GB2046502A - Improvements in or relating to sodium sulphur cells - Google Patents
Improvements in or relating to sodium sulphur cells Download PDFInfo
- Publication number
- GB2046502A GB2046502A GB7911551A GB7911551A GB2046502A GB 2046502 A GB2046502 A GB 2046502A GB 7911551 A GB7911551 A GB 7911551A GB 7911551 A GB7911551 A GB 7911551A GB 2046502 A GB2046502 A GB 2046502A
- Authority
- GB
- United Kingdom
- Prior art keywords
- sodium
- cell
- sulphur cell
- filler material
- sodium sulphur
- 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 24
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 17
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 17
- 239000011734 sodium Substances 0.000 claims abstract description 17
- 239000000945 filler Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 16
- 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 claims abstract description 15
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005864 Sulphur Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 6
- 229920001021 polysulfide Polymers 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010445 mica Substances 0.000 claims abstract description 4
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 4
- 239000000454 talc Substances 0.000 claims abstract description 4
- 229910052623 talc Inorganic materials 0.000 claims abstract description 4
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 3
- 239000010439 graphite Substances 0.000 claims abstract description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000007784 solid electrolyte Substances 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000006188 syrup Substances 0.000 description 3
- 235000020357 syrup Nutrition 0.000 description 3
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- KNXVOGGZOFOROK-UHFFFAOYSA-N trimagnesium;dioxido(oxo)silane;hydroxy-oxido-oxosilane Chemical compound [Mg+2].[Mg+2].[Mg+2].O[Si]([O-])=O.O[Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O KNXVOGGZOFOROK-UHFFFAOYSA-N 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
- H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
- H01M50/145—Primary casings; Jackets or wrappings for protecting against damage caused by external factors for protecting against corrosion
-
- 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
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
Abstract
To provide improved protection for a sodium sulphur cell against possible leakage from a neighbouring cell, the metal casing 13 of each cell in a battery has an outer coating 15 of a particulate non-inflammable filler material, preferably a flaky material such as graphite, talc, molybdenum disulphide or mica, which is inert to hot sodium and hot sulphur/sodium polysulphides, the particles of the material being bonded together with sodium silicate. <IMAGE>
Description
SPECIFICATION
Improvements in or relating to sodium sulphur cells
This invention relates to sodium sulphur cells and to batteries incorporating such cells.
A sodium sulphur cell comprises essentially a cation permeable solid electrolyte membrane separating an anodic region.containing sodium, which is liquid at the operating temperature of the cell, from a cathodic region containing sulphur and sodium polysulphides. The membrane may be a flat plate but, more commonly, is a tube, usually formed of beta-alumina. If the cathodic region is inside the tube (known as a central sulphur cell), then the anodic region is commonly an annular space between the electrolyte tube and a metal casing, which may constitute the anode connection to the cell.
Alternatively the cell may be of the type known as a central sodium cell with the cathodic region around the outside of the electrolyte tube, in which case the casing forms part of the container for the cathodic reactant. This cathodic reactant is highly corrosive and, particularly with central sodium cells, many proposals have been made for protecting the casing against corrosion from the cathodic reactant within the housing.
If the electrolyte membrane should fracture, mixing of the sodium and the cathodic reactant could occur; this reaction is exothermic and the resultant hot liquid is particularly corrosive. In sodium sulphur cells, the primary protection against damage from a fracture of the electrolyte is usually by restricting access of the sodium to the membrane, e.g. by using a capillary system. However, if one cell should fail with leakage of hot corrosive liquid, it could damage a neighbouring cell. It has been proposed therefore to provide separators between the cells, for example of porous material to absorb any liquid which leaks from an individual cell. It has also been proposed to provide a plasma-sprayed oxide coating on a cell casing.
It is an object of the present invention to provide an improved form of coating on a sodium sulphur cell for giving protection against possible leakage from a neighbouring cell.
According to this invention, in a sodium sulphur cell having a metal casing containing a solid electrolyte membrane separating sodium from a cathodic reactant, the casing has an outer coating comprising a particulate, non-inflammable filler material which is chemically inert to hot sodium and sulphur/sodium polysulphides, the particles being bound together with sodium silicate. Preferably the filler material is a flaky material. Examples of suitable filler materials are graphite, talc, molybdenum disulphide and mica.
It has been found that a coating using a filler material with sodium silicate as a binder has very good adhesive to steel such as is commonly employed for the casings of sodium sulphur cells. The coating can readily be applied as a slurry of the solid material in an aqueous solution of sodium silicate, for example, by brushing, dipping or spraying. Such methods of application are far cheaper than plasma spraying such as has previously been proposed for protective coatings on sodium sulphur cells. The water content of the slurry can be chosen to suit the particular method of application. The thickness of the coating can be adjusted by choice of the number of applications, the method of application and the water content of the slurry.
Particularly using a flaky filler, the material has a very good covering power as the flakes tend to align with the surface being coated. It is moreover found that this coating, compared with plasma-sprayed oxide coatings, is less liable to crack or spall, especially in the event of a thermal shock.
The sodium silicate can be of the formula Na2O.x
SiO2 where x is in the range of 1 to 5. The proportion of binder to filler may be in the range of 1:0.8 to 1:8 by weight. Preferably the filler comprises particles having linear dimensions of 0.1 micron to 100 microns.
In the following description, reference will be made to the accompanying drawing which is a diagrammatic cross-section through a sodium sulphur cell.
The drawing illustrates a sodium sulphurcell of the central sulphurtype with a polycrystalline ceramic electrolyte tube 10 permeable to sodium ions, typically a tube of beta-alumina, separating sulphur/sodium polysulphides in a cathodic region 11, inside the tube, from sodium in an annulus 12, forming the anodic region. This annulus 12 lies between the ceramic tube 10 and a metal casing, typically a steel casing 13 which forms the anode current collector. A cathode current collector 14 extends axially within the cathodic region 11.
The present invention is concerned more particularly with the provision of a protective coating 15 on the outer surface of the casing 13, which housing is cylindrical in form.
EXAMPLE 1
As a first example, a coating suitable for application by brush, was made by mixing 8 parts by weight of french chalk powder (powdered talc) with 5 parts by weight of waterglass syrup (Na2O 18%, SiO2 36%,
H2O 46% by weight). This mixture was painted on a steel casing for a sodium sulphur cell. A single coating was found to give a loading of 23 mg/cm2.
EXAMPLES
A coating suitable for application by dipping was made by mixing 1.5 parts by weight of mica powder with 1 part by weight of waterglass syrup (Na2O 18%,
SiO2 36%, H2O 46% by weight) and 2.6 parts by weight of water. Dipping the steel casing for a sodium sulphur cell in this mixture and allowing it to dry produced a coating giving a loading of approximately 15 mg/cm2.
EXAMPLES
Another coating suitable for application by brush was made by mixing 3 parts by weight of natural graphite powder with 7 parts by weight of waterglass syrup (Na2O 18%, sio2 36%, H2O 46% by weight) and 5 parts by weight of water. Two brush coats of this mix on the steel casing of a sodium sulphur cell
produced a coating of 0.06 mm thickness.
The powder size is not critical; in the above exam
ples, the particles had linear dimensions in the range of 0.1 micron to 100 microns.
Tests have shown that coatings as described with
reference to the foregoing examples present or retard the corrosion of a steel cell casing in a sodium sulphur battery at 350 C should a neighbouring cell about 1 cm away spray its contents at the cell with the coating on it.
Thicker coatings than those described in the above examples can readily be obtained by the application of a further layer or layers and/or by reducing the water content of the slurry.
Claims (11)
1. A sodium sulphur cell having a metal casing containing a solid electrolyte membrane separating sodium from a cathodic reactant wherein the casing has an outer coating comprising a particulate, noninflammable filler material which is chemically inert to hot sodium and sulphur/sodium polysulphides, the particles being bound together with sodium silicate.
2. A sodium sulphur cell as claimed in claim 1 wherein the filler material is a flaky material.
3. Asodium sulphurcell as claimed in either claim 1 or claim 2 wherein the filler material is graphite.
4. A sodium sulphur cell as claimed in either claim 1 or claim 2 wherein the filler material is talc.
5. A sodium sulphur cell as claimed in either claim 1 or claim 2 wherein the filler material is molybdenum disulphide.
6. A sodium sulphur cell as claimed in either claim 1 or claim 2 wherein the filler material is mica.
7. A sodium sulphur cell as claimed in any of the preceding claims wherein the proportion of binder to filler is in the range of 1:0.8 to 1:8 by weight.
8. A sodium sulphur cell as claimed in any of the preceding claims wherein the filler comprises particles having linear dimensions in the range of 0.1 micron to 100 microns.
9. A sodium sulphur cell as claimed in any of the preceding claims wherein the sodium silicate is
Na2O.x SiO2 where x is in the range of 1 to 5.
10. A sodium sulphur cell having a metal casing with an outer coating substantially as hereinbefore described with reference to the foregoing examples.
11. A battery comprising a plurality of cells as claimed in any of the preceding claims.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7911551A GB2046502B (en) | 1979-04-03 | 1979-04-03 | Sodium sulphur cells |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7911551A GB2046502B (en) | 1979-04-03 | 1979-04-03 | Sodium sulphur cells |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2046502A true GB2046502A (en) | 1980-11-12 |
| GB2046502B GB2046502B (en) | 1982-11-10 |
Family
ID=10504285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7911551A Expired GB2046502B (en) | 1979-04-03 | 1979-04-03 | Sodium sulphur cells |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2046502B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000016080A1 (en) * | 1998-09-11 | 2000-03-23 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | Method for producing a reference electrode for a galvanic cell with cation-conducting solid electrolytes |
| US20110165454A1 (en) * | 2008-09-05 | 2011-07-07 | Kazuya Iwamoto | Battery pack |
| US20110195291A1 (en) * | 2009-06-08 | 2011-08-11 | Tomohiko Yokoyama | Battery pack |
| US20120028107A1 (en) * | 2010-03-30 | 2012-02-02 | Yasunari Sugita | Battery pack |
-
1979
- 1979-04-03 GB GB7911551A patent/GB2046502B/en not_active Expired
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000016080A1 (en) * | 1998-09-11 | 2000-03-23 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | Method for producing a reference electrode for a galvanic cell with cation-conducting solid electrolytes |
| US6645548B1 (en) | 1998-09-11 | 2003-11-11 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | Method for producing a reference electrode for a galvanic cell with cation-conducting solid electrolytes |
| US20110165454A1 (en) * | 2008-09-05 | 2011-07-07 | Kazuya Iwamoto | Battery pack |
| US8846245B2 (en) * | 2008-09-05 | 2014-09-30 | Panasonic Corporation | Insulatable battery pack for secondary battery |
| US20110195291A1 (en) * | 2009-06-08 | 2011-08-11 | Tomohiko Yokoyama | Battery pack |
| US8592067B2 (en) * | 2009-06-08 | 2013-11-26 | Panasonic Corporation | Battery pack having a heat insulating layer |
| US20120028107A1 (en) * | 2010-03-30 | 2012-02-02 | Yasunari Sugita | Battery pack |
| US8592076B2 (en) * | 2010-03-30 | 2013-11-26 | Panasonic Corporation | Battery pack |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2046502B (en) | 1982-11-10 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |