US20040033157A1 - Alloy for battery grids - Google Patents

Alloy for battery grids Download PDF

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Publication number
US20040033157A1
US20040033157A1 US10/217,949 US21794902A US2004033157A1 US 20040033157 A1 US20040033157 A1 US 20040033157A1 US 21794902 A US21794902 A US 21794902A US 2004033157 A1 US2004033157 A1 US 2004033157A1
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United States
Prior art keywords
percent
weight
alloy
amount
bismuth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
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US10/217,949
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English (en)
Inventor
Charles Schaeffer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Johnson Controls Technology Co
Original Assignee
Johnson Controls Technology Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Johnson Controls Technology Co filed Critical Johnson Controls Technology Co
Priority to US10/217,949 priority Critical patent/US20040033157A1/en
Assigned to JOHNSON CONTROLS TECHNOLOGY COMPANY reassignment JOHNSON CONTROLS TECHNOLOGY COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SCHAEFFER, CHARLES J.
Priority to JP2003292810A priority patent/JP2004165149A/ja
Priority to KR1020030056152A priority patent/KR20040015697A/ko
Priority to EP03400043A priority patent/EP1403946A3/en
Priority to MXPA03007211A priority patent/MXPA03007211A/es
Priority to BR0303411-9A priority patent/BR0303411A/pt
Publication of US20040033157A1 publication Critical patent/US20040033157A1/en
Priority to US10/819,485 priority patent/US20040187986A1/en
Abandoned legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/68—Selection of materials for use in lead-acid accumulators
    • H01M4/685—Lead alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C11/00—Alloys based on lead
    • C22C11/06—Alloys based on lead with tin as the next major constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • 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

Definitions

  • the present invention relates generally to the field of lead alloys.
  • the present invention relates more specifically to a lead alloy for a battery grid having calcium, tin and bismuth.
  • Batteries typically include cell elements having positive and negative grids or plates and separators between the grids.
  • the grids are typically made of a lead alloy that includes various alloying elements intended to improve performance, life and/or manufacturability of the grids and battery.
  • a lead alloy for use in a battery grid that has an acceptable corrosion rate and life. It would also be advantageous to provide a lead alloy for a battery grid that includes bismuth. It would also be advantageous to provide a lead alloy for a battery grid that has a relatively high hardness stability (i.e. resistance to averaging). It would be desirable to provide for an alloy for a battery grid having one or more of these advantageous features.
  • FIG. 1 shows a battery-grid according to an exemplary embodiment.
  • FIG. 2A shows a bar graph of the hardness stability integral of an alloy for a battery grid according to an exemplary embodiment.
  • FIG. 2B shows a line graph of the hardness stability integral versus the amount of bismuth for of an alloy for a battery grid according to an exemplary embodiment.
  • FIG. 3A shows a photograph of an alloy for a battery grid having bands of untransformed material according to an exemplary embodiment.
  • FIG. 3B shows a photograph of the alloy of FIG. 3A having bands of untransformed material according to an exemplary embodiment.
  • the present invention relates to a lead alloy for a grid for a battery.
  • the alloy includes calcium in an amount of about 0.05 percent by weight to about 0.0725 percent by weight.
  • the alloy also includes tin in an amount of about 1.2 percent by weight to about 1.8 percent by weight.
  • the alloy also includes silver in an amount of greater than about 0.001 percent by weight.
  • the alloy also includes bismuth in an amount of about 0.0005 percent by weight to less than about 0.04 percent by weight.
  • the balance of the alloy comprises lead.
  • the present invention also relates to an alloy for a grid for a battery.
  • the alloy includes calcium in an amount of less than about 0.05 percent by weight to about 0.07 percent by weight.
  • the alloy also includes tin in an amount of about 1.2 percent by weight to about 1.5 percent by weight.
  • the alloy also includes silver in an amount of greater than about 0.001 percent by weight.
  • the alloy also includes bismuth in an amount of greater than about 0.0115 percent by weight.
  • the balance of the alloy comprises lead.
  • the present invention also relates to a method of producing an alloy for use in a battery grid.
  • the method includes alloying lead with calcium, tin, silver and bismuth.
  • the alloy includes calcium in an amount less than about 0.05 percent by weight to about 0.0725 percent by weight.
  • the alloy also includes tin in an amount of about 1.2 percent by weight to about 1.8 percent by weight.
  • the alloy also includes silver in an amount of greater than about 0.001 percent by weight.
  • the alloy also includes bismuth in an amount of 0.005 percent by weight to less than about 0.0275 percent by weight.
  • the balance of the alloy includes lead.
  • a battery plate or grid 10 is shown in FIG. 1.
  • the grid is a “stamped” or punched grid made from a wrought alloy according to a preferred embodiment, and may be made from a cast alloy according to an alternative embodiment.
  • the grid is a “positive” grid for a lead-acid battery according to a preferred embodiment, and may be a “negative” grid according to an alternative embodiment.
  • Grid 10 includes an electric current collection lug 12 .
  • vertical wires 14 extend from lug 12 .
  • Generally horizontal wires 16 intersect vertical wires 14 .
  • the grid includes a lead alloy having calcium, tin and bismuth according to a preferred embodiment.
  • the lead alloy may include silver according to an alternative embodiment.
  • the amount of calcium in the alloy is selected to provide suitable hardness of the alloy, which can aid in manufacturability of the alloy according to a preferred embodiment. Such suitable hardness of the alloy may eliminate the need for heat treatment of the alloy. The amount of calcium in the alloy should not be so great as to cause an unacceptable increase in corrosion rate or reduction in hardness stability.
  • Aluminum may be included in the alloy (or in the melt pot of the alloy) to reduce the loss of calcium according to a preferred embodiment.
  • the alloy includes calcium in an amount greater than about 0.05 percent by weight according to a preferred embodiment.
  • the alloy includes calcium in an amount of about 0.05 percent by weight to about 0.08 percent by weight according to an alternative embodiment.
  • the alloy includes calcium in an amount of 0.055 percent by weight to about 0.075 percent by weight according to another alternative embodiment.
  • the alloy includes calcium in an amount of about 0.05 percent by weight to about 0.07 percent by weight according to an alternative embodiment.
  • the alloy includes calcium in an amount of 0.055 percent by weight to about 0.07 percent by weight according to an alternative embodiment.
  • the alloy includes calcium in an amount of 0.06 percent by weight to about 0.07 percent by weight according to an alternative embodiment.
  • the amount of tin in the alloy is selected to reduce corrosion according to a preferred embodiment. Without intending to be limited to any particular theory, it is believed that tin will react with calcium to form Sn 3 Ca (which provides corrosion resistance), and that the tin will inhibit the reaction of lead with calcium, thereby reducing the formation of discontinuous Pb 3 Ca precipitate (which may promote grid growth).
  • the alloy includes tin in an amount of greater than about 1.2 percent by weight according to a preferred embodiment.
  • the alloy includes tin in an amount of about 1.2 percent by weight to about 1.65 percent by weight according to an alternative embodiment.
  • the alloy includes tin in an amount of about 1.2 percent by weight to about 1.5 percent by weight according to an alternative embodiment.
  • the ratio of tin to calcium is selected to minimize the formation of Pb 3 Ca precipitate according to a preferred embodiment.
  • the ratio of tin to calcium is greater than about 10 to 1 according to a preferred embodiment.
  • the ratio of tin to calcium is greater than about 12 to 1 according to other preferred or alternative embodiments.
  • the ratio of tin to calcium is greater than about 20 to 1 according to other preferred or alternative embodiments.
  • the alloy has a calcium content of about 0.07 percent by weight, it is preferred that the tin content exceed about 0.84 percent by weight.
  • Increasing the ratio of tin to lead may reduce “coarsening” of the precipitates in the grid by suppressing formation of precipitated Pb 3 Ca, which in turn decreases grid growth and increases the life of the grids.
  • the amount of silver in the alloy is selected to increase mechanical strength, including creep strength of grain boundaries according to a preferred embodiment.
  • the amount of silver in the alloy ⁇ is also selected to increase the hardening rate of the alloy according to a preferred embodiment.
  • silver may be included in “trace” amounts or as an impurity that is present in “secondary” or recycled lead.
  • the alloy includes silver in an amount of about 0.0005 percent by weight to about 0.02 percent by weight according to a preferred embodiment.
  • the alloy includes silver in an amount of about 0.001 percent by weight to about 0.015 percent by weight according to an alternative embodiment.
  • the alloy includes silver in an amount of about 0.001 percent by weight to about 0.01 percent by weight according to an alternative embodiment.
  • the alloy includes silver in an amount of about 0.001 percent by weight to about 0.005 percent by weight according to an alternative embodiment.
  • the amount of bismuth in the alloy is selected to provide an acceptable hardness-stability (i.e. “microhardness”) of the alloy.
  • the alloy includes bismuth in an amount of less than about 0.04 percent by weight according to a preferred embodiment.
  • the alloy includes bismuth in an amount of about 0.0005 percent by weight to about 0.0275 percent by weight according to an alternative embodiment.
  • the alloy includes bismuth in an amount of about 0.0005 percent by weight to about 0.025 percent by weight according to an alternative embodiment.
  • the alloy includes bismuth in an amount of about 0.001 percent by weight to about 0.0225 percent by weight according to an alternative embodiment.
  • the alloy includes bismuth in an amount of about 0.001 percent by weight to about 0.0190 percent by weight according to an alternative embodiment.
  • the alloy includes bismuth in an amount of about 0.0115 percent by weight to about 0.0165 percent by weight according to an alternative embodiment.
  • the alloy includes bismuth in an amount of about 0.0150 percent by weight according to a particularly preferred embodiment.
  • the alloy may include relatively low amounts of other materials according to any preferred or alternative embodiments.
  • the alloy may include background “impurities” or trace materials that are present in a commercially recycled lead stream. Impurities in the alloy in the following amounts may be acceptable: (1) zinc in an amount of less than about 0.005 percent by weight according to an alternative embodiment, zinc in an amount of less than about 0.0025 percent by weight according to a preferred embodiment; (2) antimony in an amount of less than about 0.005 percent by weight according to an alternative embodiment, antimony in an amount of less than about 0.0025 percent by weight according to a preferred embodiment; (3) arsenic in an amount of less than about 0.0025 percent by weight according to a preferred embodiment; (4) copper in an amount of less than about 0.005 percent by weight according to an alternative embodiment, cooper in an amount of less than about 0.0025 percent by weight according to a preferred embodiment.
  • the alloy includes calcium in an amount of about 0.05 percent by weight and about 0.07 percent by weight, tin in an amount of about 1.2 percent by weight and about 1.5 percent by weight, and bismuth in an amount of 0.0005 to 0.0275 percent by weight according to an exemplary embodiment, with the balance being lead.
  • Silver may optionally be included in the alloy in an amount less than about 0.015 percent by weight according to an alternative embodiment.
  • the balance may also include additional elements that are present in recycled lead (e.g. bismuth, arsenic, copper, silver, tellurium, etc.) in limited amounts (e.g. less than approximately 0.0025 percent by weight for each impurity).
  • the alloy includes calcium in the amount of about 0.065 percent by weight, tin in an amount of about 1.35 percent by weight, silver in an about of about 0.0035 percent by weight, and bismuth in an amount of about 0.0005 percent by weight to about 0.0275 percent by weight, with the balance being lead and other additional elements that are present in recycled lead, according to a preferred embodiment.
  • the alloy may include calcium in the amount of about 0.0652 percent by weight, tin in an amount of about 1.35 percent by weight, silver in an about of about 0.0036 percent by weight, and bismuth in an amount of about 0.0005 percent by weight to about 0.0236 percent by weight, with the balance being lead and other additional elements that are present in recycled lead, according to a preferred embodiment.
  • the percent by weight of the various alloy elements may vary according to alternative embodiments.
  • silver may be present in an amount between approximately 0.005 and 0.015 percent by weight.
  • tin may be present in an amount between approximately 1.2 percent by weight and about 1.8 percent by weight.
  • Alloys A, B, C, D, E and F were prepared having calcium, tin, silver and bismuth (the balance being lead) in the amounts listed in TABLE 1 through TABLE 6.
  • Alloys B1 and B2 are collectively referred to as Alloy B.
  • the average amount of silver in Alloy B was 0.0021 percent by weight.
  • the average amount of bismuth in Alloy B was 0.005 percent by weight.
  • Alloys E1, E2, E3 and E4 are collectively referred to as Alloy E.
  • the average amount of silver in Alloy E was 0.0035 percent by weight.
  • the average amount of bismuth in Alloy E was 0.0202 percent by weight.
  • the alloys were cast as a slab and flattened (e.g. by a roller) to about 10 percent the original thickness of the slab.
  • Grids for batteries each having a thickness of about 42 one-thousands of an inch were formed from the slab and stamped in a grid pattern.
  • the grids were held at 85 degrees Celsius for 3 weeks, and then tested for hardness stability (i.e. diamond pyramid hardness or “DPH”) using a diamond pyramid indentor.
  • the load was 200 grams for 15 seconds for the hardness stability test.
  • the hardness stability integral for each of Alloy A, B, C, D, E and F is shown in TABLE 7.
  • FIG. 2A shows that grids having bismuth in the amount of 0.0005 percent to 0.0236 percent by weight had a relatively acceptable hardness stability.
  • FIG. 2B shows the data of TABLE 7 fit to a curve according to a preferred embodiment.
  • Alloy E2 was cast as a slab and flattened to about 10 percent the original thickness of the slab. Grids for batteries each having a thickness of about 42 one-thousandths of an inch were formed from the slab and stamped in a grid pattern. The grids were held at 85 degrees Celsius for 5 weeks.
  • FIG. 3A shows 75 ⁇ magnification of a section of the grid.
  • FIG. 3B shows a detailed view of the section of the grid of FIG. 3A.
  • FIG. 3B shows bands of untransformed material having a relatively high hardness (shown in rectangles 22 a and 22 b ) and some bands of recrystalized material (shown in ovals 24 a and 24 b ).
  • any means-plus-function clause is intended to cover the structures described herein as performing the recited function and not only structural equivalents but also equivalent structures.
  • Other substitutions, modifications, changes and omissions may be made in the design, operating conditions and arrangement of the preferred and other exemplary embodiments without departing from the spirit of the present inventions as expressed in the appended claims.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
US10/217,949 2002-08-13 2002-08-13 Alloy for battery grids Abandoned US20040033157A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US10/217,949 US20040033157A1 (en) 2002-08-13 2002-08-13 Alloy for battery grids
JP2003292810A JP2004165149A (ja) 2002-08-13 2003-08-13 バッテリーのグリッド用の合金
KR1020030056152A KR20040015697A (ko) 2002-08-13 2003-08-13 배터리 그리드용 합금
EP03400043A EP1403946A3 (en) 2002-08-13 2003-08-13 Alloy for battery grids
MXPA03007211A MXPA03007211A (es) 2002-08-13 2003-08-13 Aleacion para rejilla de bateria.
BR0303411-9A BR0303411A (pt) 2002-08-13 2003-08-13 Liga para grades de bateria
US10/819,485 US20040187986A1 (en) 2002-08-13 2004-04-07 Alloy for battery grids

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US10/217,949 US20040033157A1 (en) 2002-08-13 2002-08-13 Alloy for battery grids

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US10/819,485 Continuation US20040187986A1 (en) 2002-08-13 2004-04-07 Alloy for battery grids

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US10/819,485 Abandoned US20040187986A1 (en) 2002-08-13 2004-04-07 Alloy for battery grids

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EP (1) EP1403946A3 (es)
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US8252464B2 (en) 1999-07-09 2012-08-28 Johnson Controls Technology Company Method of making a battery grid
US8399135B2 (en) 2005-05-23 2013-03-19 Johnson Controls Technology Company Battery grid
US8586248B2 (en) 2010-04-14 2013-11-19 Johnson Controls Technology Company Battery, battery plate assembly, and method of assembly
US9130232B2 (en) 2010-03-03 2015-09-08 Johnson Controls Technology Company Battery grids and methods for manufacturing same
US9748578B2 (en) 2010-04-14 2017-08-29 Johnson Controls Technology Company Battery and battery plate assembly
US9985276B2 (en) 2013-11-06 2018-05-29 Northstar Battery Company, Llc Corrosion resistant positive grid for lead-acid batteries
US10147953B2 (en) 2012-09-28 2018-12-04 Exide Technologies Lead-acid battery positive plate and alloy therefore
US10170768B2 (en) 2013-10-08 2019-01-01 Johnson Controls Autobatterie Gmbh & Co. Kgaa Grid assembly for a plate-shaped battery electrode of an electrochemical accumulator battery
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US10418637B2 (en) 2013-10-23 2019-09-17 Johnson Controls Autobatterie Gmbh & Co. Kgaa Grid arrangement for plate-shaped battery electrode and accumulator
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US8252464B2 (en) 1999-07-09 2012-08-28 Johnson Controls Technology Company Method of making a battery grid
US8709664B2 (en) 1999-07-09 2014-04-29 Johnson Controls Technology Company Battery grid
US8980419B2 (en) 2005-05-23 2015-03-17 Johnson Controls Technology Company Battery grid
US8974972B2 (en) 2005-05-23 2015-03-10 Johnson Controls Technology Company Battery grid
US8399135B2 (en) 2005-05-23 2013-03-19 Johnson Controls Technology Company Battery grid
WO2008109429A3 (en) * 2007-03-02 2009-07-23 Johnson Controls Tech Co Negative grid for battery
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US20100101078A1 (en) * 2007-03-02 2010-04-29 Johnson Controls Technology Company Negative grid for battery
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WO2008109429A2 (en) * 2007-03-02 2008-09-12 Johnson Controls Technology Company Negative grid for battery
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US20040187986A1 (en) 2004-09-30
EP1403946A3 (en) 2004-04-21
KR20040015697A (ko) 2004-02-19

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