EP0051897B1 - Utilisation d'un alliage plomb-antimoine - Google Patents

Utilisation d'un alliage plomb-antimoine Download PDF

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Publication number
EP0051897B1
EP0051897B1 EP81201241A EP81201241A EP0051897B1 EP 0051897 B1 EP0051897 B1 EP 0051897B1 EP 81201241 A EP81201241 A EP 81201241A EP 81201241 A EP81201241 A EP 81201241A EP 0051897 B1 EP0051897 B1 EP 0051897B1
Authority
EP
European Patent Office
Prior art keywords
weight
lead
antimony
production
tellurium
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.)
Expired
Application number
EP81201241A
Other languages
German (de)
English (en)
Other versions
EP0051897A1 (fr
Inventor
Fehmi Dr. Dipl.-Ing. Nilmen
Hartmut Dr. Dipl.-Phys. Sandig
Ulrich Dr. Dipl.-Ing. Heubner
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.)
GEA Group AG
Original Assignee
Metallgesellschaft AG
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 Metallgesellschaft AG filed Critical Metallgesellschaft AG
Priority to AT81201241T priority Critical patent/ATE8915T1/de
Publication of EP0051897A1 publication Critical patent/EP0051897A1/fr
Application granted granted Critical
Publication of EP0051897B1 publication Critical patent/EP0051897B1/fr
Expired 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
    • C22C11/00—Alloys based on lead

Definitions

  • the invention relates to the use of a lead-antimony alloy of the composition 0.1 to 3.5 wt .-% antimony, 0.01 to 0.1 wt .-% tellurium, the rest lead, with manufacturing-related impurities for the production of grids Electrodes as lead accumulators.
  • Lead-antimony alloys are used for the grids of most lead accumulators, with the trend towards alloys with a low antimony content (DE-PS 2151733, DE-AS 2 439 729).
  • Antimony influences the electrochemical behavior of the lead accumulator by releasing it when the positive grids corrode and depositing it on the surface of the negative electrode. This lowers the hydrogen overvoltage and increases self-discharge and water consumption.
  • the antimony in the positive grids improves the properties of the positive electrodes when the lead accumulator is cyclically stressed. It prevents the positive mass from descending from the grids so that an accelerated decrease in capacity is avoided.
  • the aim is to reduce the antimony content.
  • Arsenic contents of 0.02 to 0.5% by weight reduce metal losses due to oxidation during casting and at the same time increase the hardness and creep resistance of the antimony-lead alloy.
  • Copper additions of 0.01 to 0.1% by weight reduce the metal losses due to oxidation during casting and support the grain-refining effect when 0.002 to 0.012% by weight of sulfur is also added to the alloy.
  • additives of 0.005 to 0.1% by weight of selenium are suitable as foundry aids for grain refinement.
  • a satisfactory grain refinement of the cast structure is also possible with the alternative sulfur additives.
  • the grids of electrodes for lead accumulators made from the above-described low-antimony lead alloys have self-discharge security, freedom from maintenance and cycle stability.
  • the antimony content of the lead alloy is reduced, the more precisely the contents of other alloy additives such as copper, arsenic, sulfur, selenium, etc. have to be adjusted. Furthermore, a thermal improvement of the molds designed for processing the antimony-rich lead alloys is required. If the low-antimony lead alloys for grain refinement contain additives of 0.005 to 0.1% selenium, they can be cast directly into grids without hot cracks or processed over rolled strips to form expanded metal grids for the electrodes of lead accumulators (DE-OS 2 907 227). These manufacturing processes result in an increase in energy density due to the weight reduction of the individual grid.
  • a major disadvantage of the low-antimony lead alloys can be seen in the fact that they suffer rapid recrystallization combined with discontinuous structural segregation in the event of strong plastic deformation, as a result of which their good mechanical and corrosion-chemical properties are lost. A restoration of these positive properties is therefore only possible by curing the deformed material.
  • the problem here is that the deformed material tends to secondary recrystallization to a great extent during homogenization, so that after homogenization there is a very coarse-grained and therefore highly susceptible to corrosion.
  • this problem is solved by using the lead-antimony alloy mentioned at the beginning with contents of 0.1 to 3.5% by weight of antimony, 0.01 to 0.1% by weight of tellurium, the rest of lead manufacturing-related impurities which may contain one or more of the additives 0.001 to 0.008% by weight of sulfur, 0.005 to 0.035% by weight of selenium, 0.005 to 0.5% by weight of tin, 0.005 to 0.1% by weight of silver, 0 , 01 to 0.4 wt .-% arsenic, 0.01 to 0.05 wt .-% bismuth contains, for the production of a high structural stability of rolled and heat-treated sheets and strips for the production of grids of the electrodes of lead accumulators by machining .
  • Sulfur or selenium serve to improve the quality of the raw material for casting.
  • these components can be dispensed with, since the structure-stabilizing effect of the tellurium is not impaired in any way.
  • the ingredients tin, silver and bismuth bring about an improvement
  • the cycle stability of the batteries and arsenic produced helps to accelerate the increase in strength after homogenization.
  • a casting block of a low-antimony lead alloy (% by weight) of the composition Pb, 0.96 Sb and 0.072 Te was rolled at 1 mm and hardened. As a result, a very fine-grained (0.05 to 0.10 mm diameter) homogeneously segregated structure has been established.
  • the macro hardness of this material reached values of up to 10 kp / mm 2 a few hours after the heat treatment and rose steadily in the further course of aging, so that a macro hardness of 13 to 14 kp / mm 2 was reached after only one week.
  • the expanded metal grids produced from the pre-treated tape were assembled into starter batteries after pasting with negative electrodes and then tested by battery technology with the result that there was only minimal self-discharge, more than 300 charge / discharge cycles were carried out and practically maintenance-free.
  • the cells were expanded and the electrodes lichtmikrosko p ic investigated. In doing so, a surface corrosion removal on the positive mass carriers, which was hardly measurable by light microscopy, was found.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Catalysts (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • Cold Cathode And The Manufacture (AREA)
  • Electrolytic Production Of Metals (AREA)

Claims (1)

  1. Utilisation d'un alliage plomb-antimoine ayant des teneurs de 0,1 à 3,5% en poids en antimoine, de 0,01 à 0,1% en poids en tellure, le reste étant du plomb, et comportant des impuretés dues à la fabrication, ledit alliage contenant éventuellement un ou plusieurs des ajouts de 0,001 à 0,008% en poids de soufre, de 0,005 à 0,035% en poids de sélénium, de 0,005 à 0,5% en poids d'étain, de 0,005 à 0,1% en poids d'argent, de 0,01 à 0,4% en poids d'arsenic, de 0,01 à 0,05% en poids de bismuth, pour la fabrication de tôles et de bandes laminées et traitées thermiquement, ayant une stabilité de structure élevée, destinées à la production de grilles d'électrodes d'accumulateurs au plomb par une mise en forme par usinage.
EP81201241A 1980-11-07 1981-11-02 Utilisation d'un alliage plomb-antimoine Expired EP0051897B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81201241T ATE8915T1 (de) 1980-11-07 1981-11-02 Verwendung einer blei-antimon-legierung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19803042011 DE3042011A1 (de) 1980-11-07 1980-11-07 Blei-antimon-knetlegierung
DE3042011 1980-11-07

Publications (2)

Publication Number Publication Date
EP0051897A1 EP0051897A1 (fr) 1982-05-19
EP0051897B1 true EP0051897B1 (fr) 1984-08-08

Family

ID=6116201

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81201241A Expired EP0051897B1 (fr) 1980-11-07 1981-11-02 Utilisation d'un alliage plomb-antimoine

Country Status (5)

Country Link
EP (1) EP0051897B1 (fr)
AT (1) ATE8915T1 (fr)
DE (2) DE3042011A1 (fr)
ES (1) ES8303540A1 (fr)
YU (1) YU263481A (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8500768D0 (en) * 1985-01-11 1985-02-13 London & Scandinavain Metallur Grain refining metals
US4629516A (en) * 1985-04-01 1986-12-16 Asarco Incorporated Process for strengthening lead-antimony alloys
US4734256A (en) * 1986-04-21 1988-03-29 Allied-Signal Inc. Wetting of low melting temperature solders by surface active additions
US7923155B2 (en) * 2007-03-20 2011-04-12 Northstar Battery Company, Llc Lead-tin-silver-bismuth containing alloy for positive grid of lead acid batteries
CA2929792A1 (fr) 2013-11-06 2015-05-14 Northstar Battery Company Llc Grille positive resistante a la corrosion pour batteries au plomb

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB814445A (en) * 1958-02-21 1959-06-03 British Lead Mills Ltd Improved lead alloy
GB411524A (en) * 1932-12-08 1934-06-08 William Singleton Improvements in or relating to the manufacture of lead storage batteries
US4109358A (en) * 1971-04-21 1978-08-29 Esb Ray-O-Vac Management Corporation Method for making storage battery grid from lead-tin-zinc alloy
BE789345A (fr) * 1971-10-18 1973-01-15 Varta Batterie Alliage de plomb, pauvre en antimoine, pour grilles d'accumulateurs
DE2241369C3 (de) * 1972-08-23 1984-03-15 Accumulatorenfabriken Wilhelm Hagen Ag Soest-Kassel-Berlin, 4770 Soest Elektrode für Bleiakkumulatoren
FR2278779A1 (fr) * 1974-03-21 1976-02-13 Fulmen Alliage de plomb pour grille de plaque d'accumulateurs
DE2500228C2 (de) * 1975-01-04 1984-07-05 Accumulatorenfabriken Wilhelm Hagen Ag Soest-Kassel-Berlin, 4770 Soest Antimonfreie Bleilegierung für die Herstellung von Gitterplatten für Bleiakkumulatoren
DE2621398C2 (de) * 1976-05-14 1985-05-02 HAGEN Batterie AG, 4770 Soest Blei-Antimon-Legierung für die Herstellung von Gitterplatten von Bleiakkumulatoren
DE2907227C2 (de) * 1979-02-23 1985-05-09 Metallgesellschaft Ag, 6000 Frankfurt Verwendung einer Bleilegierung

Also Published As

Publication number Publication date
DE3165437D1 (en) 1984-09-13
DE3042011A1 (de) 1982-06-03
YU263481A (en) 1984-02-29
ES506951A0 (es) 1983-02-01
ES8303540A1 (es) 1983-02-01
ATE8915T1 (de) 1984-08-15
EP0051897A1 (fr) 1982-05-19

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