US3719530A - Electric batteries and alloys therefor - Google Patents

Electric batteries and alloys therefor Download PDF

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Publication number
US3719530A
US3719530A US00849284A US3719530DA US3719530A US 3719530 A US3719530 A US 3719530A US 00849284 A US00849284 A US 00849284A US 3719530D A US3719530D A US 3719530DA US 3719530 A US3719530 A US 3719530A
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percent
weight
battery
magnesium
thallium
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US00849284A
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English (en)
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J King
R Packer
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Magnesium Elektron Ltd
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Magnesium Elektron Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • 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 object of the invention is to provide magnesium base alloys having improved electrochemical properties when used as anodes in various electrical battery systems.
  • the main types of battery systems in which magnesium based alloys are used are the magnesium-sea-water cell, normally using silver chloride as the cathode, and the magnesium Leclanche type dry cell, using manganese dioxide or other materials as a depolarizer.
  • the magnesium based alloy currently most widely used for magnesium-seawater batteries is AZ61 containing about 6 percent aluminum, 1 percent zinc, and 0.2 percent manganese. This alloy was found to give the best compromise of properties required for the successful operation of a magnesium-seawater cell, namely high electrode potential when operating at high discharge rates, and formation of a very fine granular reaction product which is easily flushed out of the cell without causing any clogging or blockage of the cell. Solution treatment for several hours at 400C is essential to produce a uniform single phase structure giving the required properties in this alloy.
  • Typical cell voltages for this alloy in the form of thin scratch brushed sheets when operating in a magnesium-seawater-silver chloride cell with flowing electrolyte, with flowing seawater of a salinity 21, at 20-25C, and an electrode separation of 0.020 0.023 in. at a current density of about 2 amperes per square inch are of the order of 1.0 volts.
  • alloys which give higher electrode potentials under discharge without any significant deterioration in the form of the reaction product.
  • Such alloys may contain typically 6 percent aluminum, 1 percent zinc, 0.2 percent manganese with up to 10 percent of lead, or 1 to 10 percent of lead, and 0.5 to 5 percent of mercury and have been described in U.S. Pat. No. 3,288,649.
  • One typical alloy containing about 7 percent aluminum, 1 percent zinc, 0.2 percent manganese and 5 percent lead, was rolled to thin sheet then solution treated to produce a uniform single phase structure, and the surface was scratch brushed.
  • this alloy When operating in a magnesium-seawater-silver chloride cell with flowing electrolyte and an electrode separation of 0.020 0.023 in. at a current density of about 2 amperes per square inch, this alloy gave average cell voltages of the order of 1.15 volts.
  • alloys can be made which slow a very high electrode potential under discharge, and which do not form a thick reaction product likely to block the cell. Alloys containing thallium can be extruded or rolled to thin sheet without difficulty.
  • Table I shows typical electrode potential values and details of the reaction product as determined from tests in which the magnesium alloys were made the anodes in an electrical circuitso as to simulate the condition of discharge in a high energy density seawater cell.
  • the alloys were in the form of round cast bars which had been solution treated to produce a uniform single phase structure
  • the potential figures are volts with respect to nonpolarized AgCl and free of resistance drop across the cell.
  • the electrode potential of alloys containing thallium can be increased by raising the thallium content up to 15 percent, beyond which no further benefit is obtained.
  • FIG. 1 shows the variation in maximum and average potential during a 5 minute discharge and also hydrogen evolution with thallium content.
  • the optimum alloys are those giving the least sludging during discharge, which also corresponds to the least hydrogen evolution. These are the ones containing between 4 and 12 percent thallium, and particularly between 5 and percent, e.g. 6 to 9 percent.
  • reaction product For magnesium dry cells, and for some low drain seawater batteries, the form of the reaction product is not as critical as for seawater batteries, and consequently lower concentrations of thallium, which still give increased electrode potential, but thicker more adherent reaction products during operation, could be used.
  • Table 11 gives typical voltages and sludging behavior for various alloys obtained in a single cell test rig with flowing artificial seawater.
  • Cells 6 X 2" in dimensions were assembled by sandwiching a magnesium alloy sheet and a silver chloride sheet between silver conductors. The electrolyte gap between the magnesium and the silver chloride was maintained by glass beads embedded in the silver chloride. A separation of 0.024 ins. 35
  • the water activated battery may have a cathode chloride plate associated with silver foil or other conducting material and with an anode of the magnesium alloy in the form of thin rolled sheet of 5 to 25 (e.g. 10 to 20) thousandths of an inch thickness spaced (e.g. 20 100 thousandths inch) from the chloride.
  • the heat treatment of the alloys may be effected at temperatures ranging from 350 to 450C for 4 to 60 hours, e.g. 380 420C for 8 24 hours for alloys containing up to 12 percent thallium.
  • the alloy of the present invention contains at least 80 percent magnesium.
  • the invention may also be applied to an air battery an example of which is described in the specification of U.S. Pat. No. 1 140635, by making the anode in an alloy as above described.
  • the anode may be rolled or extruded alloy e.g. about 0.05 to 0.15 inch thickness.
  • a battery as claimed in claim 2 wherein the foil is from 10 to 20 thousandths inch thick.
  • a battery as claimed in claim 5 wherein the anode is the magnesium alloy in extruded form.
  • a magnesium base alloy consisting of:
  • Thallium 6 to 8 percent by weight Aluminum 4 to 6 percent by weight Mercury 0 to 5 percent by weight Lead 0 to 5 percent by weight Zinc 0 to 3 percent by weight Manganese 0 to 1 percent by weight Calcium 0 to 1 percent by weight Cadmium O to 1 percent by weight Thallium 6 to 8 percent by weight Aluminum 4 to 6 percent by weight Mercury 0 to 5 percent by weight Lead 0 to 5 percent by weight Zinc 0 to 3 percent by weight Manganese 0 to 1 percent by weight Calcium 0 to 1 percent by weight Cadmium 0 to 1 percent by weight Magnesium at least percent by weight and at least 0.5 percent total by weight of at least one of lead and mercury.

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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)
  • Battery Electrode And Active Subsutance (AREA)
  • Hybrid Cells (AREA)
US00849284A 1968-08-09 1969-08-06 Electric batteries and alloys therefor Expired - Lifetime US3719530A (en)

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GB3808768 1968-08-09

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US3719530A true US3719530A (en) 1973-03-06

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US (1) US3719530A (enrdf_load_stackoverflow)
CA (1) CA932389A (enrdf_load_stackoverflow)
DE (1) DE1939794C3 (enrdf_load_stackoverflow)
FR (1) FR2100573B1 (enrdf_load_stackoverflow)
GB (1) GB1251223A (enrdf_load_stackoverflow)
NO (1) NO129315B (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1317781C (zh) * 2002-08-06 2007-05-23 李华伦 镁干电池
CN103236540A (zh) * 2013-05-17 2013-08-07 重庆大学 一种镁电池用的正极材料和其制备方法及镁电池

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19638764A1 (de) * 1996-09-21 1998-03-26 Daimler Benz Ag Magnesiumwerkstoff und dessen Verwendung
RU2244987C2 (ru) * 2003-02-28 2005-01-20 ОАО "Аккумуляторная компания "Ригель" Анод водоактивируемого источника тока
FR3118995B1 (fr) 2021-01-21 2023-04-28 Psa Automobiles Sa Procede de securisation d’une fonction d’apprentissage d’un modele d’actionneurs de moteur thermique

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US303611A (en) * 1884-08-19 Paper box
US2233953A (en) * 1940-03-30 1941-03-04 Dow Chemical Co Magnesium base alloy
US2270195A (en) * 1940-12-23 1942-01-13 Dow Chemical Co Magnesium base alloy
US2286869A (en) * 1940-12-23 1942-06-16 Dow Chemical Co Magnesium base alloy
US2715653A (en) * 1952-02-27 1955-08-16 Dow Chemical Co Primary cell
US3288649A (en) * 1963-07-23 1966-11-29 Gen Electric Water-activated battery
US3432350A (en) * 1967-06-29 1969-03-11 Us Navy Sea water battery
US3615371A (en) * 1967-04-08 1971-10-26 Furukawa Electric Co Ltd Aluminum alloy for electric conductor

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US303611A (en) * 1884-08-19 Paper box
US2233953A (en) * 1940-03-30 1941-03-04 Dow Chemical Co Magnesium base alloy
US2270195A (en) * 1940-12-23 1942-01-13 Dow Chemical Co Magnesium base alloy
US2286869A (en) * 1940-12-23 1942-06-16 Dow Chemical Co Magnesium base alloy
US2715653A (en) * 1952-02-27 1955-08-16 Dow Chemical Co Primary cell
US3288649A (en) * 1963-07-23 1966-11-29 Gen Electric Water-activated battery
US3615371A (en) * 1967-04-08 1971-10-26 Furukawa Electric Co Ltd Aluminum alloy for electric conductor
US3432350A (en) * 1967-06-29 1969-03-11 Us Navy Sea water battery

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1317781C (zh) * 2002-08-06 2007-05-23 李华伦 镁干电池
CN103236540A (zh) * 2013-05-17 2013-08-07 重庆大学 一种镁电池用的正极材料和其制备方法及镁电池
CN103236540B (zh) * 2013-05-17 2015-06-10 重庆大学 一种镁电池用的正极材料和其制备方法及镁电池

Also Published As

Publication number Publication date
NO129315B (enrdf_load_stackoverflow) 1974-03-25
GB1251223A (enrdf_load_stackoverflow) 1971-10-27
DE1939794C3 (de) 1978-09-07
DE1939794B2 (de) 1978-01-12
FR2100573A1 (enrdf_load_stackoverflow) 1972-03-24
DE1939794A1 (de) 1972-05-25
FR2100573B1 (enrdf_load_stackoverflow) 1973-04-06
CA932389A (en) 1973-08-21

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