GB2178589A - Composite ceramic structure for use in a sodium sulphur cell - Google Patents
Composite ceramic structure for use in a sodium sulphur cell Download PDFInfo
- Publication number
- GB2178589A GB2178589A GB08512805A GB8512805A GB2178589A GB 2178589 A GB2178589 A GB 2178589A GB 08512805 A GB08512805 A GB 08512805A GB 8512805 A GB8512805 A GB 8512805A GB 2178589 A GB2178589 A GB 2178589A
- Authority
- GB
- United Kingdom
- Prior art keywords
- glass
- composite ceramic
- ceramic structure
- seal
- sulphur cell
- 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.)
- Granted
Links
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000000919 ceramic Substances 0.000 title claims description 23
- 239000002131 composite material Substances 0.000 title claims description 22
- 239000011521 glass Substances 0.000 claims abstract description 66
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 34
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 238000007789 sealing Methods 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002667 nucleating agent Substances 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003607 modifier Substances 0.000 claims abstract description 6
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 5
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 abstract description 18
- 238000010899 nucleation Methods 0.000 abstract description 17
- 230000006911 nucleation Effects 0.000 abstract description 17
- 239000005385 borate glass Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- 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 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 4
- 238000000280 densification Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 101100441251 Arabidopsis thaliana CSP2 gene Proteins 0.000 description 1
- 101100222091 Arabidopsis thaliana CSP3 gene Proteins 0.000 description 1
- 101100222094 Arabidopsis thaliana CSP4 gene Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 101100322791 Schizosaccharomyces pombe (strain 972 / ATCC 24843) ago1 gene Proteins 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
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
- H01M10/3909—Sodium-sulfur cells
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0054—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing PbO, SnO2, B2O3
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/14—Silica-free oxide glass compositions containing boron
- C03C3/145—Silica-free oxide glass compositions containing boron containing aluminium or beryllium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/20—Compositions for glass with special properties for chemical resistant glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
-
- 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
- H01M50/184—Sealing members characterised by their shape or structure
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Geochemistry & Mineralogy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
In a sodium sulphur cell, the electrolyte element of beta alumina has a non metallic element bonded to it by a seal formed of glass-ceramic. A glass ceramic seal is made by sealing in the normal way with an alumina-borate glass with an alkaline earth oxide modifier and then heat treating the glass seal to encourage nucleation of crystals and subsequently to encourage crystallisation. The glass used should be free of alkali metal oxide but should include a nucleating agent such as PO25 or TiO2.
Description
SPECIFICATION
Composite ceramic structure for use in a sodium sulphur cell
The present invention is concerned with composite ceramic structures where a first ceramic element is bonded to a further non metallic element to form the composite structure. Such structures are required in sodium sulphur cells which employ a beta alumina electrolyte material and normally require an additional non metallic element to be bonded to the solid electrolyte to form a seal which is impervious and resistant to sodium and polysulphides.
Hitherto such bonds have been made by means of glass seals for example between the beta alumina electrolyte tube of the cell and an alpha alumina plate or collar used to close an end of the tube. Such glass seals work reasonably satisfactorily but the inherent strength of the glass can be not much more than about a tenth of the strength of the ceramic materials which it is being used to bond. Furthermore, the subsequent manufacturing process of the sodium sulphur cell results in further heating of the bonded elements which tends to stress the glass seal which can cause cracking. Still further, densification of the glass seals occurs at the operating temperature of the sodium sulphur cell which can again generate harmful stresses.
According to one aspect of the present invention, a composite ceramic structure for use in a sodium sulphur cell comprises an electrolyte element of beta alumina and a further non metallic element which is bonded to the electrolyte element by means of a seal formed of glass-ceramic.
Glass-ceramics are defined as polycrystalline solids prepared by controlled crystallisation of glasses by nucleating and crystallising. Appropriate glass compositions can be heat treated to stimulate crystal nucleation within the glass and subsequently to stimulate crystal growth, to produce such glass ceramics. A preferred glass ceramic is formed of an alumina-borate glass with an alkaline earth oxide modifier. This modifier may comprise at least one of MgO, BaO or
SrO. The glass may additionally contain an alkali metal oxide, such as Na20 or Li20.
The two elements of the composite ceramic structure are bonded together with glasses as described above in the usual way but the glass sells so formed are then heat treated initially to encourage the nucleation of crystals within the glass and subsequently to encourage crystallisation, thereby forming glass ceramic seals. It has been found that such glass ceramic seals can be highly resistant to sodium and further tend to have lower densification characteristics when the resultant sodium sulphur cell is at its operating temperature. As a result there are fewer problems with stresses being produced. Furthermore, the glass ceramics have substantially higher strength than glass.
It is normally needed to reduce as much as possible the thermal expansion coefficient of the glasses used in the bonding of the alumina elements in sodium sulphur cells, to bring the expansion coefficient as close as possible to that of the beta alumina.
It has been found preferable to completely eliminate alkali metal oxide from the glass used in forming the glass ceramic seals, in order to obtain the desirable low thermal coefficient of expansion. However, the presence of for example of Li20 has been found to improve the nucleation of crystals in the glass throughout its bulk. Accordingly, if the glass is alkali metal free, there is preferably included some additional nucleating agent which otherwise has minimal effect on the glass system and resultant glass ceramic. Appropriate nucleating agents include PO2s and TO2.
Typically, the further non metallic element bonded to the beta alumina electrolyte element is made of alpha alumina.
According to another aspect of the present invention, a composite ceramic structure for use in the sodium sulphur cell comprises an electrolyte element of beta alumina and a further element of glass-ceramic which is bonded to the electrolyte element. The above mentioned preferred characteristics and compositions of glass may be employed also for forming the glass ceramic element in this aspect of the invention Furthermore, it may be especially convenient if the glass ceramic element is bonded to the electrolyte element by means of a seal formed of a glass ceramic.
The invention also includes within its scope a sodium sulphur cell containing a composite ceramic structure as described above. In a further aspect, the invention provides a method of making a composite ceramic structure for use in a sodium sulphur cell and having an electrolyte element of beta alumina and a further non metallic element bonded thereto, comprising the steps of selecting a glass sealing composition capable of being heat treated so as to crystallise, bonding said elements together with said glass composition by the application of heat to form a glass seal between the elements, and heat treating said glass seal to stimulate crystallisation of the glass to form a glass ceramic seal.
Examples of the present invention will now be described. The accompanying drawing is a graphical representation showing a typical temperature profile with time for the heat treatment of a glass ceramic seal.
Table 1 illustrates various glass compositions based principally on the system: MgO Al203-B2O3. Glasses in accordance with each of the above compositions were made up in 2009 batches using Analar grade reagents. In the case of glasses with Na2O or BaO additions, these components were in the form of carbonates. To ensure homogeneity in the resultant glass, the powder batches were tumbled for at least three hours prior to melting. The glasses were melted in a Pt/2% Rh crucible in an electric furnace for one hour. Glass rods of between 2 to 3mm diameter were pulled from the melt at 30 minute intervals up to five hours. After this time, the remaining melt was discarded and replaced by a fresh batch of powder.
Glass ceramics are formed from the controlled crystallisation of glasses, and the crystallisation of the glass takes place via the processes of nucleation and crystal growth. Therefore glass ceramics can usually be formed by subjecting the glasses to a two stage heat treatment programme, where the first stage is used to induce the formation of nuclei and the second stage is used to promote the growth of the nuclei. In the present application, it is desired to produce glass ceramics having fine micro structures and high volume fractions of crystals thereby increasing the resistance to sodium attack, improving the mechanical behaviour and minimising the rate of densification at the operating cell temperature.It is therefore necessary to select a temperature in the first stage of the heat treatment for which the rate of nucleation is a maximum and to heat treat for as long as it is feasible to obtain the maximum number of nuclei. For each of the above samples, the optimum nucleation temperature was obtained by systematically varying the temperature of the first stage heat treatment whilst keeping the other parameters (nucleation time, crystal growth, temperature and time) constant and then observing the resultant volume fraction of crystals formed. The second stage heat treatment was chosen using the criterion that the glass, after the nucleation stage, could be crystaliised in a reasonable length of time (a few hours), and this temperature was arrived at on a trial and error basis.
The thermal expansion coefficient of the glass, prior to heat treatment, and also of the glassceramic produced by heat treatment were measured over a range of temperatures embracing the operating temperature of the sodium sulphur cell. The values for thermal expansion given in table 1 for the various compositions is the value at 350 C. This value is determined by the slope of the expansion curve at the 3500C point and is not corrected for any expansion of the sillica holder used in the testing process. Accordingly the indicated values should be regarded as relative values (to each other).
The glass compositions listed in table 1 were all employed to form seals between alpha and beta alumina elements. Two methods of performing the sealing operating were attempted. The first method involves forming a ring (or preform) of the glass in question, sized to be located between the alpha and beta alumina elements to be sealed together. The preform is then heated to a suitable temperature until it "wets" the alpha and beta alumina components.
The second method involves dipping the beta alumina element into molten glass and then joining the alpha and beta alumina components together while the glass is still fluid.
In either case, it is necessary to find a suitable temperature where the glass will flow and wet the alpha and beta alumina components without undergoing devitrification. The optimum sealing temperatures for each of the glasses prepared were deduced from sessile drop experiments.
To produce glass-ceramic seals between the components, the full heat treatment programme involves three stages, sealing, nucleation and crystal growth.
The attached figure represents schematically a typical temperature profile showing initially a rise in temperature at a rate of 10 C per minute to a holding temperature at which the glass flows to wet the two components, identified as the sealing stage, then a fall in temperature at about 50C per minute to a reduced temperature at which the glass is held for a prolonged period to stimulate the formation of crystal nuclei, designated the nucleation stage, followed by a rise of temperature again at about 50C per minute to an elevated temperature at which crystal growth is promoted, designated as the crystal growth stage, finally followed by a gentle cooling to room temperature at about 20C per minute. The above process was applied to the first method of sealing using a glass preform.
The second method of sealing was carried out by preheating the beta alumina component and the alpha alumina element to about 10000C and 8000C respectively. The beta alumina element was dipped into crucible of the molten glass kept at about 1300 C and then quickly fitted to the preheated collar. The whole assembly was then transferred to be furnaced for the nucleation and crystal growth stages.
Table 2 gives the compositions of a further set of glasses also based on the magnesium alumino-borate system. For these glass compositions, glass ceramics were prepared using different nucleation and crystal growth treatments. The relative thermal expansion coefficients at 3500C for these compositions are shown in table 3 for the glass state, and glass ceramic states derived by three different heat treatment routes. The notation in table 3 indicates the temperature and time in hours of the nucleation and crystal growth stages of the heat treatment respectively. Thus the notation 600/3 775/2 indicates a nucleation stage of 6000C for three hours followed by a crystal growth stage of 7750C for two hours.
The right hand column in table 3, designates the ratio of glass modifier to glass former in the compositions, essentially represented by the sum of the alkali metal (A) and alkaline earth (AE) components relative to B203 (B).
From tables 2 and 3 it can be seen that the thermal expansion coefficient is generally lower for lower values of this ratio. This would imply that minimum thermal expansion values can be obtained by minimising the alkali metal and alkaline earth content of the glass. However, MgO must be kept relatively high to encourage a high volume fraction of the crystal phase in the glass ceramic. Also, Li20 has been found to improve the level of bulk nucleation.
Nevertheless, the alkali free composition CSP12 has desirably low expansion coefficients, but nucleation and subsequent crystallisation of this glass was poor.
Examples CSP12P and CSP12T correspond to CSP12 but with the inclusion of a small proportion of an additional nucleating agent to overcome this problem.
In summary, it can be seen that glass ceramics can be produced which have desirably low thermal expansion coefficients and even values approaching the ideal value at 350 C of 53X107 C-1. The resulting glass ceramic seals are highly sodium resistant have a substantially increased seal strength compared to glass, and have improved thermal stability, i.e. do not suffer from densification at the operating temperature of the sodium sulphur cell. Furthermore, there should be a reduction in interdiffusion because the glass phase of the proposed compositions can be used to seal the elements together at relatively lower temperatures.The above described glass compositions may also be employed to form the additional ceramic components in a sodium sulphur cell, such as the electrolyte tube lid or collar which is customarily formed of alpha alumina.
Table 1
Example Thermal expansion
No. coefficient at 350C Composition Mop. 96 (10 70C 1)
MgO Awl2 03 B203 BaO Na2O Li2 Glass Glass
Ceramic
CSP2 30 20 45 5 - - 64.6 62.7
CSP3 30 20 40 10 - - 71.4 67.6
CSP4 30 20 45 - - 5 -
CSP5 30 20 40 5 - 5 76 71.6
CSP6 25 20 45 5 - 5 66 67
CSP7 25 20 45 10 - - 67 70.1
CSP8 30 20 45 - 2.5 2.5 69 73
CSP9 30 20 40 5 5 - 76 82.6
CSP10 30 20 40 5 2.5 2.5 79 75.5
Table 2: Glass Compositions Mol.%
Example Additional Mol. %
No. MgO Awl2 03 B203 Na2O Li2O Nucleating agent
CSP11 35 20 40 2.5 2.5
CSP12 35 20 45 - -
CSP13 32.5 20 45 - 2.5
CSP14 32.5 20 45 2.5 -
CSP12P 35 20 45 - - 1.0 PO25 CSP12T 35 20 45 - - 1.0 TiO2 Table 3: Relative Thermal Expansion Coefficients at 3500C (X107 0C 12 Example 600/3 650/3 650/2 ASAB No. Glass 775/2 825/2 900/5 B
CSP11 74 72 71 1
CSP12 64.6 64.6 - 0.78
CSP13 68 63 65.7 0.78
CSP14 69 76 72.8 69.1 0.78
CSP12P 63.7 65.3 65.4 0.78
CSP12T 65.6 67.4 - 58.7 0.78
Claims (13)
1. A composite ceramic structure for use in a sodium sulphur cell comprising an electrolyte element of beta alumina and a further non metallic element which is bonded to the electrolyte element by means of a seal formed of glass-ceramic.
2. A composite ceramic structure as claimed in claim 1 wherein the glass-ceramic is formed of an alumina-bora.e glass with an alkaline earth oxide modifier.
3. A composite ceramic structure as claimed in claim 2 wherein the modifier is at least one of MgO, BaO or SrO.
4. A composite ceramic structure as claimed in claim 2 or claim 3 wherein the glass additionally contains an alkali metal oxide.
5. A composite ceramic structure as claimed in claim 4 wherein the alkali metal oxide is at least one of Na2O, Li2.
6. A composite ceramic structure as claimed in any of claims 2 to 5, wherein the glass additionally includes a nucleating agent.
7. A composite ceramic structure as claimed in claim 6 wherein the nucleating agent is at least one of PO2s and TiO2.
8. A composite ceramic structure as claimed in claim 6 or claim 7 wherein the glass is alkalifree.
9. A composite ceramic structure as claimed in any preceding claims wherein the further nonmetallic element is of alpha alumina.
10. A composite ceramic structure for use in a sodium sulphur cell comprising an electrolyte element of beta alumina and a further element of glass-ceramic which is bonded to the electrolyte element.
11. A composite ceramic structure as claimed in claim 10 wherein the glass-ceramic element is bonded to the electrolyte element by means of a seal formed of glass-ceramic.
12. A sodium sulphur cell containing a composite ceramic structure as claimed in any preceding claim.
13. A method of making a composite ceramic structure for use in a sodium sulphur cell and having an electrolyte element of beta alumina and a further non-metallic element bonded thereto, comprising the steps of selecting a glass sealing composition capable of being heat treated so as to crystallise, bonding said elements together with said glass composition by the application of heat to form a glass seal between the elements, and heat treating said glass seal to stimulate crystallisation of the glass to form a glass-ceramic seal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08512805A GB2178589B (en) | 1985-05-21 | 1985-05-21 | Composite ceramic structure for use in a sodium sulphur cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08512805A GB2178589B (en) | 1985-05-21 | 1985-05-21 | Composite ceramic structure for use in a sodium sulphur cell |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8512805D0 GB8512805D0 (en) | 1985-06-26 |
| GB2178589A true GB2178589A (en) | 1987-02-11 |
| GB2178589B GB2178589B (en) | 1988-08-17 |
Family
ID=10579444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08512805A Expired GB2178589B (en) | 1985-05-21 | 1985-05-21 | Composite ceramic structure for use in a sodium sulphur cell |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2178589B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0503776A1 (en) * | 1991-03-11 | 1992-09-16 | Hughes Aircraft Company | Glass sealing materials for sodium-sulfur batteries and batteries made therewith |
| GB2261764A (en) * | 1991-11-22 | 1993-05-26 | Chloride Silent Power Ltd | Method of making seal in alkali metal energy conversion devices |
| EP2617688A1 (en) * | 2012-01-19 | 2013-07-24 | General Electric Company | Sealing glass composition and article |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0018190A1 (en) * | 1979-04-19 | 1980-10-29 | Chloride Silent Power Limited | Glass seals for sealing beta-alumina in electro-chemical cells or other energy conversion devices, glasses for use in such seals and cells or other energy conversion devices with such seals |
| GB2056753A (en) * | 1979-07-03 | 1981-03-18 | Duracell Int | Resistant glass in glass-metal seal and cell terminal structures suitable for lithium electrochemical cells |
| US4341849A (en) * | 1978-10-24 | 1982-07-27 | General Electric Company | Sodium resistant sealing glasses and sodium-sulfur cells sealed with said glasses |
-
1985
- 1985-05-21 GB GB08512805A patent/GB2178589B/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4341849A (en) * | 1978-10-24 | 1982-07-27 | General Electric Company | Sodium resistant sealing glasses and sodium-sulfur cells sealed with said glasses |
| EP0018190A1 (en) * | 1979-04-19 | 1980-10-29 | Chloride Silent Power Limited | Glass seals for sealing beta-alumina in electro-chemical cells or other energy conversion devices, glasses for use in such seals and cells or other energy conversion devices with such seals |
| GB2056753A (en) * | 1979-07-03 | 1981-03-18 | Duracell Int | Resistant glass in glass-metal seal and cell terminal structures suitable for lithium electrochemical cells |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0503776A1 (en) * | 1991-03-11 | 1992-09-16 | Hughes Aircraft Company | Glass sealing materials for sodium-sulfur batteries and batteries made therewith |
| GB2261764A (en) * | 1991-11-22 | 1993-05-26 | Chloride Silent Power Ltd | Method of making seal in alkali metal energy conversion devices |
| EP2617688A1 (en) * | 2012-01-19 | 2013-07-24 | General Electric Company | Sealing glass composition and article |
| US9067818B2 (en) | 2012-01-19 | 2015-06-30 | General Electric Company | Sealing glass composition and article |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2178589B (en) | 1988-08-17 |
| GB8512805D0 (en) | 1985-06-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19930521 |