.
Each composition weight percent content in table 1 alloy
| Composition | Sn | Ca | Al | Pb | Sn/Ca |
| Content (%) | 0.07 | 0.06 | 0.02 | 99.85 | 1.16 |
2, the mechanical property after the beta alloy different time timeliness.
Press the general Pb-Ca-Sn-Al alloy of column weight amount percentage preparation: Sn:0.4%, Ca:0.08%, Al:0.02%, Pb:95%, this alloy is numbered A.
2.1 the hot strength of beta alloy A, B
According to following method of testing, the hot strength of A, B alloy is tested, and compare.
The pulling force ability to bear of test sample on the pulling experiment machine, the gravity G that affords when noting sample fracture in the readout instrument of transducer measures the sectional area S of sample.Hot strength=G/S.
Table 2 is the data of this experiment tension-compression sensor of 2,4,8,24 and 48 hours of timeliness after casting.
The G value (unit K N/m) of table 2 alloy A and the different timeliness of alloy B
| The alloy numbering | 2h | 4h | 8h | 24h | 48h |
| A | 468 | 475.5 | 486 | 490.5 | 477 |
| |
300 | 301 | 308 | 313 | 311 |
The sectional area S of alloy sample is respectively in this experiment: alloy A is 10 * 1.5mm
2, alloy B is 8 * 1.25mm
2
The timeliness hot strength that the above-mentioned formula of test data substitution of above two kinds of alloys is calculated two kinds of alloys is as shown in table 3.
The timeliness hot strength (units MPa) of table 3 alloy A and alloy B
| The alloy numbering | 2h | 4h | 8h | 24h | 48h |
| A | 31.2 | 31.7 | 32.4 | 32.7 | 31.8 |
| |
30 | 30.1 | 30.8 | 31.3 | 31.1 |
As can be seen from the above table, the hot strength of alloy is along with slight decline has taken place in the reduction of tin content, and accompanying drawing 1 is the timeliness hot strength change curve of alloy A and alloy B.By calculating, the mean value of alloy B hot strength is 96% of alloy A, and is very approaching with the hot strength of alloy A, reached grid casting requirement, to the not influence of performance of grid.
2.2 Brinell hardness test
Utilize 2,4,6,8,24 and 48 hours timeliness Brinell hardness (table 4) of Brinell hardness tester test two kinds of alloys of A, B, and investigate the aging characteristic between them.
The timeliness hardness of table 4 alloy A and alloy B (HBS of unit)
| The alloy numbering | 2h | 4h | 6h | 8h | 24h | 48h |
| A | 7.65 | 7.96 | 8.2 | 8.44 | 9.1 | 9.9 |
| B | 7.4 | 7.67 | 7.84 | 8.08 | 8.92 | 9.77 |
As can be seen from the above table, along with the reduction of tin content, slight decline has taken place in Brinell hardness, and accompanying drawing 2 is the timeliness Brinell hardness change curve of alloy A and alloy B.By calculating, the hardness of alloy B timeliness after 48 hours is 97% of alloy A.Can reach the needed requirement of strength of grid coated plate fully.
3, the liberation of hydrogen ability of test A, two kinds of alloys of B.
Utilize multichannel potentiostat beta alloy A and the alloy B liberation of hydrogen electric current under-1.3V current potential to be respectively 1.63 mA and 1.52mA, be respectively 1.181mA and 1.126mA with the Pb/PbSO4 reduction peak current.The size of the liberation of hydrogen current value that tests out and the ratio of reduction peak current value is represented the liberation of hydrogen ability of its every kind alloy.By calculating, two kinds of alloys of A, B under-1.3V current potential the liberation of hydrogen electric current and the ratio of Pb/PbSO4 reduction peak current be respectively 1.38 and 1.35, illustrate that tin content is reduced to 0.07% in the negative electrode lead Ca-Sn-Al alloy, the overpotential of hydrogen evolution of alloy is more or less the same, for the not influence of battery operation process liberation of hydrogen.
4, utilize above-mentioned alloy A, alloy B casting grid, assembling 12V100AH battery and 4V1AH battery, and the performance of testing two kinds of batteries.
The initial capacity of battery when 4.1 two kinds of alloys of A, B are adopted in test respectively, the data statistics of 12V100AH battery discharge is as shown in table 5, and the data statistics of 4V1AH battery discharge is as shown in table 6.Adopt the battery of A alloy to be numbered m, adopt the battery of B alloy to be numbered n.
Table 5 12V100AH battery discharge data
| The battery numbering | m | n |
| 20h leads average discharge time (h) | 23.53 | 22.05 |
| 10h leads average discharge time (h) | 11.82 | 11.3 |
| 3h leads average discharge time (h) | 4.13 | 3.89 |
Data statistics of 4V1AH battery discharge such as table 6:
Table 6 4V1AH battery discharge data
| The battery numbering | m | n |
| 10h leads average discharge time (h) | 11.1 | 11.32 |
| 3h leads average discharge time (h) | 3.67 | 3.75 |
| 1h leads average discharge time (h) | 1.38 | 1.42 |
Data from table 5, table 6 can be found out: the initial capacity of two kinds of negative pole alloy test cells all can satisfy standard-required, the initial capacity of two kinds of batteries differs seldom, and with respect to the 4V1AH compacted accumulator, after tin content reduced, relatively also outline was higher for the initial capacity of battery.
4.2 test two kinds of cycle performance of battery
The battery of 12V100Ah is with 5I
20(25A) current discharge 3h is immediately with 2I
20(10A) current charges 9h, composition once charges and discharge circulation, and circulates by this circulation pattern, and every circulation is used I 50 times
20(25A) current discharge stops when voltage reaches 1.75V, surveys the primary cell capacity.Fig. 3 is the capacity attenuation curve of these two kinds of batteries.
The battery of 4V1AH was banished electricity 1 hour with the 0.2A battery, with 0.2A charging 3.5 hours, formed a circulation then, and every circulation is that 3.5V stops with 0.6A current discharge to every cell voltage 10 times, surveys the primary cell capacity.Fig. 4 is the capacity attenuation curve of these two kinds of batteries.
After the cycle performance test of above-mentioned two kinds of batteries can illustrate that the negative pole Sn content in alloys reduces, the cycle performance of battery not only was not affected, and makes the cycle performance of battery better on the contrary.The battery of 12V100Ah is after circulation 300 times, and the Capacity Ratio battery m capacity of battery n is higher; The 4V1Ah battery is in cyclic process, and the capacity of battery n is always than the capacity height of battery m.
The degree of tin is reduced to 0.07% in the negative plate grid alloy provided by the invention, at this moment, do not need to add in alloying furnace expensive pure tin in the process for preparation of negative pole alloy, the anodal tin that reclaims in the alloy just can reach the tin content about 0.07% in the negative pole.Make the battery terminal negative production cost reduce 0.5-1%.
Embodiment 2
1, take by weighing each composition of alloy by weight percent content shown in the table 7, alloyage in lead pan, this alloy is numbered D.
Each composition weight percent content in table 7 alloy
| Composition | Sn | Ca | Al | Pb | Sn/Ca |
| Content (%) | 0.08 | 0.10 | 0.05 | 99.77 | 0.8 |
2, the mechanical property after the beta alloy different time timeliness.
Press the general Pb-Ca-Sn-Al alloy of column weight amount percentage preparation: Sn:0.5%, Ca:0.08%, Al:0.03%, Pb95%, this alloy is numbered C.
2.1 press the hot strength of the foregoing description 1 described process test alloy C and alloy D.
Table 8 is the data of this experiment tension-compression sensor of 2,4,8,24 and 48 hours of timeliness after casting.
The G value (unit K N/m) of table 8 alloy C and the different timeliness of alloy D
| The alloy numbering | 2h | 4h | 8h | 24h | 48h |
| C | 496.5 | 481.5 | 489 | 492 | 478.5 |
| D | 460.5 | 465 | 477 | 481.5 | 468 |
The sectional area S of alloy sample is respectively in this experiment: alloy C is 10 * 1.5mm
2, alloy D is 10 * 1.5mm
2
The timeliness hot strength that the above-mentioned formula of test data substitution of above two kinds of alloys is calculated two kinds of alloys is as shown in table 9.
The timeliness hot strength (units MPa) of table 9 alloy C and alloy D
| The alloy numbering | 2h | 4h | 8h | 24h | 48h |
| C | 31.3 | 32.1 | 32.6 | 32.8 | 31.9 |
| D | 30.7 | 31 | 31.8 | 32.1 | 31.2 |
As can be seen from the above table, the hot strength of alloy is along with slight decline has taken place in the reduction of tin content.By calculating, the mean value of the hot strength of alloy D is 97.6% of alloy C, and is very approaching with the hot strength of alloy C, reached grid casting requirement fully, to the not influence of serviceability of grid.
2.2 Brinell hardness test
Utilize 2,4,6,8,24 and 48 hours timeliness Brinell hardness (table 10) of Brinell hardness tester test two kinds of alloys of C, D, and investigate the aging characteristic between them.
The timeliness hardness of table 10 alloy C and alloy D (HBS of unit)
| The alloy numbering | 2h | 4h | 6h | 8h | 24h | 48h |
| C | 7.68 | 7.99 | 8.13 | 8.55 | 9.21 | 10.43 |
| D | 7.51 | 7.71 | 8.32 | 8.44 | 9.14 | 9.97 |
As can be seen from the above table, along with the reduction of tin content, slight decline has taken place in Brinell hardness.By calculating, the hardness of alloy D timeliness after 48 hours is 98.2% of alloy C.Can reach the needed requirement of strength of grid coated plate fully.
3, the liberation of hydrogen ability of test C, two kinds of alloys of D.
Liberation of hydrogen ability by embodiment 1 described process test alloy C and alloy D is respectively 1.44 and 1.42, as seen tin content is reduced to 0.08% in the negative electrode lead Ca-Sn-Al alloy, the overpotential of hydrogen evolution of alloy differs very little, for the almost not influence of battery operation process liberation of hydrogen.
4, utilize above-mentioned alloy C, alloy D to cast grid, assembling 12V100AH battery and 4V1AH battery, and the performance of testing two kinds of batteries.
The initial capacity of battery when 4.1 two kinds of alloys of C, D are adopted in test respectively, the data statistics of 12V100AH battery discharge is as shown in table 11, and the data statistics of 4V1AH battery discharge is as shown in table 12.Adopt the battery of C alloy to be numbered v, adopt the battery of D alloy to be numbered w.
Table 11 12V100AH battery discharge data
| The battery numbering | v | w |
| 20h leads average discharge time (h) | 24.13 | 23.65 |
| 10h leads average discharge time (h) | 12.22 | 11.94 |
| 3h leads average discharge time (h) | 4.74 | 4.16 |
Data statistics of 4V1AH battery discharge such as table 12:
Table 12 4V1AH battery discharge data
| The battery numbering | v | w |
| 10h leads average discharge time (h) | 11.6 | 11.73 |
| 3h leads average discharge time (h) | 3.81 | 3.83 |
| 1h leads average discharge time (h) | 1.4 | 1.47 |
Data from table 11, table 12 can be found out: the initial capacity of two kinds of negative pole alloy test cells all can satisfy standard-required, the initial capacity of two kinds of batteries differs seldom, and with respect to the 4V1AH compacted accumulator, the initial capacity that tin content is reduced to the battery that 0.08% alloy makes is relatively also wanted the battery of a little higher than original lead-calcium alloy assembling.
4.2 test two kinds of cycle performance of battery
After the cycle performance test of above-mentioned two kinds of batteries can illustrate that the negative pole Sn content in alloys reduces, the cycle performance of battery not only was not affected, and makes the cycle performance of battery better on the contrary.The battery of 12V100Ah is after circulation 300 times, and the Capacity Ratio battery v capacity of battery w is higher; The 4V1Ah battery is in cyclic process, and the capacity of battery w is always than the capacity height of battery v.
Negative pole Sn content in alloys provided by the invention is reduced to 0.08%, at this moment, does not need to add expensive pure tin in the process for preparation of negative pole alloy in alloying furnace, and the anodal tin that reclaims in the alloy can reach the tin content about 0.08% in the negative pole.Make the accumulator negative plate production cost reduce 0.5-1%.
Claims (1)
1. a negative plate grid alloy of lead-acid accumulator comprises lead, calcium, aluminium and tin, it is characterized in that: wherein the each component weight percent content is: calcium 0.06-0.10%, aluminium 0.02-0.05%, tin 0.07-0.08%, plumbous 99.77-99.85%.
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|---|---|---|---|
| CNA2007101652159A CN101174692A (en) | 2007-10-31 | 2007-10-31 | Negative plate grid alloy of lead-acid accumulator |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106148743A (en) * | 2016-07-11 | 2016-11-23 | 山东久力工贸集团有限公司 | A kind of Pb-Ca-Sn-Al alloy and production method thereof and application |
| CN109004114A (en) * | 2018-08-04 | 2018-12-14 | 佛山赛能新能源有限公司 | A kind of 4V navigation mark lead-acid accumulator |
| CN110546791A (en) * | 2017-12-11 | 2019-12-06 | 株式会社高崎电化工业所 | Electrode body for lead-acid battery and lead-acid battery using the same |
-
2007
- 2007-10-31 CN CNA2007101652159A patent/CN101174692A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106148743A (en) * | 2016-07-11 | 2016-11-23 | 山东久力工贸集团有限公司 | A kind of Pb-Ca-Sn-Al alloy and production method thereof and application |
| CN106148743B (en) * | 2016-07-11 | 2018-02-09 | 山东久力工贸集团有限公司 | A kind of Pb-Ca-Sn-Al alloy and its production method and application |
| CN110546791A (en) * | 2017-12-11 | 2019-12-06 | 株式会社高崎电化工业所 | Electrode body for lead-acid battery and lead-acid battery using the same |
| CN109004114A (en) * | 2018-08-04 | 2018-12-14 | 佛山赛能新能源有限公司 | A kind of 4V navigation mark lead-acid accumulator |
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