• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a lead alloy for a battery grid. The alloy comprises, by weight, about 0.05-0.0725% calcium, about 1.2-1.8% tin, more than about 0.001% silver, and about 0.0005-0.04% bismuth. The invention also relates to an alloy for battery grid comprising, by weight percent, about 0.05 to 0.07% calcium, about 1.2 to 1.5% tin, more than about 0.001% silver, and more than about 0.0115% bismuth. It is disclosed.
    公开号:KR20040015697A
    申请号:KR1020030056152
    申请日:2003-08-13
    公开日:2004-02-19
    发明作者:섀퍼찰스제이.
    申请人:존슨 컨트롤스 테크놀러지 컴퍼니；
    IPC主号:
    专利说明:

    Alloy for Battery Grid {ALLOY FOR BATTERY GRID}
    [10] The present invention relates to lead alloys, and more particularly to lead alloys for battery grids containing calcium, tin and bismuth.
    [11] In general, batteries (eg, lead-acid electrical storage batteries) include cell elements with positive and negative grids, plates, and separators between the grids. Typically the grids are made of lead alloys containing various alloying elements for improving performance, lifespan and / or processability of the grid and battery.
    [12] It is well known to provide any of a variety of alloying elements to improve performance, life and / or workability of the battery grid. For example, it is known to add calcium to the alloy to increase the grid formability by increasing the hardness. However, certain amounts of calcium increase grid corrosion due to the formation of Pb 3 Ca precipitates or increase grid growth due to premature overaging.
    [13] It is also known to add silver for the purpose of increasing mechanical strength (eg creep resistance) and curing rate. However, relatively large amounts of silver and / or bismuth can cause drossing or undesirable grain growth. In addition, relatively large amounts of bismuth can generate isolated discontinuous precipitates in the grid (e.g., non-hardened precipitates formed by the reaction of bismuth with lead and / or tin). Accelerated corrosion penetration and grid growth can adversely affect the life of the grid.
    [14] Thus, it would be advantageous to be able to provide lead alloys for battery grids with acceptable corrosion rates and lifetimes. It would also be advantageous to be able to provide lead alloys for battery grids including bismuth. It would also be advantageous to be able to provide lead alloys for battery grids having relatively high hardness stability (eg, resistance to overaging). It would be desirable to provide a lead alloy for a battery grid having one or more of these features.
    [1] 1 shows a battery grid according to an embodiment of the invention.
    [2] FIG. 2A is a bar graph of the hardness stability integral of the alloy for battery grid according to the embodiment of the present invention. FIG.
    [3] 2B is a line graph showing the relationship between the total hardness stability versus the amount of bismuth in the alloy for battery grids according to an embodiment of the invention.
    [4] Figure 3a is a photograph of the alloy for the battery grid having a band of unaffected material according to an embodiment of the present invention.
    [5] 3B is a photograph of the alloy of FIG. 3A with a band of untransformed material in accordance with an embodiment of the present invention.
    [6] ** Description of symbols for the main parts of the drawing **
    [7] 10: grid 12: current integrated lug
    [8] 14: vertical wire 16: horizontal wire
    [9] 22a, 22b untranslated material band 24a, 24b: recrystallized material band
    [15] The present invention relates to a lead alloy for a battery grid. The alloy comprises from about 0.05 to 0.0725% calcium by weight. The alloy also includes from about 1.2 to 1.8% tin by weight. The alloy also includes more than about 0.001% silver by weight. The alloy also comprises from about 0.0005% to less than about 0.04% bismuth by weight. The balance of the alloy consists of lead.
    [16] The invention also relates to an alloy for a battery grid. The alloy comprises from about 0.05 to 0.07% calcium by weight. The alloy also includes from about 1.2 to 1.5% tin by weight. The alloy also includes more than about 0.001% silver by weight. The alloy also comprises more than about 0.0115% bismuth by weight. The balance of the alloy consists of lead.
    [17] The present invention also relates to a method for producing an alloy for a battery grid. The method includes alloying lead with calcium, tin, silver, and bismuth. The alloy comprises from about 0.05 to 0.0725% calcium by weight. The alloy also includes from about 1.2 to 1.8% tin by weight. The alloy also includes more than about 0.001% silver by weight. The alloy also comprises from about 0.005% to less than about 0.0275% bismuth by weight. The balance of the alloy consists of lead.
    [18] A battery plate or grid 10 is shown in FIG. 1. The grid is a “stamped” or perforated grid from a wrought alloy according to a preferred embodiment, but may also be made from a cast alloy according to another embodiment. The grid is a "positive" grid for lead-acid batteries according to a preferred embodiment, but may also be a "negative" grid according to other embodiments. The grid 10 includes a current integrating lug 12. Generally vertical wire 14 extends from lug 12. In general, the horizontal wire 16 intersects the vertical wire 14. The grid comprises a lead alloy containing calcium, tin and bismuth according to a preferred embodiment. In another embodiment, the lead alloy may comprise silver.
    [19] The amount of calcium in the alloy is chosen to impart an appropriate hardness to the alloy, which may aid in the processability of the alloy according to the preferred embodiment. If adequate hardness is obtained, heat treatment for the alloy may not be necessary. The amount of calcium in the alloy should not be high enough to cause an increase in corrosion rate or a decrease in hardness stability. According to a preferred embodiment, aluminum can be added to the alloy (or into the melting vessel of the alloy) to reduce the loss of calcium.
    [20] According to a preferred embodiment, the alloy comprises more than about 0.05% calcium by weight. According to another embodiment, the alloy comprises about 0.05 to 0.08% calcium by weight. According to yet another embodiment, the alloy comprises about 0.055 to 0.075% calcium by weight. According to yet another embodiment, the alloy comprises about 0.05 to 0.07% calcium by weight. According to yet another embodiment, the alloy comprises about 0.055 to 0.07% calcium by weight. According to yet another embodiment, the alloy comprises about 0.06% to 0.07% calcium by weight.
    [21] According to a preferred embodiment, the amount of tin in the alloy is chosen so as to reduce corrosion. Tin will react with calcium to form Sn 3 Ca (which provides corrosion resistance), and inhibit lead from reacting with calcium, thereby reducing the formation of discrete Pb 3 Ca precipitates, which may promote grid growth. It is to be understood that this is not intended to limit the subject matter of the present invention to any particular theory.
    [22] According to a preferred embodiment, the alloy comprises more than 1.2% tin by weight. According to another embodiment, the alloy comprises 1.2 to 1.65% tin by weight. According to yet another embodiment, the alloy comprises 1.2 to 1.5% tin by weight.
    [23] According to a preferred embodiment, the ratio of tin to calcium is chosen to minimize the formation of Pb 3 Ca precipitates. According to a preferred embodiment, the ratio of tin to calcium is about 10 to 1. In another embodiment, the ratio of tin to calcium is greater than about 12 to 1. According to another embodiment, the ratio of tin to calcium is greater than about 20 to 1. For example, when the alloy contains about 0.07% calcium by weight, the content of tin preferably exceeds about 0.84 by weight. Increasing the ratio of tin to lead can inhibit the formation of Pb 3 Ca precipitates, thereby reducing precipitate "coarsening" in the grid, thereby reducing grid growth and extending the life of the grid.
    [24] According to a preferred embodiment, the amount of silver in the alloy is chosen such that it can increase the mechanical strength, including creep strength at grain boundaries. According to a further preferred embodiment, the amount of silver in the alloy is chosen so as to increase the cure rate of the alloy. According to another embodiment, the silver in the alloy may be included in the form of impurities contained in a "trace amount" or in a "secondary" or recycled lead.
    [25] According to a preferred embodiment, the alloy comprises from about 0.0005 to 0.02% silver by weight. According to another embodiment, the alloy comprises about 0.001 to 0.015% silver by weight. According to yet another embodiment, the alloy comprises about 0.001 to 0.01% silver by weight. According to yet another embodiment, the alloy comprises about 0.001 to 0.005% silver by weight.
    [26] The amount of bismuth in the alloy is chosen to provide adequate hardness stability (ie, "microhardness") for the alloy. According to a preferred embodiment, the alloy comprises less than about 0.04% bismuth by weight. According to another embodiment, the alloy comprises from about 0.0005 to 0.0275% bismuth by weight. According to yet another embodiment, the alloy comprises from about 0.0005 to 0.025% bismuth by weight. According to another embodiment, the alloy comprises from about 0.001 to 0.0225% bismuth by weight. According to yet another embodiment, the alloy comprises from about 0.001 to 0.0190% bismuth by weight. According to yet another embodiment, the alloy comprises from about 0.0115 to 0.0165% bismuth by weight. According to a particularly preferred embodiment, the alloy comprises about 0.0150% bismuth by weight.
    [27] In all of the above embodiments, the alloy may comprise a relatively small amount of other materials. For example, the alloy may comprise a background “impurity” or trace amount of material present in a commercially recycled lead stream. The following amounts of impurities in the alloy may be acceptable. That is, (1) less than about 0.005% zinc by weight in optional embodiments, and less than about 0.0025% zinc by weight in preferred embodiments; (2) less than about 0.005% antimony by weight in optional embodiments, and less than 0.0025% antimony by weight in preferred embodiments; (3) less than about 0.0025% arsenic by weight in preferred embodiments; And (4) less than about 0.005% copper by weight in optional embodiments, and less than about 0.0025% copper by weight in preferred embodiments.
    [28] According to an exemplary embodiment, the alloy comprises about 0.05 to 0.07% calcium by weight, about 1.2 to 1.5% tin and about 0.0005 to 0.0275% bismuth, the balance being lead. According to an alternative embodiment, the alloy may optionally contain less than about 0.015% silver by weight. The balance is also limited by the amount of ancillary elements (e.g. bismuth, arsenic, copper, silver, tellurium, etc.) present in the recycled lead (e.g., less than about 0.0025% by weight in each impurity element). May be included.
    [29] According to a preferred embodiment, the alloy comprises, by weight%, about 0.065% calcium, about 1.35% tin, about 0.0035% silver, about 0.0005 to 0.0275% bismuth, the balance being lead and It consists of ancillary elements present in recycled lead.
    [30] According to a preferred embodiment, the alloy comprises, by weight, about 0.0652% calcium, about 1.35% tin, about 0.0036% silver, about 0.0005 to 0.0236% bismuth, the balance being lead and It consists of ancillary elements present in recycled lead.
    [31] According to an alternative embodiment, the weight percentage of various alloying elements (eg calcium, tin, silver and bismuth) may vary. For example, according to an alternative embodiment, silver may be present in a weight percent of from about 0.005 to 0.015%. According to another optional embodiment, tin may be present in about 1.2 to 1.8% by weight.
    [32] Example
    [33] Alloys A, B, C, D, E and F containing the prescribed amounts of calcium, tin, silver and bismuth listed in Tables 1-6 were prepared.
    [34] Alloy A calcium0.0645 wt.% Remark1.39 wt.% silver0.0021 wt.% Bismuth0.0005 wt.%
    [35] Alloy B1Alloy B2 calcium0.0652 wt.%0.0672 wt.% Remark1.4 wt.%1.38 wt.% silver0.0038 wt.%0.0038 wt.% Bismuth0.0005 wt.%0.0005 wt.%
    [36] Alloys B1 and B2 are collectively referred to as alloy B. The average content of silver in alloy B was 0.0021% by weight (wt.%). The average content of bismuth in alloy B was 0.005% by weight.
    [37] Alloy C calcium0.07 wt.% Remark1.38 wt.% silver0.0035 wt.% Bismuth0.0005 wt.%
    [38] Alloy D calcium0.069 wt.% Remark1.35 wt.% silver0.0036 wt.% Bismuth0.0126 wt.%
    [39] Alloy E1Alloy E2 calcium0.0684 wt.%0.0645 wt.% Remark1.37 wt.%1.33 wt.% silver0.0037 wt.%0.0032 wt.% Bismuth0.0199 wt.%0.0207 wt.% Alloy E2Alloy E4 calcium0.0654 wt.%0.644 wt.% Remark1.33 wt.%1.31 wt.% silver0.0036 wt.%0.0034 wt.% Bismuth0.0208 wt.%0.0194 wt.%
    [40] Alloys E1, E2, E3 and E4 are referred to collectively as alloy E. The average content of silver in alloy E was 0.0035% by weight. The average content of bismuth in alloy E was 0.0202% by weight.
    [41] Alloy F calcium0.0654 wt.% Remark1.37 wt.% silver0.0037 wt.% Bismuth0.0236 wt.%
    [42] The alloys were cast in slab form and flattened to 10% of the original slab thickness. From the slab, grids for batteries having a thickness of about 42 × 10 −3 inches were formed in a grid pattern. The grids were maintained at 80 degrees Celsius for 3 weeks and then subjected to hardness stability test (ie, Vickers hardness or "diamond pyramid hardness") using a Vickers hardness tester. A load of 200 grams was applied for 15 seconds for the hardness stability test. The total hardness stability for each of alloys A, B, C, D, E and F is shown in Table 7.
    [43] alloy% By weight of bismuth (average)% By weight of silver (average)Total hardness stability (DPH * frequency) A0.00050.002152.4 B0.00050.003552.4 C0.00050.004055 D0.01260.003560.4 E0.02020.003555.1 F0.02360.003558.5
    [44] The sum of hardness stability for each of the alloys A, B, C, D, E and F is shown in FIG. 2A. 2A shows that the hardness stability of grids containing from 0.0005 to 0.0236% bismuth by weight is relatively acceptable. FIG. 2B shows that the data in Table 7 fits well with the curve of FIG. 2B according to a preferred embodiment.
    [45] Alloy E2 was cast in slab form and flattened to 10% of the original thickness of the slab. Grids for batteries having a thickness of about 42 × 10 −3 inches from the slab were stamped into a grid pattern. The grids were kept at 85 degrees Celsius for 5 weeks. 3A shows an enlarged 75 times grid of one section. 3b shows the grids according to FIG. 3a in more detail. FIG. 3B shows an untransformed material band (represented by squares 22a and 22b) and several recrystallized material bands (represented by ellipses 24a and 24b) with relatively high hardness values.
    [46] It should be noted that the structure and design of the alloying elements for the battery grid shown in the above preferred and other exemplary embodiments are merely exemplary. Although only a few embodiments of the invention have been described in detail herein, those skilled in the art having reviewed the invention readily appreciate that many modifications are possible within the scope of the novel technical spirit and features of the invention as set forth in the claims herein. Able to know. For example, alloying elements may be substituted and added, and the content of alloying elements may vary. Accordingly, all such modifications are intended to be included within the scope of this invention as defined in the appended claims. The order of processes or steps may be altered or reconfigured in accordance with optional embodiments. Functional claims in the claims are intended to cover all such constructions, both as equivalents and equivalents, as described herein to perform those functions. Other substitutions, modifications, changes and omissions are possible in design, in working conditions and in the construction of the preferred and exemplary embodiments without departing from the spirit of the invention as set forth in the appended claims.
    [47] The lead alloy according to the present invention has an acceptable corrosion rate and lifetime and has a relatively high hardness stability, making it suitable for lead alloys for battery grids.
    权利要求:
    Claims (21)
    [1" claim-type="Currently amended] By weight, comprising about 0.05 to 0.0725% calcium, about 1.2 to 1.8% tin, more than about 0.001% silver, and about 0.0005 to 0.04% bismuth,
    Lead alloy for battery grid, with the balance being lead.
    [2" claim-type="Currently amended] 2. The lead alloy for battery grid according to claim 1, wherein the calcium content is about 0.055 to 0.07% by weight.
    [3" claim-type="Currently amended] 3. The lead alloy of claim 2, wherein the calcium content is about 0.06 to 0.07% by weight.
    [4" claim-type="Currently amended] 2. The lead alloy of claim 1, wherein the tin content is about 1.2 to 1.65% by weight.
    [5" claim-type="Currently amended] 2. The lead alloy of claim 1, wherein the ratio of calcium to tin is greater than about 12 to 1.
    [6" claim-type="Currently amended] 2. The lead alloy of claim 1, wherein the silver content is about 0.001 to 0.015% by weight.
    [7" claim-type="Currently amended] 7. The lead alloy of claim 6, wherein the silver content is about 0.001 to 0.01% by weight.
    [8" claim-type="Currently amended] 8. The lead alloy of claim 7, wherein the silver content is about 0.001 to 0.005% by weight.
    [9" claim-type="Currently amended] 9. The lead alloy of claim 8, wherein the content of bismuth is about 0.0005 to 0.0275% by weight.
    [10" claim-type="Currently amended] 10. The lead alloy of claim 9, wherein the bismuth content is about 0.0005 to 0.0225% by weight.
    [11" claim-type="Currently amended] 11. The lead alloy of claim 10, wherein the content of bismuth is about 0.001 to 0.0190% by weight.
    [12" claim-type="Currently amended] 12. The lead alloy of claim 11, wherein the bismuth content is greater than about 0.0115% by weight.
    [13" claim-type="Currently amended] By weight, including about 0.05-0.07% calcium, about 1.2-1.5% tin, more than about 0.001% silver, and more than about 0.0115% bismuth,
    Alloy for battery grid, with the balance being lead.
    [14" claim-type="Currently amended] The alloy of claim 13, wherein the content of silver is about 0.001 to 0.015% by weight.
    [15" claim-type="Currently amended] 15. The alloy for battery grid of claim 14, wherein the content of silver is about 0.001 to 0.01% by weight.
    [16" claim-type="Currently amended] 16. The alloy for battery grid of claim 15, wherein the content of silver is about 0.001 to 0.005% by weight.
    [17" claim-type="Currently amended] 15. The alloy of claim 14, wherein the bismuth content is less than about 0.0275% by weight.
    [18" claim-type="Currently amended] 18. The alloy of claim 17, wherein the bismuth content is less than about 0.0225% by weight.
    [19" claim-type="Currently amended] 19. The alloy of claim 18, wherein the bismuth content is less than about 0.019% by weight.
    [20" claim-type="Currently amended] 20. The alloy of claim 19, wherein the content of bismuth is about 0.015 to 0.0165 by weight.
    [21" claim-type="Currently amended] As a method of manufacturing an alloy for a battery grid,
    The method includes alloying lead with calcium, tin, silver and bismuth,
    The alloy comprises, by weight percent, about 0.05 to 0.0725% calcium, about 1.2 to 1.8% tin, more than about 0.001% silver, and less than about 0.0005 to 0.0275% bismuth, the balance being lead Method for producing an alloy for a battery grid, characterized in that made.
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    同族专利:
    公开号 | 公开日
    US20040033157A1|2004-02-19|
    JP2004165149A|2004-06-10|
    EP1403946A3|2004-04-21|
    BR0303411A|2004-09-08|
    EP1403946A2|2004-03-31|
    US20040187986A1|2004-09-30|
    MXPA03007211A|2005-04-19|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2002-08-13|Priority to US10/217,949
    2002-08-13|Priority to US10/217,949
    2003-08-13|Application filed by 존슨 컨트롤스 테크놀러지 컴퍼니
    2004-02-19|Publication of KR20040015697A
    优先权:
    申请号 | 申请日 | 专利标题
    US10/217,949|US20040033157A1|2002-08-13|2002-08-13|Alloy for battery grids|
    US10/217,949|2002-08-13|
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