US3713891A - Chloride free leaching process for porous zinc anodes - Google Patents

Chloride free leaching process for porous zinc anodes Download PDF

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Publication number
US3713891A
US3713891A US00114349A US3713891DA US3713891A US 3713891 A US3713891 A US 3713891A US 00114349 A US00114349 A US 00114349A US 3713891D A US3713891D A US 3713891DA US 3713891 A US3713891 A US 3713891A
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United States
Prior art keywords
chloride free
zinc
amalgam
anode
acid
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Expired - Lifetime
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US00114349A
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English (en)
Inventor
E Curelop
N Marincic
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Duracell Inc USA
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PR Mallory and Co Inc
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Assigned to DURACELL INC., A CORP. OF DEL. reassignment DURACELL INC., A CORP. OF DEL. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: DURACELL INTERNATIONAL INC.,
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Classifications

    • 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
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12479—Porous [e.g., foamed, spongy, cracked, etc.]

Definitions

  • the essential step in the invention is free acid leaching with an acid'other than hydrochloric acid in order to form a water soluble salt of the free acid.
  • the efficiency of a battery depends to great extent on the surface area of theanode structure used therein.
  • the present invention provides an anode of greatly improved characteristics comprising compacted porous zinc amalgam, and utilizing an aqueous solution leachant of a'chloride free acid in combination with the salt of this chloride free acid as a fillerin contact with this acid.
  • a zinc mercury amalgam is created by an electrochemical reaction eementation process, and a water soluble salt of the chloride free acid is formed simultaneously.
  • the reactive cementation process utilizes the electro-chemical reaction of zinc powder with mercury oxide to produce an alloying or amalgam bond between the zinc particles.
  • a free acid other than hydrochloric acid is used as afluxing agent for the zinc particles to facilitate their intimate contact with each other, along with the use of a chloride free filler that is a soluble salt of the chloride free acid.
  • chloride free acids and of their corresponding chloride free fillers include acetic acid and sodium acetate, or boric acid and sodium borate, or oxalic acid and sodium oxalate.
  • gassing may occur from zinc anodes produced by the ammonium chloride process, with this instability toward gassing being due to the presence of unremoved zinc.oxide and/or zinc chloride impurity sites on the zinc anodethat had notbeen displaced by mercury metal during. the electrochemical displacement reaction.
  • va porous anode structure of specific shape in the form of a selfsupporting open three dimensional zinc mercury metal network consisting essentially of chloride free zinc and mercury amalgam metal particles which are pressure welded one to another having communicating'voids therebetween and further consisting, of trace amounts of inert nonchloride ions selected from the group consisting of acetate ions, borate ions,oxalate ions present therein up to 1 percent by weight of said structure integrally united at specific lattice sites to reduce anode gassing.
  • Still another object of the present invention is to provide a primary'cell including azinc amalgam porous anode for a battery.
  • the present invention provides a new battery system in which the problem of anode gassing is substantially reduced.
  • This substantial reduction is the direct result of the presence, in the battery, of a novel anode consisting of porous zinc amalgam containing trace amounts of an inert nonchloride ion selected from the group consisting of acetate ions, borate ions and oxalate'ions present up to 1% by weight of the anode.
  • the anode is forr ned as a uniformly porous pellet by means of reactive cementationof admixed materials such'as zinc powder, mercuric oxide,
  • chloride free .filler selected from the'group con sisting of sodium acetate, sodium borate,'and sodium oxalate, and by leaching out the chloride free filler with an aqueous solution of the corresponding chloride free acid selected from the group consisting of acetic acid,
  • the blending was carried out for, 10-12 minutes at speed of -30 r.p.m. About 1.68 to 1.70 grams of the above mixture was pressed into a green anode 77-80 mils thick. The pressure required was about 12,000 psi.
  • the leaching of the anodes was carried out with acetic acid diluted in the ratio of l part by weight acid to 3 parts by weight water.
  • the amounts of acid should be in a controlled-relation to the weight and number of anodes, at least during the first 15 minutes of leaching.
  • About 2 ml. of the above solution is the maximum allowed for the above anodes; in other words approximately 1 ml. of the above solution per each gram of the green anode of anysize and shape.
  • the excess of the above leaching solution can be added for faster leaching but only after the initial 15 minute period.
  • the acetate leaching process is generally faster than the chloride leaching process. It is completed in 5-6 hours at room temperature when the above size anodes are processed. The leached anodes were washed in distilled water, until the effluent showed a pH value of 6 or higher. The anodes were then washed with alcohol, dried in air, and had a dry weight of 1.14 grams i 0.05 grams and had a porosity of 70 percent and contained 12 percent mercury.
  • EXAMPLE 2 Anodes of various porosities can be produced using the same procedure except for the mix composition.
  • the following is another variation of the above mix, used for the productionof large anodes: 5000 grams of zinc powder, 1300 grams of sodium acetate, 780 grams H,O, and 30 ml. kerosene. i 48.5 grams of the abovemix were pressed into a retangular anode 3.2 inches by 1.6 inches with a force of 30 tons (5.86 tons per square inch).
  • the same type of anode was pressed with a copper screen in the middle as a current collector for the rechargeable cell application.
  • the copper screen was amalgamated during the leaching process and provided a good contact to the porous anode body over the entire anode cross-section.
  • EXAMPLE 3 Other combinations of acids as leachants and their salts as fillers were also utilized. The following mixture of 5000 grams zinc powder, 2100 grams sodium metaborate, 780 grams 11,0 was prepared and the pressed anodes were. leached inacorr'e'spondingly diluted boric acid in the ratio ofl ml. per gram of green anode as in Example l and produced a zinc anode of about the same weight, porosity,' and mercury content of Example 1.
  • EXAMPLE 4 The-following mixture of 5000 grams zinc powder, l300grams sodiumkmetaborate, 780 grams H O,,and 30 ml. kerosene was treated with thesame quantity of boric acid as in Example .3 and produced a zinc anode of about the same weight porosity, and mercury content of Example 2. r
  • EXAMPLE 5 The following mixture of 5000 grams zinc powder, 2100 grams sodium oxalate, 780 grams H,O, and 30 ml. kerosene was treated with correspondingly diluted oxalic acid in the ratio of 1 ml. per gram of green anode as in Example 1 and produced a zinc anode of about the same weight porosity, and mercury content of Example 1.
  • EXAMPLE 6 The following mixture of 5000 grams zinc powder, 1300 grams sodium oxalate, 780 grams 11,0, and 30 ml. kerosene was treated with the same quantity of oxalic acid as in Example 5 and produced a zinc anode of about the same weight, porosity, and mercury content of Example 2.
  • Zinc particles in anodes produced by the above 6 examples measured between 25 to 40 microns.
  • A" zinc anode prepared according to each of the above six examples was tested as follows.
  • the anode wherever necessary, was reshaped into the form of a disc pellet having a diameter of v 0.5 inches and a thickness of 0.1 inches.
  • the pellet was then inserted as an anode into an alkaline cell/of flat cylindrical construction .in contact with an absorbent spacer impregnated with an alkaline electrolyte, such as 35-40% KOH, 3.5-6.5% ZnO, and the balance water.
  • an alkaline electrolyte such as 35-40% KOH, 3.5-6.5% ZnO
  • a suitable depolarizer such as the metal oxide H O, M,,O or Ag O containing from 5-25 percent graphite.
  • This sealed cell was subjected to F for 24 hours with the result that about 0.05-0.07 cu. cm. of gas were produced.
  • the gassing rate was determined to be 0.20 cu. cm. to 0.25 cu. cm. for a 24 hour period at 180F.
  • gassing rates for the chloride free leaching are very satisfactory relative to the gassing rate for the chloride process and indicate the superiority of the present invention over conventional anode structures.
  • a method of fabricating a highly porous amalgamated chloride free zinc anode for an electric current producing device comprising the steps of: preparing a reactive mixture: consisting of zinc powder, mercuric oxide powder, and a chloride free filler material selected from the groupconsisting of sodium acetate, sodium borate and sodium oxalate and leaching said mixture with a chloride free acid leachant selected from the group consisting of acetic acid, boric acid and oxalic acid for dissolving out said filler material to produce a mercury zinc amalgam.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
US00114349A 1971-02-10 1971-02-10 Chloride free leaching process for porous zinc anodes Expired - Lifetime US3713891A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US11434971A 1971-02-10 1971-02-10

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US3713891A true US3713891A (en) 1973-01-30

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US00114349A Expired - Lifetime US3713891A (en) 1971-02-10 1971-02-10 Chloride free leaching process for porous zinc anodes

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US (1) US3713891A (enrdf_load_stackoverflow)
JP (1) JPS5629340B1 (enrdf_load_stackoverflow)
AU (1) AU474783B2 (enrdf_load_stackoverflow)
BE (1) BE779147A (enrdf_load_stackoverflow)
CA (1) CA970827A (enrdf_load_stackoverflow)
CH (1) CH585466A5 (enrdf_load_stackoverflow)
DE (1) DE2205528C3 (enrdf_load_stackoverflow)
FR (1) FR2124589B1 (enrdf_load_stackoverflow)
GB (1) GB1341928A (enrdf_load_stackoverflow)
IL (1) IL38731A (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4017665A (en) * 1974-05-21 1977-04-12 Prazska Akumulatorka, Narodni Podnik Composition for a zinc electrode
US4279709A (en) * 1979-05-08 1981-07-21 The Dow Chemical Company Preparation of porous electrodes
US4871703A (en) * 1983-05-31 1989-10-03 The Dow Chemical Company Process for preparation of an electrocatalyst
US5599637A (en) * 1992-02-10 1997-02-04 Electric Fuel Limited (E.F.L) Performance zinc anode for batteries

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CS176569B1 (enrdf_load_stackoverflow) * 1974-07-30 1977-06-30
GB0802686D0 (en) * 2008-02-14 2008-03-19 Ceram Res Ltd High surface area metal production

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US413438A (en) * 1889-10-22 Process of manufacturing battery-zincs
US2938064A (en) * 1958-03-12 1960-05-24 Union Carbide Corp Air-depolarized cell
US2983777A (en) * 1956-07-23 1961-05-09 Yardney International Corp Rechargeable battery
US3007994A (en) * 1958-07-10 1961-11-07 Union Carbide Corp Amalgamation of zinc
US3060254A (en) * 1959-08-03 1962-10-23 Union Carbide Corp Bonded electrodes
US3236690A (en) * 1963-01-16 1966-02-22 Mallory & Co Inc P R Rechargeable alkaline cell and liquid phase-containing amalgam anode therefor
US3427204A (en) * 1966-11-14 1969-02-11 Mallory & Co Inc P R Leached amalgamated zinc anode
US3427203A (en) * 1966-07-20 1969-02-11 Esb Inc Large surface area electrodes and a method for preparing them
US3565695A (en) * 1968-04-01 1971-02-23 Gen Electric Method of forming an amalgamated zinc electrode

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1331691A (fr) * 1962-07-26 1963-07-05 Lucas Industries Ltd Procédé de fabrication de métaux poreux

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US413438A (en) * 1889-10-22 Process of manufacturing battery-zincs
US2983777A (en) * 1956-07-23 1961-05-09 Yardney International Corp Rechargeable battery
US2938064A (en) * 1958-03-12 1960-05-24 Union Carbide Corp Air-depolarized cell
US3007994A (en) * 1958-07-10 1961-11-07 Union Carbide Corp Amalgamation of zinc
US3060254A (en) * 1959-08-03 1962-10-23 Union Carbide Corp Bonded electrodes
US3236690A (en) * 1963-01-16 1966-02-22 Mallory & Co Inc P R Rechargeable alkaline cell and liquid phase-containing amalgam anode therefor
US3427203A (en) * 1966-07-20 1969-02-11 Esb Inc Large surface area electrodes and a method for preparing them
US3427204A (en) * 1966-11-14 1969-02-11 Mallory & Co Inc P R Leached amalgamated zinc anode
US3565695A (en) * 1968-04-01 1971-02-23 Gen Electric Method of forming an amalgamated zinc electrode

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4017665A (en) * 1974-05-21 1977-04-12 Prazska Akumulatorka, Narodni Podnik Composition for a zinc electrode
US4279709A (en) * 1979-05-08 1981-07-21 The Dow Chemical Company Preparation of porous electrodes
US4871703A (en) * 1983-05-31 1989-10-03 The Dow Chemical Company Process for preparation of an electrocatalyst
US5599637A (en) * 1992-02-10 1997-02-04 Electric Fuel Limited (E.F.L) Performance zinc anode for batteries

Also Published As

Publication number Publication date
DE2205528B2 (de) 1980-10-09
CA970827A (en) 1975-07-08
FR2124589A1 (enrdf_load_stackoverflow) 1972-09-22
AU3764172A (en) 1973-07-12
IL38731A (en) 1975-04-25
BE779147A (fr) 1972-08-09
DE2205528C3 (de) 1981-12-03
CH585466A5 (enrdf_load_stackoverflow) 1977-02-28
AU474783B2 (en) 1976-08-05
FR2124589B1 (enrdf_load_stackoverflow) 1975-10-24
JPS5629340B1 (enrdf_load_stackoverflow) 1981-07-08
DE2205528A1 (de) 1972-08-24
GB1341928A (en) 1973-12-25
IL38731A0 (en) 1972-04-27

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Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:DURACELL INTERNATIONAL INC.,;REEL/FRAME:004089/0593

Effective date: 19820524