WO1999065642A1 - Brazing composition and seal for electrochemical cell - Google Patents
Brazing composition and seal for electrochemical cell Download PDFInfo
- Publication number
- WO1999065642A1 WO1999065642A1 PCT/IB1999/001112 IB9901112W WO9965642A1 WO 1999065642 A1 WO1999065642 A1 WO 1999065642A1 IB 9901112 W IB9901112 W IB 9901112W WO 9965642 A1 WO9965642 A1 WO 9965642A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal
- collar
- cathode
- anode
- cell
- Prior art date
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- 238000005219 brazing Methods 0.000 title claims abstract description 43
- 239000000203 mixture Substances 0.000 title claims description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 70
- 239000002184 metal Substances 0.000 claims abstract description 70
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000919 ceramic Substances 0.000 claims abstract description 33
- 239000000956 alloy Substances 0.000 claims abstract description 32
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 31
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010936 titanium Substances 0.000 claims abstract description 19
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 19
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 18
- 239000010955 niobium Substances 0.000 claims abstract description 18
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 150000002739 metals Chemical class 0.000 claims abstract description 8
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 229910000573 alkali metal alloy Inorganic materials 0.000 claims abstract description 5
- 239000006182 cathode active material Substances 0.000 claims abstract description 5
- 239000004020 conductor Substances 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 3
- 229910000684 Cobalt-chrome Inorganic materials 0.000 claims abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 3
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 3
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 3
- 239000010952 cobalt-chrome Substances 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 239000011572 manganese Substances 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims description 20
- 238000005304 joining Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 238000003466 welding Methods 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 7
- 229910021381 transition metal chloride Inorganic materials 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000010405 anode material Substances 0.000 claims description 4
- 239000002923 metal particle Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 14
- 239000011734 sodium Substances 0.000 description 14
- 229910052708 sodium Inorganic materials 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- -1 liquid sodium Chemical class 0.000 description 6
- 229910000048 titanium hydride Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 241000283070 Equus zebra Species 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000005382 thermal cycling Methods 0.000 description 2
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910020598 Co Fe Inorganic materials 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910002519 Co-Fe Inorganic materials 0.000 description 1
- 229910003271 Ni-Fe Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000005385 borate glass Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3033—Ni as the principal constituent
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/32—Selection of soldering or welding materials proper with the principal constituent melting at more than 1550 degrees C
-
- 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
- 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
- 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
-
- 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, it relates to a method of making seals for electrochemical cells and of making seals for reference electrodes. Still more particularly, the invention relates to a method of making metal-ceramic seals suitable for rechargeable alkali metal anode high temperature electrochemical cells having alkali metal anodes, and precursors of such cells, also being suitable for alkali metal thermoelectric conversion devices, and also being suitable for alkali metal high-temperature reference electrodes. The invention also relates to seals for such cells, devices and electrodes.
- a method of making a seal for 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 comprising at least one chloride selected from the group consist
- a brazing composition suitable for sealing ceramics in a high-temperature rechargeable electrochemical cell of the type which comprises a molten alkali metal or alkali metal alloy active anode material and a transition metal chloride active cathode material dispersed in a porous electrolyte-permeable electronically conductive matrix impregnated by a molten salt electrolyte and separated from the molten active anode material by an alkali metal ion-conductive solid electrolyte separator, the brazing composition being provided as a paste having metal particles with a median particle size of between 20/vm and 70 ⁇ m dispersed in a binder medium, the binder medium being eliminated by brazing .
- the metal particles of the brazing composition may be of an alloy containing less than 1 0% and at least 3% by mass titanium, and containing niobium in a proportion of 1 0% to 70% by mass, relative to its combined nickel and niobium contents.
- the alloy may also include iron. Both aspects also apply to sealing reference electrodes to be used in a high temperature environment, and to sealing alkali metal thermoelectrical conversion devices.
- high temperature is meant to comprise temperatures below the eutectic point of the brazing alloy.
- the invention extends to a method of making a seal for a high temperature rechargeable alkali metal/transition metal chloride cell or for a precursor of such cell, the precursor containing, after loading, a cathode composition which corresponds to an overdischarged state of the cathode of the cell and the precursor containing no metallic alkali metal, the alkali metal being generated on charging the sealed cell precursor.
- the solid electrolyte separator is usually a yS-alumina-type ceramic, typically in the shape of a tube closed off at one end, the other end being open and joined to a ceramic insulating collar, usually of ⁇ -alumina, to which in turn are joined both an outer metal collar and an inner metal collar.
- the artefact ⁇ -alumina insulating collar with the two metal collars
- both metal collars are welded after joining thereof to the insulating collar, the outer collar to a metal canister serving as a cell housing, and the inner metal collar to a current collector extending into the separator tube and in contact with the active electrode material contained therein, the inner collar being welded shut to close the cell after assembly.
- the joint between the solid electrolyte and the ceramic insulating member of the header is usually made by glassing, i.e. glass welding, after making the header, suitable glass compositions being known in the art.
- suitable glass compositions being known in the art.
- the metal-ceramic seals required for joining the ⁇ -alumina insulating member to either the metal canister of the housing or to the metal collars cannot be made reliably by glassing. Seals in high-temperature cells must withstand both thermal cycling and corrosive media, which in the case of ZEBRA-type cells are liquid sodium and the sodium aluminium chloride melt, together with additives which include sulphur or sulphur compounds. Therefore, thermocompression bonded seals have usually been used in those cells and in their precursors, eg as described in US 5 009 357.
- braze for such cells by brazing would appear advantageous from the point of view of cost and speed, but no braze has been known to withstand the environment referred to above, the braze requiring, in combination, at the operating temperature of the ZEBRA cells, resistance to molten alkali metals such as liquid sodium, resistance to molten salt electrolytes such as molten sodium aluminium chloride under electrochemical stress, and resistance to oxidation.
- braze a suitably ductile behaviour of the braze
- elements such as boron and silicon which react with titanium to form high-melting alloys
- brazing times and temperatures to achieve good fracture strength by avoiding unacceptable crystal growth in the metals to be joined .
- the present invention provides such a braze, and with it, a method of sealing the above cells or their precursors, respectively.
- a method of making a seal for a high temperature rechargeable alkali metal/transition metal chloride ceil or for a precursor of such a cell the precursor containing, after loading, a cathode composition which corresponds to an overdischarged state of the cathode of the cell and the precursor containing no metallic alkali metal, the alkali metal being generated on charging the sealed cell precursor, the method including joining a solid electrolyte separator, in the form of a tube closed off at one end with the other end being open, at its open end to a ceramic insulating collar; joining an outer metal collar and an inner metal collar to the ceramic insulating collar by means of a brazing alloy; joining the outer metal collar to a metal canister serving as a cell housing; joining the inner metal collar to a current collector extending into the solid electrolyte separator tube; and closing off the inner metal collar after active electrode material has been loaded into the solid electrolyte separator tube.
- the brazing alloy may contain less than 1 0% and at least 3% by mass titanium, and may contain niobium in a proportion of 10% to 70% by mass, relative to its combined nickel and niobium contents.
- the brazing alloy may also include iron.
- Joining the outer metal collar to the metal canister may be effected by welding, joining the inner metal collar to the current collector may be effected by welding, closing off the inner metal collar may be effected by welding the inner metal collar shut, and joining the solid electrolyte separator to the ceramic insulating collar may be effected by glassing.
- the invention may be used for brazing a variety of metals, including nickel and nickel/cobalt/iron alloys, to alumina-based ceramics.
- a guide for selection of a particular composition from the general compositions outlined above is to include the base metal of the metal part to be brazed in the composition of the braze.
- iron is included in the composition of the braze for brazing iron-based metal parts.
- alloys with coefficients of thermal expansion approaching as closely as possible that of the ceramic in the temperature range covered by the thermal cycling of the brazed join are preferred .
- iron alloys well known in the art for metal/ceramic joints and which may be brazed in accordance with the invention to alumina-based ceramics are Co-Fe alloys with or without a nickel constituent such as Vacon and Vacodil , and Ni-Fe alloys with or without a chromium constituent such as Vacovit , KovarTM and Dilver .
- Such alloys are often used in metal/ceramic joins because of their low coefficient of thermal expansion which is closer to that of the ceramic than that of iron or nickel, in the temperature range of operation and also in the temperature range of glass transformation of the glasses used in manufacturing glassed joins.
- a preferred composition for brazing DilverTM or Vacon is (in % by mass) Ni 41 .6%, Fe 30.9%, Nb 1 4.1 %, Co 9.4%, Ti 4,0%, melting between 1 1 81 and 1 1 90°C, with a preferred brazing temperature between 1 230 °C and 1 280°C. To achieve good flow and wetting of the braze the temperature is raised by about 20°C for a few minutes after melting of the braze has set in. Subsequently, rapid cooling of the workpiece is permitted .
- the brazing alloy may be employed as a metal foil or wire, or may be formulated into a paste containing water and/or organic fluids.
- a brazing alloy precursor metal powder mixture may be prepared from commercial metal powders, including powders obtained by spraying molten metals into a vacuum or into an inert gas.
- the powder mixture may be prepared by a paste formulating process using a viscous binder, and the paste or dispersion thus obtained may be stored in an alternating electromagnetic field to counteract sedimentation of the metal in the paste.
- the precursor metals or metal alloys may be melted to form homogeneous melts before either forming them into particles or shaping them into foils or wires.
- Forming them into particles may comprise spraying the alloy melts into a vacuum or into an inert gas to obtain a pre-alloyed powder of the braze, or may be by milling ingots or pellets of the alloy.
- the titanium component essential for active brazing may be added as titanium powder or titanium hydride powder or as a water- based titanium hydride paste to a precursor powder mix or to a pre-alloyed powder prepared beforehand .
- the titanium content may be incorporated by including titanium in the alloying process of the precursor metals.
- the titanium which is essential for reactive bonding to the ceramic, may be applied first as a titanium hydride paste or dispersion to the ceramic, and after this primer has been caused to adhere, eg by drying the primer, the remainder of the brazing alloy, known as filler metal in the art, may be applied separately in either of the forms mentioned above, together with location thereof in place on the ceramic or on the metal part(s) to be joined, or thereafter.
- the brazes of the present invention show a high solubility for titanium, and, consequently, the titanium can diffuse in the molten braze very quickly to the reaction zone on the ceramic surface. Painting of the ceramic surface with titanium hydride paste is thus not essential.
- the precursor paste or braze paste may be formulated to allow automated application thereof to one or both of the surfaces to be joined by brazing, eg by a printing process or other dispensing process.
- the brazing alloy material according to the invention may be made into a brazing foil or wire which in use is suitably positioned for bonding the surfaces to be joined at the brazing temperature.
- Figure 1 shows a schematic sectional side elevation of a header used in trials performed to test the present invention.
- Figure 2 shows a schematic sectional side elevation of a sodium reference electrode half cell made in accordance with the method of the present invention.
- Figure 1 shows a header used in such trials, generally designated 1 0 and consisting of an ⁇ -alumina collar 1 2 having rebates 1 4 and 1 6 into which respectively an inner metal collar 1 8 and an outer metal collar 20 are joined, the collar 1 2 being joined to the collars 1 8 and 20 by brazing via brazing fillers 22 and 24 respectively, to form ceramic/metal joins of height H .
- the collars 1 8 and 20 were made of nickel having a thickness of 0.5 mm. There were 1 1 samples whose fracture strengths are listed below and these samples were exposed to different environments. The environments are described in Table 1 hereunder and the fracture strengths are set forth in Table 2 hereunder.
- Cyclovoltammetry was used to test the corrosion-stability of brazing alloys in the cathode compartment of a sodium/transition metal chloride cell.
- the experimental setup operated in a dry box, comprised a working electrode formed from a brazed specimen, an aluminium metal counterelectrode, and a nickel reference electrode, immersed in a sodium aluminium chloride melt contained in a glass beaker.
- the working electrode and counterelectrode were separated from each other by a glass frit. The temperature of the melt was kept at 200°C.
- the outer metal collar 20 brazed to the ⁇ -insulating collar 1 2 in this case was FeN ⁇ 46 (Vacodil 46 M ), the inner collar 1 8 was nickel and the brazing was carried out at 1 230 °C at about 1 0 millibars pressure with a dwell time of 1 0 minutes, with heating and cooling rates of 360 °C/m ⁇ nute respectively.
- Example 1 The tests described in Example 1 were repeated and yielded analogous satisfactory results.
- the outer metal collar 20 in this case was FeN ⁇ 42 (Imphy, D ⁇ sseldorf), the inner collar 1 8 was nickel, and the brazing was carried out at
- Example 1 The tests described in Example 1 were repeated and yielded analogous satisfactory results.
- Figure 2 illustrates application of the braze for sealing a sodium reference electrode half-cell generally designated 26 comprising an ⁇ -alumma tube 28 of about 2 mm exterior and 1 mm interior diameter, and a length of about 200 mm, fitted with two metal sleeves 30, 32 of Dilver alloy which are joined to said ⁇ -alumina tube 28 by two seals 34, 36, the brazed seal 34 sealing the tube 28 hermetically at one end .
- Seal 36 may also be braze seal but is preferably a glass seal
- the other end of the tube is sealed by a sodium lon- conductive /?-alum ⁇ na ceramic plug 38 which is glass welded to said alpha alumina tube by borate glass 40.
- a nickel wire 42 of 0.5 mm diameter extends between the braze seal 34 and the beta alumina plug 38 and is used as an electrode for filling sodium into the ⁇ -alumina tube cavity from a sodium salt melt by electrolysis, with sodium passing through the ion-conductive ?-alumina plug, the wire 42 being thereafter used as a reference electrode conductor.
- the other electrode is constituted by the Dilver alloy sleeve 32 which is brazed or welded to a metal part of the cell in which the reference electrode is to be used .
- Sleeve 32 may be fitted with a flange or collar for that purpose.
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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)
- Mechanical Engineering (AREA)
- Secondary Cells (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU39523/99A AU3952399A (en) | 1998-06-15 | 1999-06-15 | Brazing composition and seal for electrochemical cell |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ZA98/5198 | 1998-06-15 | ||
ZA985198 | 1998-06-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999065642A1 true WO1999065642A1 (en) | 1999-12-23 |
Family
ID=25587079
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/IB1999/001112 WO1999065642A1 (en) | 1998-06-15 | 1999-06-15 | Brazing composition and seal for electrochemical cell |
Country Status (2)
Country | Link |
---|---|
AU (1) | AU3952399A (en) |
WO (1) | WO1999065642A1 (en) |
Cited By (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006127045A3 (en) * | 2004-11-30 | 2007-03-01 | Univ California | Sealed joint structure for electrochemical device |
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