US2712564A - Primary cell - Google Patents

Primary cell Download PDF

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Publication number
US2712564A
US2712564A US322822A US32282252A US2712564A US 2712564 A US2712564 A US 2712564A US 322822 A US322822 A US 322822A US 32282252 A US32282252 A US 32282252A US 2712564 A US2712564 A US 2712564A
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US
United States
Prior art keywords
per cent
over
cell
cells
anode
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 - Lifetime
Application number
US322822A
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English (en)
Inventor
Ashford B Fry
Percy F George
Roy C Kirk
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.)
Dow Chemical Co
Original Assignee
Dow Chemical 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
Priority to BE524612D priority Critical patent/BE524612A/xx
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Priority to US322822A priority patent/US2712564A/en
Priority to GB28375/53A priority patent/GB735005A/en
Priority to FR1092622D priority patent/FR1092622A/fr
Priority to DED16427A priority patent/DE1090866B/de
Priority to JP2154153A priority patent/JPS353460B1/ja
Application granted granted Critical
Publication of US2712564A publication Critical patent/US2712564A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00Primary cells; Manufacture thereof
    • H01M6/04Cells with aqueous electrolyte
    • H01M6/06Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C23/00Alloys based on magnesium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C23/00Alloys based on magnesium
    • C22C23/04Alloys based on magnesium with zinc or cadmium as the next major constituent
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46Alloys based on magnesium or aluminium
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00Primary cells; Manufacture thereof

Definitions

  • United States Patent PRMARY CELL also contain zirconium in amount between 0.001 per cent and 0.1 per cent, the higher amounts of Zirconium are usable with the alloys containing little or no aluminum While the lower amounts of zirconium are usable in the 5 alloys containing the higher amounts of aluminum. If Ashford B. Fry, Percy F. George, and Roy C. Kirk, Middesired, beryllium in amount between 0.0005 and 0.005
  • a generally desirable anode alloy com- relates to an improved primary cell position is: l per cent of aluminum, 0.4 per cent of zinc, utilizing magnesium as the anode material, a cathode of 0.15 per cent of calcium, and 0.001 per cent of beryllium carbon depolarized with manganese dioxide, and an elecwith or Without 0.05 per cent of zirconium, the balance trolyte comprising a water-soluble bromide of an alkali being commercial magnesium containing not more than metal, alkaline earth metal or ammonium. 0.002 per cent of iron, not more than 0.001 per cent of A number of disadvantakes inure to primary cells of nickel, and not more than 0.05 per cent of manganese.
  • the larly when in the form of non-spillable or dry cells in anode is generally made in the form of a cup or the like which the anode is the container for the electrolyte and usually cylindrical in shape so as to form the container for cathode.
  • the other principal elements of the cell viz. the cathode.
  • the anode material is prea rest period after a use.
  • the delay may be as much as pared by melting a suitable quantity of magnesium of the 100 seconds or more depending upon the amount of use requisite purity preferably in a graphite or alloy steel and intervening rest as Well as the age of the cell.
  • An- 7 crucible so as to avoid excessively contaminating the other disadvantage is that the anode whether flat or in cup magnesium with other metallic elements especially iron, form as the container of the cell oftentimes cracks or copper, and nickel. The metallic elements to be alloyed leaks before the cell is exhausted.
  • magnesium in the anode a manganese dioxide depolarized After melting together the metallic elements of the cathode, and an aqueous electrolyte comprising an alkali alloy, it is cast into billet form, scalped to remove the metal, alkaline earth metal or ammonium bromide in casting skin, and then die-expressed (extruded) into rod which the foregoing disadvantages are eliminated, if not of a suitable diameter for impact extrusion into cell cans substantially overcome.
  • the molten alloy may be cast the invention Will appear as the description proceeds. into billets about 4 inches in diameter and 1 foot long,
  • the foregoing and related objects are attained in and, after scalping, the billet is extruded into rod 1% accordance with the invention by forming the anode of the inches in diameter.
  • Slugs for impact extrusion are made cell of an especially formulated magnesiurn-base alloy by cutting the extruded rod into pieces of suitable length. as herein set forth.
  • a suitable thickness for the wall of the can is 0.05 inch per cent of nickel, and not over 0.1 per cent of manganese. but other thicknesses may be used.
  • the alloy may also include up to about Examples of dry cells embodying the invention are 1.5 per cent of aluminum, the aluminum having the effect tabulated in the following table which also sets forth of giving the cell a higher capacity.
  • the anode alloy may performance data of the cells.
  • the electrolyte used consisted of an aqueous solution containing 250 grams per liter of magnesium bromide (MgBrz) and 0.2 gram per liter of sodium chromate (NHZCIO).
  • the cathode mix was composed of 91 parts of African manganese dioxide, 3 parts of barium chromate (BaCrOi) and 6 parts of acetylene black per 100 parts of the mix which was moistened with the foregoing electrolyte solution in the proportion of 300 cc.
  • the moistened cathode mix was die-expressed into cylindrical form with a diameter slightly smaller than The extruded cathode mix was cut into pieces about /2 inch shorter than the depth of the cans and a piece inserted into each can.
  • the weight of the cathode mix for the D-size cans was grams, for the F-size cans 102 grams. A graphite rod inch in diameter and longer than the can was then forced into the center of the cathode mix in each can to -T.
  • the electrode for the cathode mix The forcing of the electrode into the cathode mix caused it to become tightly packed against the lining of the can.
  • a cardboard washer was then inserted over the protruding end or the electrode and the remaining space in the top of the can above the washer was filled with molten sealing wax which formed'a seal for the top of the cell between the central electrode and the inside of the top of the can.
  • each of 3 cells was discharged through a resistance of 4 ohms for 5 minutes each day until the voltage of each cell (after delayed action) declined to 1.0 volt.
  • the average of the total number of minutes of discharge of each cell is entered in the table under Capacity in the column headed General purpose, minutes to 0 volt.
  • the seconds of time required for each D-size cell to attain 1 volt at the beginning of each of the 5 minute discharge period was recorded, and, in the table in the column headed General purpose under delayed action, there was entered the minimum, maximum, and
  • each of a group of 3 cells was discharged through the resistances for the first "/2 hour ofevery consecutive hour for 8 hours each day (total of 4 hours of discharge per day) until the voltage of each cell declined to 1.2 volts.
  • the average or the total number of hours of such discharging was entered in the table as capacity under the column headed R. R. lantern, hours to 1.2 volt for groups numbered 2 to 6, inclusive, 8, 9, and 10.
  • the delayed action of these cells was observed at the beginning of the first and last of the /2 hour discharges each day.
  • the electrolyte concentration does not appear to be sharply critical and may range from about to 500 grams of the bromide salt per liter of solution, generally desirable concentrations being from about 200 to 300 grams per liter.
  • a corrosion inhibiting amount of a chromic acid salt such as an alkali metal, alkaline earth metal (including magnesium), or ammonium salt of chromic acid may be included in the electrolyte, as already indicated in the examples, in a concentration of 0.01 to 5 grams per liter.
  • cathode mix is shown containing a small amount of an insoluble chromate, e. g. barium chromate, it is to be understood that other insoluble chromates may be used or omitted entirely, if desired.
  • insoluble chromate e. g. barium chromate
  • anode comprising a magensium-base alloy containing up to 1.5 per cent of aluminum, from 0.1 to 0.7 per cent of zinc, from 0.05 to 0.5 per cent of calcium, the balance being commercial magnesium containing not'over 0.005 per cent of iron, not over 0.002 per cent of nickel, and not over 0.1 per cent of manganese, a magnanese dioxide depolarized cathode, and an electrolyte comprising an aqueous solution of an inorganic bromide selected from the group consisting of the water-soluble bromides of the alkali metals, alkaline earth metals, and ammonium.
  • anode comprising a magnesium-base alloy containing up to 1.5 per cent of aluminum, from 0.l to 0.7 per cent of zinc, from 0.05 to 0.5 per cent'of calcium, from 0.0005 to 0.005 per cent beryllium, the balance being commercial magnesium containing not over 0.005 per cent of iron, not over 0.002 per cent of nickel, and not over 0.1 per cent of manganese, a manganese dioxide depolarized cathode, and an electrolyte comprising an aqueous solution of an inorganic bromide selected from the group consisting of the water-soluble bromides of the alkali metals, alkaline earth metals, and ammonium.
  • anode comprising a ma nesium-base alloy containing from 0.75 to 1.2 per cent of aluminum, from 0.25 to 0.5 per cent of zinc, from 0.1 to 0.3 per cent of calcium, from 0.001 to 0.003 per cent of beryllium, from 0.01 to 0.05 percent of zirconium, the balance being commercial magnesium containin not over-0.005 per cent of iron, not over 0.002 per cent of nickel, and not over 0.1 per cent of manganese,
  • a manganese dioxide depolarized cathode and an electrolyte comprising an aqueous solution of an inorganic bromide selected from the group consisting of the watersoluble bromides of the alkali metals, alkaline earth metals and ammonium.
  • a primary cell having in combination a manganese dioxide depolarized cathode, an aqueous electrolyte comprising a water-soluble bromide of an alkali, alkaline earth metal or ammonium, the improvement which consists in forming the anode of commercial magnesium alloyed With from 0.1 to 0.7 per cent of Zinc, from 0.05 to 0.5 per cent of calcium, said commercial magnesium containing not over 0.1 per cent of manganese, not over 0.005 per cent of iron and not over 0.002 per cent of nickel.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Prevention Of Electric Corrosion (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
US322822A 1952-11-26 1952-11-26 Primary cell Expired - Lifetime US2712564A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BE524612D BE524612A (fi) 1952-11-26
US322822A US2712564A (en) 1952-11-26 1952-11-26 Primary cell
GB28375/53A GB735005A (en) 1952-11-26 1953-10-14 Primary cell
FR1092622D FR1092622A (fr) 1952-11-26 1953-11-13 Perfectionnements relatifs à un alliage à base de magnésium et à un élément primaire de pile dont l'anode est constituée par un tel alliage
DED16427A DE1090866B (de) 1952-11-26 1953-11-23 Primaerelement mit einer Anode aus einer Magnesiumlegierung
JP2154153A JPS353460B1 (fi) 1952-11-26 1953-11-24

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US322822A US2712564A (en) 1952-11-26 1952-11-26 Primary cell

Publications (1)

Publication Number Publication Date
US2712564A true US2712564A (en) 1955-07-05

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Family Applications (1)

Application Number Title Priority Date Filing Date
US322822A Expired - Lifetime US2712564A (en) 1952-11-26 1952-11-26 Primary cell

Country Status (6)

Country Link
US (1) US2712564A (fi)
JP (1) JPS353460B1 (fi)
BE (1) BE524612A (fi)
DE (1) DE1090866B (fi)
FR (1) FR1092622A (fi)
GB (1) GB735005A (fi)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2796456A (en) * 1955-02-08 1957-06-18 Aluminum Co Of America Primary cell anode
US3038019A (en) * 1958-11-03 1962-06-05 Dow Chemical Co Primary cell and anode for use therein
US3080443A (en) * 1960-02-15 1963-03-05 Dow Chemical Co Extruded magnesium alloy battery anodes
US3134698A (en) * 1960-11-18 1964-05-26 Dow Chemical Co Depolarized primary cell
US3190285A (en) * 1960-05-19 1965-06-22 Telefunken Patent Construction of a battery electrode for an endo-radiosonde
US3320055A (en) * 1964-08-19 1967-05-16 Dow Chemical Co Magnesium-base alloy
US6139651A (en) * 1998-08-06 2000-10-31 Dead Sea Magnesium Ltd Magnesium alloy for high temperature applications

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3146096A (en) * 1962-11-23 1964-08-25 Dow Chemical Co Weldable high strength magnesium base alloy
US3496035A (en) * 1966-08-03 1970-02-17 Dow Chemical Co Extruded magnesium-base alloy

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1527293A (en) * 1920-03-18 1925-02-24 Max Brown Friction member
US2011613A (en) * 1934-10-06 1935-08-20 Magnesium Dev Corp Magnesium duplex metal
GB511291A (en) * 1937-02-16 1939-08-16 Alais & Froges & Camarque Cie Magnesium alloys
US2185453A (en) * 1937-09-01 1940-01-02 Magnesium Dev Corp Method of heat treating magnesium base alloys
GB560108A (en) * 1942-03-03 1944-03-21 Tennyson Fraser Bradbury Magnesium alloy
FR892369A (fi) * 1944-04-20
US2380200A (en) * 1942-07-10 1945-07-10 Aluminum Co Of America Magnesium base alloy
US2481204A (en) * 1947-07-02 1949-09-06 Dow Chemical Co Magnesium primary cell
US2535742A (en) * 1948-02-18 1950-12-26 Burgess Battery Co Primary cell with electrodes of magnesium and magnesium permanganate
US2612533A (en) * 1951-05-29 1952-09-30 Burgess Battery Co Primary cell
US2616940A (en) * 1949-12-22 1952-11-04 Dow Chemical Co Primary cell

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR961149A (fi) * 1950-05-05
GB591225A (en) * 1944-08-08 1947-08-12 Magnesium Elektron Ltd Improvements in or relating to the production of magnesium base alloys
DE387278C (de) * 1921-02-15 1924-01-19 Griesheim Elektron Chem Fab Magnesiumlegierung
US2304093A (en) * 1941-12-16 1942-12-08 Dow Chemical Co Removing iron from magnesium alloys
US2380201A (en) * 1942-07-10 1945-07-10 Aluminum Co Of America Manufacture of castings
US2547907A (en) * 1949-01-27 1951-04-03 Dow Chemical Co Magnesium primary cell
US2547908A (en) * 1949-01-27 1951-04-03 Dow Chemical Co Primary cell

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR892369A (fi) * 1944-04-20
US1527293A (en) * 1920-03-18 1925-02-24 Max Brown Friction member
US2011613A (en) * 1934-10-06 1935-08-20 Magnesium Dev Corp Magnesium duplex metal
GB511291A (en) * 1937-02-16 1939-08-16 Alais & Froges & Camarque Cie Magnesium alloys
US2185453A (en) * 1937-09-01 1940-01-02 Magnesium Dev Corp Method of heat treating magnesium base alloys
GB560108A (en) * 1942-03-03 1944-03-21 Tennyson Fraser Bradbury Magnesium alloy
US2380200A (en) * 1942-07-10 1945-07-10 Aluminum Co Of America Magnesium base alloy
US2481204A (en) * 1947-07-02 1949-09-06 Dow Chemical Co Magnesium primary cell
US2535742A (en) * 1948-02-18 1950-12-26 Burgess Battery Co Primary cell with electrodes of magnesium and magnesium permanganate
US2616940A (en) * 1949-12-22 1952-11-04 Dow Chemical Co Primary cell
US2612533A (en) * 1951-05-29 1952-09-30 Burgess Battery Co Primary cell

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2796456A (en) * 1955-02-08 1957-06-18 Aluminum Co Of America Primary cell anode
US3038019A (en) * 1958-11-03 1962-06-05 Dow Chemical Co Primary cell and anode for use therein
US3080443A (en) * 1960-02-15 1963-03-05 Dow Chemical Co Extruded magnesium alloy battery anodes
US3190285A (en) * 1960-05-19 1965-06-22 Telefunken Patent Construction of a battery electrode for an endo-radiosonde
US3134698A (en) * 1960-11-18 1964-05-26 Dow Chemical Co Depolarized primary cell
US3320055A (en) * 1964-08-19 1967-05-16 Dow Chemical Co Magnesium-base alloy
US6139651A (en) * 1998-08-06 2000-10-31 Dead Sea Magnesium Ltd Magnesium alloy for high temperature applications

Also Published As

Publication number Publication date
GB735005A (en) 1955-08-10
FR1092622A (fr) 1955-04-25
JPS353460B1 (fi) 1960-04-12
BE524612A (fi)
DE1090866B (de) 1960-10-13

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