US3476604A - Method of making an electrode grid - Google Patents

Method of making an electrode grid Download PDF

Info

Publication number
US3476604A
US3476604A US668006A US3476604DA US3476604A US 3476604 A US3476604 A US 3476604A US 668006 A US668006 A US 668006A US 3476604D A US3476604D A US 3476604DA US 3476604 A US3476604 A US 3476604A
Authority
US
United States
Prior art keywords
filaments
web
making
grid
coating
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
US668006A
Inventor
Peter Faber
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.)
RWE AG
Original Assignee
Rheinisch Westfaelisches Elektrizitaetswerk 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 Rheinisch Westfaelisches Elektrizitaetswerk AG filed Critical Rheinisch Westfaelisches Elektrizitaetswerk AG
Application granted granted Critical
Publication of US3476604A publication Critical patent/US3476604A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • 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
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • 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
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • My present invention relates to a grid for an electrode of an electrochemical cell, e.g. a fuel cell or a unit of a primary or secondary battery.
  • Such grids serve the dual purpose of supporting the active electrode material and provide a low-resistance current path between the particles of such material.
  • An object of this invention is to provide a grid of this description which, taken by itself or when loaded with active electrode material, constitutes a porous body of large effective surface and low specific weight.
  • a web of carbonized and at least superficially graphitized filaments as a coherent skeleton on which a metallic coating is deposited to confer the necessary rigidity and conductivity upon the web.
  • the metallic coating may be deposited from a suitable metalizing bath, with or without the application of a galvanizing voltage.
  • this coating consists predominantly of nickel, the presence of a small proportion of boron (e.g. of about by weight) in the composition being preferred.
  • a coating of this description can be deposited, for example, from an aqueous solution of a nickel salt (e.g. NiCl or NiNO in the presence of a reducing boron compound (e.g.
  • a borohydride such as LiBH Metalization by a simple redox process, without applied voltage results in a substantially uniform distribution of the metallic deposit; the use of an electrolytic plating process, on the other hand, may lead to a denser deposit near the outer boundaries of the web which will usually not be objectionable.
  • a thickness of about 5 to a for the metallic layer has been found very satisfactory.
  • the web of carbonaceous filaments to be metalized may be produced by charring a fabric or felt of cellulosic fibers and thereafter heating these fibers to a temperature on the order of 2000 C. for a time suflicient to result in at least superficial graphitization thereof.
  • the charring step may 3,476,604- Patented Nov. 4, 1969 be carried out in an evacuated heating chamber or in a protective atmosphere.
  • Carbonaceous and graphitized filaments so obtained may have an overall thickness, together with their metallic coating, ranging between about 10 and 20
  • the plateshaped web itself may be originally up to 3.5 mm. thick, with a specific gravity of about 0.0 7 g./cm. and an elfective surface of up to 150 times its geometric area.
  • the filaments may be sintered together by their coating, in order to strengthen the structure, by heating to a suitable temperature after metalization; this is advantageously done, e.g. in vacuo or in an atmosphere of a protective gas such as hydrogen, by the passage of a heating current through the web whose conductive filaments form a continuous current path.
  • the porous body so obtained may be further compacted in a press before, during or after the sintering process; the resulting plate may have a thickness of 1-2 mm., though higher degrees of compaction (down to a fraction of a millimeter) are also possible.
  • the grid so produced may be loaded with active material, e.g. nickel hydroxide, cadmium hydroxide, silver oxide or zinc, by conventional processes such as pasting or vibration filling; this step may be omitted in the case of a fuel-cell electrode, e.g. for a cell of the air-zinc type.
  • active material e.g. nickel hydroxide, cadmium hydroxide, silver oxide or zinc
  • FIG. 1 shows a web of metalized carbonaceous filaments forming part of a grid according to the invention
  • FIG. 2 is a fragmentary perspective view of one of the filaments of FIG. 1, drawn to a larger scale;
  • FIG. 3 is a perspective view of a grid produced from the web of FIG. 1.
  • each filament 3 consists of an inner core 2a of carbon coated with a metal layer 2b preferably having the aforedescribed composition of nickel and 5% boron.
  • a plate of this description is characterized by a surprising degree of elasticity, especially when compared with conventional electrodes made from sintered granular particles with or without imbedded reinforcements.
  • charring and metalization may be carried out in a continuous assembly-line-type process.
  • a method of making a grid for an electrode of an electrochemical cell comprising the steps of carbonizing a web of cellulosic filaments, heating the carbonized web to a temperature on the order of 2000" C. for at least superficial graphitization, subsequently metalizing the filaments so obtained to provide them with a metallic coating and a low-resistance current path, and sintering said filaments together at their points of contact by passing an electric heating current through said filaments so coated.
  • a method as defined in claim 2 wherein said coating is a composition of nickel and boron, the latter being present in a proportion of substantially 5% by weight.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Inert Electrodes (AREA)
  • Powder Metallurgy (AREA)

Description

Nov. 4, 1969 P. FABER METHOD OF MAKING AN ELECTRODE GRID Filed Sept 15, 196'? 2a. Graphi ized carbonaceous Filament Pe fer Fabe INVEN'TOR.
United States Patent 3,476,604 METHOD OF MAKING AN ELECTRODE GRID Peter Faber, Kahl am Main, Germany, assignor to Rheinisch-Westfalisches Elektrizitatswerk Aktiengesellschaft, Essen, Germany, a corporation of Germany Filed Sept. 15, 1967, Ser. No. 668,006 Claims priority, application 2G2'e7rmany, Sept. 29, 1966,
Int. Cl. noim 35/04 US. Cl. 136-36 6 Claims ABSTRACT OF THE DISCLOSURE My present invention relates to a grid for an electrode of an electrochemical cell, e.g. a fuel cell or a unit of a primary or secondary battery. Such grids serve the dual purpose of supporting the active electrode material and provide a low-resistance current path between the particles of such material.
An object of this invention is to provide a grid of this description which, taken by itself or when loaded with active electrode material, constitutes a porous body of large effective surface and low specific weight.
It is also an object of this invention to provide a simple and efiicient method of producing such a body.
These objects are realized, in accordance with my present invention, by utilizing a web of carbonized and at least superficially graphitized filaments as a coherent skeleton on which a metallic coating is deposited to confer the necessary rigidity and conductivity upon the web. The metallic coating may be deposited from a suitable metalizing bath, with or without the application of a galvanizing voltage. Advantageously, this coating consists predominantly of nickel, the presence of a small proportion of boron (e.g. of about by weight) in the composition being preferred. A coating of this description can be deposited, for example, from an aqueous solution of a nickel salt (e.g. NiCl or NiNO in the presence of a reducing boron compound (e.g. a borohydride such as LiBH Metalization by a simple redox process, without applied voltage, results in a substantially uniform distribution of the metallic deposit; the use of an electrolytic plating process, on the other hand, may lead to a denser deposit near the outer boundaries of the web which will usually not be objectionable.
Particularly with a nickel-containing coating, a thickness of about 5 to a for the metallic layer has been found very satisfactory.
The web of carbonaceous filaments to be metalized may be produced by charring a fabric or felt of cellulosic fibers and thereafter heating these fibers to a temperature on the order of 2000 C. for a time suflicient to result in at least superficial graphitization thereof. The charring step may 3,476,604- Patented Nov. 4, 1969 be carried out in an evacuated heating chamber or in a protective atmosphere.
Carbonaceous and graphitized filaments so obtained may have an overall thickness, together with their metallic coating, ranging between about 10 and 20 The plateshaped web itself may be originally up to 3.5 mm. thick, with a specific gravity of about 0.0 7 g./cm. and an elfective surface of up to 150 times its geometric area. The filaments may be sintered together by their coating, in order to strengthen the structure, by heating to a suitable temperature after metalization; this is advantageously done, e.g. in vacuo or in an atmosphere of a protective gas such as hydrogen, by the passage of a heating current through the web whose conductive filaments form a continuous current path. If desired, the porous body so obtained may be further compacted in a press before, during or after the sintering process; the resulting plate may have a thickness of 1-2 mm., though higher degrees of compaction (down to a fraction of a millimeter) are also possible.
The grid so produced may be loaded with active material, e.g. nickel hydroxide, cadmium hydroxide, silver oxide or zinc, by conventional processes such as pasting or vibration filling; this step may be omitted in the case of a fuel-cell electrode, e.g. for a cell of the air-zinc type.
The invention will be described in greater detail with reference to the accompanying drawing in which:
FIG. 1 shows a web of metalized carbonaceous filaments forming part of a grid according to the invention;
FIG. 2 is a fragmentary perspective view of one of the filaments of FIG. 1, drawn to a larger scale; and
FIG. 3 is a perspective view of a grid produced from the web of FIG. 1.
As shown in the drawing, a web 1 of metalized carbon filaments 3 is shaped into a rectangular plate having a terminal tab 4 attached thereto by spotwelding. As particularly illustrated in FIG. 2, each filament 3 consists of an inner core 2a of carbon coated with a metal layer 2b preferably having the aforedescribed composition of nickel and 5% boron.
A plate of this description is characterized by a surprising degree of elasticity, especially when compared with conventional electrodes made from sintered granular particles with or without imbedded reinforcements.
If a strip of felt or fabric of indefinite length is used to produce the web of FIG. 1, charring and metalization may be carried out in a continuous assembly-line-type process.
An electroless nickel-plating process of the type mentioned above has been disclosed in US. Patent No. 3,338,741.
I claim:
1. A method of making a grid for an electrode of an electrochemical cell, comprising the steps of carbonizing a web of cellulosic filaments, heating the carbonized web to a temperature on the order of 2000" C. for at least superficial graphitization, subsequently metalizing the filaments so obtained to provide them with a metallic coating and a low-resistance current path, and sintering said filaments together at their points of contact by passing an electric heating current through said filaments so coated.
2. A method as defined in claim 1 wherein said coating consists at least in major part of nickel.
3. A method as defined in claim 2 wherein said coating is a composition of nickel and boron, the latter being present in a proportion of substantially 5% by weight.
4. A method as defined in claim 2 wherein said coating has a thickness ranging substantially between 5 and 10 5. A method as defined in claim 4 wherein said filaments have an overall thickness ranging between substantially 10 and 20,u..
6. A method as defined in claim 1, further comprising the step of compacting said web of filaments.
References Cited UNITED STATES PATENTS Barnett 136-121 Basset 136-121 Hartman et a1 136-64 10 Horn et a1 136-36 Haworth.
WINSTON A. DOUGLAS, Primary Examiner C. F. LEFEVOUR, Assistant Examiner US. Cl. X.R.
US668006A 1966-09-29 1967-09-15 Method of making an electrode grid Expired - Lifetime US3476604A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DER44227A DE1299056B (en) 1966-09-29 1966-09-29 Method for the production of a porous Stromableitgeruestes consisting of metallized, in particular nickel-plated, finest-fiber carbon or graphite fleece by sintering

Publications (1)

Publication Number Publication Date
US3476604A true US3476604A (en) 1969-11-04

Family

ID=7407228

Family Applications (1)

Application Number Title Priority Date Filing Date
US668006A Expired - Lifetime US3476604A (en) 1966-09-29 1967-09-15 Method of making an electrode grid

Country Status (4)

Country Link
US (1) US3476604A (en)
DE (1) DE1299056B (en)
GB (1) GB1146939A (en)
SE (1) SE332245B (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3807996A (en) * 1972-07-10 1974-04-30 Union Carbide Corp Carbon fiber reinforced nickel matrix composite having an intermediate layer of metal carbide
US3926674A (en) * 1973-02-12 1975-12-16 Battelle Memorial Institute Method of manufacturing electrical connection elements for supporting electrodes for storage cells
US4215190A (en) * 1979-06-08 1980-07-29 Ferrando William A Lightweight battery electrode
US4360417A (en) * 1980-07-03 1982-11-23 Celanese Corporation Dimensionally stable high surface area anode comprising graphitic carbon fibers
US4464446A (en) * 1982-06-11 1984-08-07 Societe Civile Des Composites Electrolytiques Anodes of composite materials and accumulators using solid anodes
US5077153A (en) * 1989-09-22 1991-12-31 Saft Process for making an electrode with a porous support for an electrochemical cell and electrode obtained by said process
US5114812A (en) * 1989-07-07 1992-05-19 Hoechst Aktiengesellschaft Electrodes for primary and secondary electric cells
US5154993A (en) * 1990-04-27 1992-10-13 Eveready Battery Company, Inc. Electrode strips for coiled assemblies and method of producing them
US5670278A (en) * 1995-02-03 1997-09-23 Hoechst Trevira Gmbh & Co Kg Supports and electrodes for primary and secondary electric cells

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US536996A (en) * 1895-04-09 Harry theodore barnett
US2658099A (en) * 1948-10-20 1953-11-03 Basset Lucien Paul Microporous carbon and graphite articles, including impregnated battery electrodes and methods of making the same
FR1155740A (en) * 1955-08-22 1958-05-07 Yardney International Corp Process for manufacturing porous electrodes from laying metals
US2865973A (en) * 1953-06-24 1958-12-23 Electric Storage Battery Co Storage battery plates
US3071637A (en) * 1959-01-27 1963-01-01 Accumulatoren Fabrik Ag Process of producing porous, electrically conductive sheet material
US3183123A (en) * 1962-03-19 1965-05-11 Allis Chalmers Mfg Co Fuel cell electrode
US3192071A (en) * 1960-12-27 1965-06-29 Union Carbide Corp Dry cell electrodes containing fibrous graphite and process of making same
US3222224A (en) * 1961-05-10 1965-12-07 Shell Oil Co Electrodes for fuel cells
US3343990A (en) * 1963-01-02 1967-09-26 Shell Oil Co Fuel cells with weftless fabric collectors

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1071788B (en) * 1920-09-16 1959-12-24 AcouimiuHatorien - Fabrik Aktoeneselilschafit, Hagen. Erlf.: Dr.-Ing. Lutz lorn, Hagen, Dipl.-Chem. Dr. Rolf Dieberg, Dorflmundl-Aplerbeck, Fritz Philipp, Hagen-Hasipe und Siegfried Dicklfeldt, Bmnepetall-Milspe (Wesfif.) Porous metal fleece1, especially for the electrodes of electrical cells and processes for their manufacture

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US536996A (en) * 1895-04-09 Harry theodore barnett
US2658099A (en) * 1948-10-20 1953-11-03 Basset Lucien Paul Microporous carbon and graphite articles, including impregnated battery electrodes and methods of making the same
US2865973A (en) * 1953-06-24 1958-12-23 Electric Storage Battery Co Storage battery plates
FR1155740A (en) * 1955-08-22 1958-05-07 Yardney International Corp Process for manufacturing porous electrodes from laying metals
US3071637A (en) * 1959-01-27 1963-01-01 Accumulatoren Fabrik Ag Process of producing porous, electrically conductive sheet material
US3192071A (en) * 1960-12-27 1965-06-29 Union Carbide Corp Dry cell electrodes containing fibrous graphite and process of making same
US3222224A (en) * 1961-05-10 1965-12-07 Shell Oil Co Electrodes for fuel cells
US3183123A (en) * 1962-03-19 1965-05-11 Allis Chalmers Mfg Co Fuel cell electrode
US3343990A (en) * 1963-01-02 1967-09-26 Shell Oil Co Fuel cells with weftless fabric collectors

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3807996A (en) * 1972-07-10 1974-04-30 Union Carbide Corp Carbon fiber reinforced nickel matrix composite having an intermediate layer of metal carbide
US3926674A (en) * 1973-02-12 1975-12-16 Battelle Memorial Institute Method of manufacturing electrical connection elements for supporting electrodes for storage cells
US4215190A (en) * 1979-06-08 1980-07-29 Ferrando William A Lightweight battery electrode
US4360417A (en) * 1980-07-03 1982-11-23 Celanese Corporation Dimensionally stable high surface area anode comprising graphitic carbon fibers
US4464446A (en) * 1982-06-11 1984-08-07 Societe Civile Des Composites Electrolytiques Anodes of composite materials and accumulators using solid anodes
US5114812A (en) * 1989-07-07 1992-05-19 Hoechst Aktiengesellschaft Electrodes for primary and secondary electric cells
US5077153A (en) * 1989-09-22 1991-12-31 Saft Process for making an electrode with a porous support for an electrochemical cell and electrode obtained by said process
US5154993A (en) * 1990-04-27 1992-10-13 Eveready Battery Company, Inc. Electrode strips for coiled assemblies and method of producing them
US5670278A (en) * 1995-02-03 1997-09-23 Hoechst Trevira Gmbh & Co Kg Supports and electrodes for primary and secondary electric cells

Also Published As

Publication number Publication date
SE332245B (en) 1971-02-01
DE1299056B (en) 1969-07-10
GB1146939A (en) 1969-03-26

Similar Documents

Publication Publication Date Title
US2636916A (en) Electrode for galvanic cells
US3933521A (en) Anode for a secondary, high-temperature electrochemical cell
US5965298A (en) Electrode plate for battery and process for producing the same
US3833421A (en) Secondary electrochemical cells with a chalcogen cathode
US3486940A (en) Storage battery having a positive electrode comprising a supporting base of titanium nitride having a surface film of non-polarizing material
US4169120A (en) Sulfur electrode for sodium-sulfur batteries
US3071637A (en) Process of producing porous, electrically conductive sheet material
CN109802129B (en) Metal sodium battery negative electrode material and preparation method and application thereof
US3560262A (en) Electrode with a non-woven fabric base and electroplated coatings of nickel
US3476604A (en) Method of making an electrode grid
CN111613773B (en) Composite of glass fiber with hierarchical structure and metallic lithium and preparation method thereof
US3260576A (en) Porous sintered body and method of preparation
US3600230A (en) Gas-depolarized cell with hydrophobic-resin-containing cathode
CN108550808A (en) A kind of composition metal cathode of lithium and preparation method thereof
US4011373A (en) Uncharged positive electrode composition
CA2763462C (en) Method of producing current collectors for electrochemical devices
US3657014A (en) Porous electrode-support for alkaline accumulators
US3409474A (en) Hydrogen storing electrode and process for its manufacture
US4006034A (en) Method of preparing an electrochemical cell in uncharged state
US3689320A (en) Method for making a battery plate using cellulosic material
US3859139A (en) Novel composite fuel cell electrode
US5045349A (en) Silver-nickel composite cathodes for alkaline secondary batteries
GB1220096A (en) Improvements in and relating to electrochemical cells
US3305401A (en) Electrodes for galvanic primary and secondary cells and methods of producing such electrodes
US3274028A (en) Manufacture of nickel electrodes