US2683181A - Negative electric plates for alkaline accumulators and methods for making same - Google Patents

Negative electric plates for alkaline accumulators and methods for making same Download PDF

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Publication number
US2683181A
US2683181A US351479A US35147953A US2683181A US 2683181 A US2683181 A US 2683181A US 351479 A US351479 A US 351479A US 35147953 A US35147953 A US 35147953A US 2683181 A US2683181 A US 2683181A
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US
United States
Prior art keywords
plates
iron
negative electric
methods
making same
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
US351479A
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English (en)
Inventor
Salauze Jean
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.)
SAFT Societe des Accumulateurs Fixes et de Traction SA
Original Assignee
SAFT Societe des Accumulateurs Fixes et de Traction SA
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Publication of US2683181A publication Critical patent/US2683181A/en
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Expired - Lifetime legal-status Critical Current

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    • 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
    • H01M4/665—Composites
    • H01M4/666—Composites in the form of mixed materials
    • 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
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/26—Processes of manufacture
    • H01M4/30—Pressing
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0433—Molding
    • 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
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M4/74—Meshes or woven material; Expanded metal
    • 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
    • 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
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • 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
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12042—Porous component

Definitions

  • the plate is formed of a basic material which is copper in finely divided condition consisting of minute acicular, dendritic or arborescent crystals, said copper being thoroughly mixed with pulverulent iron or an iron. providing compound adapted to produce iron when the battery is being charged, said iron or iron providing substance being used as the active elements of the plate.
  • the mixture is compressed under a relatively high pressure on suitable frames embedded in it.
  • the compression and the simultaneous interlacing action of the copper crystals result in the formation of a coherent and porous solid structure including the iron material, wherein the preferably perforated frame acts as a supporting srtucture and as a conductor.
  • the compression applied must be very high. It must attain at least 1 ton/ sq. cm. and can exceed, without any inconvenience, 3 tons/sq. cm., the results improving as this upper end of the range is approached.
  • One of the objects of the present invention is to reduce to a certain extent the required pressures used in these methods while yielding as a final product, battery plates having the desired electrical characteristics and a very good resistance to shocks without scaling off or even local disintegration.
  • the accompanying drawing is a diagrammatic illustration on a greatly enlarged scale of a fragmentary portion of an electrode plate made in accordance with the methods of this invention and illustrating diagrammatically the struc ture and inter-relationship of the components forming the plate.
  • the improved method of this invention is characterized in that it consists in subjecting the plates, after they have been shaped by a press, to a thermal treatment, hereinafter termed sintering since its effect is to sinter the copper content of the plates, that is, to bring about between the copper particles by means of superficial coalescence, a system of local bonds obtained through welding.
  • This sintering is carried out by heating the formed plates to a temperature ranging between 600" and 650 C. While these temperature limits are not limiting or absolute, yet applicant has observed that by heating the plate below 600 C. the sintering was defective and that by heating above 650 C. the electrical characteristics of the plates weakened as the temperature increased.
  • the atmosphere of the furnace must be free from oxidizing agents; it should be either neutral or reducing.
  • nitrogen or hydrogen, or a mixture in variable proportions of both gases may be resorted to.
  • economical operation is obtained by utilizing nitrogen containing about 10% to 20% of hydrogen.
  • Continuous or discontinuous sintering furnaces may be used. For mass production, continuous furnaces are more advantageous.
  • This sintering treatment is a source of improvement especially for those plates which have been insufficiently pressed, for instance, under pressures below 1 ton/sq. cm. These plates are rather brittle and prone to spall off during their handling, so that their physical behavior as Well as their electrical characteristicsare substantially improved with this treatment.
  • the iron providing substance utilized in admixture with copper in finely divided condition consisting of minute acicular, dendritic or arborescent crystals could have different origins.
  • the iron providing substance is derived from ferric oxide F8203 through thermal reduction by means of hydrogen.
  • copper-ferric oxide powder mixtures could be utilized by compressing the same when cold at pressures below 1 ton/sq. cm. on plate metal frames, as described in the co-pending applications. If these plates are passed through a sintering furnace having a reducing atmosphere and heated at about 600-650 C., the ferric oxide undergoes a thermal reduction through the hydrogen and is converted either into iron or into magnetic oxide, or into a mixture of both. While this reduction proceeds, a sintering occurs whereby the copper crystals coalesce together. With this invention, the manufacture of negative plates is made more economical since two steps are merged into one.
  • the invention is also concerned with the plates obtained by carrying out the above method, as a new article of manufacture.
  • a method of manufacturing negative electric plates for alkaline accumulators comprising the step of mixing together a basic material composed of finely divided copper having the shape of microscopic acicular, arborescent or dendritical crystals with an active material which consists of a finely divided iron or iron providing substance, the step of compressing the said mixture under a high pressure on suitable supporting frames, and the step consisting of subjecting the plates after they have been compressed to a thermal or sintering treatment '4 resulting in the sintering of copper particles and establishing among the copper particles, by superficial coalescence, a system of local welded bonds.
  • thermo or sintering treatment is effected in a reducing atmosphere at a temperature range of about 600-650 C. and wherein said reducing atmosphere consists of a mixture of nitrogen and hy-- drogen, and wherein said treatment is effected for a period that is substantially less than one hour.
  • thermo or sintering treatment is effected by passing the plates through a furnace where a reducing atmosphere is maintained so as to subject the plates to heat in a zone of the furnace in a temperature range of from about 600-650 C. for a period that is substantially less than an hour and removing said plates from the zone when cooled nearly to usual room temperatures.
  • the iron providing substance is an iron product obtained by thermal reduction of ferric oxide by hydrogen.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Powder Metallurgy (AREA)
  • Compounds Of Iron (AREA)
  • Secondary Cells (AREA)
US351479A 1952-05-05 1953-04-27 Negative electric plates for alkaline accumulators and methods for making same Expired - Lifetime US2683181A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR62860T 1952-05-05

Publications (1)

Publication Number Publication Date
US2683181A true US2683181A (en) 1954-07-06

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ID=32299591

Family Applications (1)

Application Number Title Priority Date Filing Date
US351479A Expired - Lifetime US2683181A (en) 1952-05-05 1953-04-27 Negative electric plates for alkaline accumulators and methods for making same

Country Status (4)

Country Link
US (1) US2683181A (de)
DE (3) DE869981C (de)
FR (2) FR62860E (de)
GB (3) GB704461A (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2891034A (en) * 1949-08-12 1959-06-16 Ciba Ltd Composition comprising a reaction product of a polyester and a polyepoxide and process for preparation
FR2540675A1 (fr) * 1983-02-08 1984-08-10 Accumulateurs Fixes Procede de fabrication d'une electrode pour generateur electrochimique, et electrode obtenue par ce procede
US5523183A (en) * 1991-07-19 1996-06-04 Pall Corporation Apparatus for use in a battery

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL182964B (nl) * 1952-11-19 Novo Industri As Werkwijze voor het bereiden van menselijke insuline.
FR1079869A (fr) * 1953-03-17 1954-12-03 Accumulateurs Fixes Procédé de fabrication continue de plaques négatives pour accumulateurs alcalins
DE1128492B (de) * 1954-03-17 1962-04-26 Accumulateurs Fixes Verfahren zur kontinuierlichen Herstellung von duennen Elektrodenplatten
FR1217788A (fr) * 1958-12-08 1960-05-05 Yardney International Corp Procédé de fabrication d'électrodes, notamment d'électrodes en zinc, pour générateurs électrochimiques d'énergie
DE1134432B (de) * 1959-09-18 1962-08-09 Accumulatoren Fabrik Ag Verfahren zur Herstellung eines Elektrodensatzes fuer galvanische Elemente, insbesondere elektrische Akkumulatoren, und Vorrichtung zur Durchfuehrung des Verfahrens
SE400856C (sv) * 1975-12-08 1982-02-22 Svenska Utvecklings Ab Poros elektrod for en kemoelektrisk cell, forfarande for framstellning av densamma samt kemoelektrisk cell med sadan elektrod

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2267918A (en) * 1940-03-27 1941-12-30 Gen Motors Corp Porous article and method of making same

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB311141A (de) * 1900-01-01
DE162199C (de) *
DE491498C (de) * 1928-07-06 1930-02-18 Ig Farbenindustrie Ag Elektroden fuer Sekundaerelemente, insbesondere solche mit alkalischen Elektrolyten
GB331540A (en) * 1929-01-04 1930-07-04 Ig Farbenindustrie Ag Improvements in the manufacture and production of electrodes for secondary cells, in particular for those which have alkaline electrolytes
BE532706A (de) * 1947-05-17

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2267918A (en) * 1940-03-27 1941-12-30 Gen Motors Corp Porous article and method of making same

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2891034A (en) * 1949-08-12 1959-06-16 Ciba Ltd Composition comprising a reaction product of a polyester and a polyepoxide and process for preparation
FR2540675A1 (fr) * 1983-02-08 1984-08-10 Accumulateurs Fixes Procede de fabrication d'une electrode pour generateur electrochimique, et electrode obtenue par ce procede
EP0116365A1 (de) * 1983-02-08 1984-08-22 Société Anonyme dite SAFT Verfahren zur Herstellung einer Elektrode für elektrochemischen Generator und in dieser Weise hergestellte Elektrode
US4514473A (en) * 1983-02-08 1985-04-30 Societe Anonyme Dite: Saft Method of manufacturing an electrode for an electrochemical cell, and an electrode manufactured by the method
US5523183A (en) * 1991-07-19 1996-06-04 Pall Corporation Apparatus for use in a battery

Also Published As

Publication number Publication date
GB735793A (en) 1955-08-31
DE976563C (de) 1963-11-21
GB704461A (en) 1954-02-24
FR63037E (fr) 1955-07-13
FR62860E (fr) 1955-06-27
GB737290A (en) 1955-09-21
DE976906C (de) 1964-07-23
DE869981C (de) 1953-03-09

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