WO1999066570A1 - Cellule electrochimique haute temperature pourvue d'un joint d'etancheite - Google Patents

Cellule electrochimique haute temperature pourvue d'un joint d'etancheite Download PDF

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Publication number
WO1999066570A1
WO1999066570A1 PCT/IB1999/001113 IB9901113W WO9966570A1 WO 1999066570 A1 WO1999066570 A1 WO 1999066570A1 IB 9901113 W IB9901113 W IB 9901113W WO 9966570 A1 WO9966570 A1 WO 9966570A1
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WO
WIPO (PCT)
Prior art keywords
metal
solid electrolyte
ceramic
coating
anode
Prior art date
Application number
PCT/IB1999/001113
Other languages
English (en)
Inventor
Bernd Wegner
Original Assignee
Bi-Patent Holding S.A.
Van Der Walt, Louis, Stephanus
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 Bi-Patent Holding S.A., Van Der Walt, Louis, Stephanus filed Critical Bi-Patent Holding S.A.
Priority to AU39524/99A priority Critical patent/AU3952499A/en
Publication of WO1999066570A1 publication Critical patent/WO1999066570A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/186—Sealing members characterised by the disposition of the sealing members
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/191—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/197—Sealing members characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
    • H01M10/3909—Sodium-sulfur cells
    • H01M10/3963—Sealing means between the solid electrolyte and holders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0048—Molten electrolytes used at high temperature
    • 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

  • THIS INVENTION relates to electrochemical cells. More particularly, the invention relates to seals for electrochemical cells. Still more particularly, the invention relates to metal-ceramic seals and headers for rechargeable high temperature electrochemical cells having alkali metal anodes and solid electrolyte ceramic separators, and to precursors of such cells.
  • a rechargeable high temperature electrochemical cell which includes a housing containing an anode and a cathode, the housing having an interior divided by a solid electrolyte separator into an anode compartment and a cathode compartment, the anode compartment and the cathode compartment containing respectively the anode and the cathode, the cell having a charged state in which the anode includes an alkali metal or alkali metal alloy, and the cell having an operating temperature at which the anode is molten, the separator comprising a conductor of alkali metal ions, and the cathode comprising, at said operating temperature and in said charged state, an electronically conductive porous electrolyte-permeable matrix having a porous interior impregnated with a molten salt electrolyte, the matrix containing, dispersed in its porous interior, active cathode material, and the housing including a lower metal part and an upper metal part or lid, the solid electroly
  • the first and second sealing zones thus includes the following interfaces: metal/active braze-bonded ceramic insulating material/glass.
  • the third sealing zone includes a solid electrolyte/glass interface.
  • the seals to the lower and/or the upper metal parts of the housing may be made directly to said parts or to metal collars welded or brazed to said parts of the housing .
  • the solid electrolyte separator may be sealed in the first sealing zone to the lower part of the housing by being sealed to a metal collar welded or brazed to the lower part of the housing.
  • the sealing member to which the separator is sealed in the second sealing zone may be a collar or may be the housing lid.
  • a solid electrolyte-metal seal for sealing a rechargeable high temperature electrochemical cell, the seal including, in combination, a solid electrolyte, at least one metal part, a glass sealing layer, and an active braze-bonded ceramic coating on the metal part.
  • the material of the solid electrolyte separator is a ceramic consisting of at least one member of the ⁇ -alumina class of compounds, /?"- alumina being preferred for sodium/sulphur and sodium/transition metal halide type cells.
  • Suitable glasses for glassing to the solid electrolyte are selected on the basis of thermal expansion properties and stability against cell reactants such as alkali metals, and for the case of sodium anodes include commercial glasses such as Schott glass No. 8245, Corning glass No. 7059, or composites made from these glass types and suitable ceramic powders.
  • Suitable ceramics for the active braze-bonded ceramic insulating material and for active braze-bonded ceramic coating of the metal parts are also selected on the basis of thermal expansion properties and stability against cell reactants and on the basis of bonding to the active braze, and may include a ceramic selected from the group consisting of zirconia, ce ⁇ a, titania, niobia, ⁇ -alumina, and mixtures of two or more thereof
  • the active braze material is selected on the basis of thermal expansion properties and stability against cell reactants and bonding strength, from compositions comprising alloys of nickel, niobium and titanium, and, optionally, of iron and cobalt.
  • the preferred active braze material has a composition which is the subject of a co-pending patent application and comprises nickel, titanium and niobium, being characterised by a titanium content of less than 1 0% by mass and at least 3% by mass, and a niobium content of 1 0% to 70% by mass, relative to the combined nickel and niobium contents.
  • the active braze-bonded ceramic coating may be a double layer composite formed by: preparing a paste comprising particulate active braze material, a fluid and, optionally, a suitable binder; - coating the metal part with said paste; distributing over said paste coating, prior to drying of the paste, particulate ceramic material such as to provide the coating with a surface of particulate ceramic material; and drying and heat-treating the metal part to effect active brazing and bonding of the ceramic material to form a composite active braze-bonded ceramic coating on the metal part.
  • the active braze-bonded ceramic coating may be formed by preparing a paste comprising particulate active braze material, a fluid, particulate ceramic material in sufficient quantity to form, after drying and heat-treating, an essentially ceramic surface for the composite coating, and, optionally, a suitable binder; coating the metal part with said paste; and drying and heat-treating the metal part to effect active brazing and bonding of the ceramic material to form a composite active braze-bonded ceramic coating on the metal part.
  • the coating may be applied to the metal by any suitable method known in the art such as screen printing, roll coating, spraying, dipping or the like.
  • the particle size of the particulate ceramic material is selected to be between 1 0O ⁇ m and 600 ⁇ m, to impart graininess of the ceramics surface. Graininess of the surface involves provision of discrete small islands of ceramic interlocking with the melt during the glassing procedure and may lead to roughness of the surface, but roughness, though advantageous, is not a necessary feature of the double layer composite coating .
  • the ceramic-to-metal seal according to the invention is formed by glassing the ceramic surface of the composite coating described above to the solid electrolyte separator.
  • the glass melt will essentially fill any open interstices (macroscopic open pores) in the ceramic surface of the composite active braze-bonded ceramic coating of the metal part, interlocking and bonding with what then becomes a ceramic interlayer between metal and solid electrolyte separator, the glass melt bonding, on the other hand, to said solid electrolyte separator.
  • the glassing material may be particulate, in the form of a paste or provided as one or more preformed parts.
  • Figure 1 shows a schematic sectional side elevation of part of a cell precursor comprising a seal in accordance with the present invention
  • Figure 2 shows a schematic sectional side elevation of a cell precursor assembly having a single metal collar and comprising a seal in accordance with the present invention
  • Figure 3 shows a schematic sectional side elevation of a cell precursor assembly having two metal collars, in an inverted condition on a centering tool and comprising a seal in accordance with the present invention
  • Figure 4 shows a schematic sectional side elevation of a flat plate cell precursor comprising a seal in accordance with the present invention.
  • Figure 5 shows a schematic sectional side elevation of the seal of the cell of Figure 4 in more detail.
  • the cell part is designated 1 0 and the drawing shows schematically, from left to right and suitably enlarged, a section of a metal wall 1 2, an active braze coating 14 on the wall 1 2 (hatched) , and, penetrating and interlocking with the braze coating 1 4, a ceramic particulate coating 1 6, with the rightmost ceramic surface essentially free of glass.
  • Coatings 14 and 1 6 constitute a double layer of composite active braze-bonded ceramic coating on the metal wall 1 2.
  • reference numeral 1 8 generally designates a cell precursor assembly
  • numeral 20 generally designates a solid electrolyte separator, centred in a cell housing in the form of a cylindrical metal canister 22 and in turn centering a sealing member in the form of a cylindrical metal collar 24, in electrical contact with a current collector (not shown) .
  • An open end of the metal canister 22 is coated in a first sealing zone 26 with an active braze-bonded composite double layer coating according to Figure 1 , and the radially outwardly facing surface of the metal collar 24 is likewise coated with said composite double layer coating in a second sealing zone 28.
  • a glass ring 30 is inserted into the toroidal or annular gap defined between the sealing zones 26 and 28 above a radially outwardly projecting circumferential flange 32 of the ceramic solid electrolyte separator 20.
  • the glass ring 30 is heated to melt it and bond it to the three ceramic surfaces, namely, to the outer ceramic layers of the composite coatings at zones 26 and 28, and to the solid electrolyte separator 20 in a third sealing zone bounded by and formed by said flange 32 of the solid electrolyte separator 20.
  • FIG 3 an assembly 1 8 is shown, in an inverted condition for heat-sealing .
  • a solid electrolyte separator tube 20 is shown about to be joined to an outer metal collar 34 and to a sealing member in the form of an inner metal collar 24, the metal collars respectively being supported on a supporting and centering platen tool 36 via an outer groove 38 and an inner groove 40, said grooves respectively fixing the outer and inner collars 34 and 24 securely in a radial direction.
  • the inner collar 24 is held and aligned in the solid electrolyte ceramic tube via at least three resilient tabs or centering elements 42 equally circumferentially spaced along the circumference of said collar, and said collar 24 is supported so that its lower edge is at about half the depth of the inner groove 40, above its bottom, when assembled prior to glassing, whereas the outer collar 20 rests against the bottom of the outer groove 38.
  • the metal collars 34 and 24 are respectively pre-coated with composite double layer coatings at sealing zones 26 and 28 on faces thereof which are bonded to a pre-fabricated glass ring 30, which is fitted in a space defined by the metal collars 34, 24 and by the inner surface of the open end of the solid electrolyte tube 20.
  • the outer metal collar is welded to a metal canister housing (not shown) after glassing of the assembly.
  • the assembly is heated to melt the glass and to bond the glass in three distinct sealing zones, namely at a first sealing zone 26 to the outer metal collar 34, at a second sealing zone 28 to the inner metal collar 24, and at a third sealing zone to the solid electrolyte tube 20.
  • the resiliency of the tabs 42 is lost and the inner collar 24 is allowed to move axially downwardly under gravity to rest against the bottom of the inner groove 40 when the glass ring 30 melts, thus enhancing the filling of the sealing zones with molten glass.
  • Figure 4 shows a flat-plate cell precursor generally designated 44, fully assembled and in an intermediate state of charge/discharge.
  • the original cell construction which is improved upon by the present invention, is described in South African patent No 95/8252 and incorporates a curved dish-shaped solid electrolyte separator and a circular dish- shaped metal canister cell housing .
  • the metal canister designated 22, is constructed so that it has a peripheral groove or trench 46 radially inwardly of, and extending along, its upper rim.
  • the interior space between the solid electrolyte, designated 20, and the canister floor or bottom forms a cathode space and is essentially filled by an active cathode mass 48 impregnated by a halide salt electrolyte which is molten at the operating temperature of the cell.
  • An anode space is formed by a space between the solid electrolyte 20 and a flexible metal disk 50 and houses a molten sodium active anode mass 52.
  • the disk 50 which forms both cell lid or cover and anode terminal, flexes to follow the volume changes of the molten alkali metal contained in the anode space during charging and discharging of the cell.
  • the solid electrolyte separator 20 is profiled at its rim to be encased and sealed in a glass ring 30 contained in and sealed to the walls of the groove 46 of the metal canister 22.
  • the disk 50 is also profiled to conform approximately with the profile of the separator at its rim or outer circumference.
  • the metal inner surface of the groove 46 and the periphery of the disk 50 are coated with the composite sealing coating described above, in sealing zones in contact with the glass 30 filling groove 46.
  • a first sealing zone is formed between the glass 30 and the inner surface of the metal groove 46 via a composite double layer coating (not shown) on the interior surfaces of said groove;
  • a second sealing zone is formed between the glass 30 and the outer periphery of the anode terminal disk 50 via a double layer composite coating (not shown) on the periphery of the disk 50 and
  • a third sealing zone is formed between the glass 30 and the solid electrolyte separator 20 where said separator is immersed in molten glass 30 during glassing .
  • Opposite sides of the anode terminal disk 50 may be coated at its periphery with the composite coating, where it is immersed in the molten glass during sealing .
  • the seal of Figure 4 is shown in more detail and is designated 54.
  • the groove 46 of the metal canister 22 of Figure 4 is manufactured as a separate part in this example and is welded or brazed later, after insertion of the cathode active mass into the canister, at its upper rim, at 56, to said canister (the canister is not shown) .
  • the groove 46 is coated on its inside with a composite double layer coating 26 as described above and receives the rims of both the solid electrolyte separator 20 and the anode terminal cover 50.
  • the outermost portion of the rim of the anode terminal cover 50 is coated both inside and outside thereof with the composite double layer coating 58 as described above, and a sealing glass melt 30 is introduced into the groove 46 to seal the components contained therein in the sealing zones signified by the Roman numerals I, II and III and indicated by circles, between the interfaces described with reference to Figure 4.
  • Experimental verification of the sealing was performed using metal samples of Ni-Fe-Co alloy (Dilver , Imphy, D ⁇ sseldorf, Germany), glass No. 8245 (Schott, Mainz, Germany) or sodium-resistant glass according to EP 0459674, and ⁇ -alumina granules with diameters between 0.1 and 0.5 mm.
  • the composite double layer coating was subjected to metallographic sectioning and grinding and showed under the microscope both complete filling of the interstices of the ceramic granulate layer and complete interlocking with said ceramic layer.
  • the invention thus provides means for simple cell designs and, accordingly, simple cell assemblies.
  • pre-fabricated ceramic sealing elements usually of ⁇ -alumina or other non ion- conductive ceramic, which pose demands on close dimensional tolerances and contribute substantially to the cost of sealing high-temperature cells with alkali metal anodes, can be eliminated .

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention concerne une cellule électrochimique haute température rechargeable qui comporte un logement pourvu d'une anode et d'une cathode et dont l'intérieur est divisé par un séparateur à électrolyte solide en un compartiment anodique et en un compartiment cathodique. Ce compartiment anodique et ce compartiment cathodique contiennent respectivement l'anode et la cathode. La cellule présente un état chargé dans lequel l'anode comporte un métal alcalin ou un alliage métallique alcalin, ainsi qu'une température de fonctionnement à laquelle l'anode fond. Le séparateur comprend un conducteur de ions métalliques alcalins tandis que la cathode comprend, à ladite température de fonctionnement et dans ledit état chargé, une matrice poreuse, perméable aux électrolytes et à conductivité électronique, laquelle matrice présente un intérieur poreux imprégné d'un électrolyte à sels fondus. Une matière active de cathode est dispersée sur la partie intérieure poreuse de cette matrice. Le logement est constitué d'une partie métallique inférieure et d'une partie métallique supérieure ou couvercle. Le séparateur à électrolyte solide est appliqué de manière étanche, en une première zone d'étanchéité (26), sur la partie métallique inférieure et en une seconde zone d'étanchéité (28), sur un élément métallique d'étanchéité en contact électrique avec un collecteur de courant destiné à un terminal de la cellule. Au moins une desdites parties métalliques revêtue d'une matière céramique, isolante, active et brasée est appliquée de manière étanche et par vitrification, en une troisième zone d'étanchéité (32), sur l'électrolyte solide (20).
PCT/IB1999/001113 1998-06-15 1999-06-15 Cellule electrochimique haute temperature pourvue d'un joint d'etancheite WO1999066570A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU39524/99A AU3952499A (en) 1998-06-15 1999-06-15 High temperature electrochemical cell including a seal

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ZA98/5197 1998-06-15
ZA985197 1998-06-15

Publications (1)

Publication Number Publication Date
WO1999066570A1 true WO1999066570A1 (fr) 1999-12-23

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB1999/001113 WO1999066570A1 (fr) 1998-06-15 1999-06-15 Cellule electrochimique haute temperature pourvue d'un joint d'etancheite

Country Status (2)

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AU (1) AU3952499A (fr)
WO (1) WO1999066570A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006127045A3 (fr) * 2004-11-30 2007-03-01 Univ California Structure de joint scelle pour dispositif electrochimique
EP1829112A2 (fr) * 2004-11-30 2007-09-05 The Regents of the University of California Jonction de materiaux dissemblables
ITRM20090593A1 (it) * 2009-11-16 2011-05-17 V L T Vacuum Lasers Technology S R L "collare ermetico ed isolante per elemento di batteria a sali fusi di sodio o di altri metalli alcalini, e metodo per la sua realizzazione"

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3839779A (en) * 1973-09-07 1974-10-08 Atomic Energy Commission Ceramic brazing method
US5279909A (en) * 1992-05-01 1994-01-18 General Atomics Compact multilayer ceramic-to-metal seal structure
ZA958252B (en) * 1994-10-13 1996-04-15 Programme 3 Patent Holdings Electrochemical cell

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3839779A (en) * 1973-09-07 1974-10-08 Atomic Energy Commission Ceramic brazing method
US5279909A (en) * 1992-05-01 1994-01-18 General Atomics Compact multilayer ceramic-to-metal seal structure
ZA958252B (en) * 1994-10-13 1996-04-15 Programme 3 Patent Holdings Electrochemical cell
GB2294803A (en) * 1994-10-13 1996-05-08 Programme 3 Patent Holdings High-temperature cell having curved solid electrolyte separator and flexible anode cover to accommodate volume changes during charging/discharging

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006127045A3 (fr) * 2004-11-30 2007-03-01 Univ California Structure de joint scelle pour dispositif electrochimique
EP1829112A2 (fr) * 2004-11-30 2007-09-05 The Regents of the University of California Jonction de materiaux dissemblables
EP1829112A4 (fr) * 2004-11-30 2009-11-18 Univ California Jonction de materiaux dissemblables
AU2005332026B2 (en) * 2004-11-30 2011-06-09 The Regents Of The University Of California Sealed joint structure for electrochemical device
US8445159B2 (en) * 2004-11-30 2013-05-21 The Regents Of The University Of California Sealed joint structure for electrochemical device
ITRM20090593A1 (it) * 2009-11-16 2011-05-17 V L T Vacuum Lasers Technology S R L "collare ermetico ed isolante per elemento di batteria a sali fusi di sodio o di altri metalli alcalini, e metodo per la sua realizzazione"

Also Published As

Publication number Publication date
AU3952499A (en) 2000-01-05

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