GB2293916A - Solid electrolyte/electrode assembly for fuel cell and sensor manufactured by transfer of electrolyte layer to electrode substrate - Google Patents
Solid electrolyte/electrode assembly for fuel cell and sensor manufactured by transfer of electrolyte layer to electrode substrate Download PDFInfo
- Publication number
- GB2293916A GB2293916A GB9420030A GB9420030A GB2293916A GB 2293916 A GB2293916 A GB 2293916A GB 9420030 A GB9420030 A GB 9420030A GB 9420030 A GB9420030 A GB 9420030A GB 2293916 A GB2293916 A GB 2293916A
- Authority
- GB
- United Kingdom
- Prior art keywords
- electrolyte
- electrode
- transfer
- substrate
- layer
- 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
- 239000003792 electrolyte Substances 0.000 title claims abstract description 34
- 239000000758 substrate Substances 0.000 title claims abstract description 25
- 239000000446 fuel Substances 0.000 title claims description 12
- 239000007784 solid electrolyte Substances 0.000 title 1
- 238000000034 method Methods 0.000 claims description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 11
- 238000010304 firing Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 6
- 239000000976 ink Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
- G01N27/4073—Composition or fabrication of the solid electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
-
- 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
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
- H01M2300/0074—Ion conductive 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Fuel Cell (AREA)
Abstract
A thin flexible transfer composed of an electrolyte component together with organic component(s) are applied to an electrode substrate, eg a tube, and the combination is fired to drive off the organic component(s) and adhere a thin, continuous layer of the electrolyte to the electrode.
Description
FUEL CELL PRODUCTION
The present invention concerns the production of fuel cells, and more especially it concerns the production of electrode/electrolyte assemblies for solid oxide fuel cells (SOFC's).
Solid oxide fuel cells appear to offer certain technical advantages over other types of fuel cells, for example there is one SOFC system offered by
Westinghouse. Some literature suggests that SOFC's should use tubular cells, rather than a "filter press" type stack using planar cells. One problem area in SOFC's is the difficulty in start-up from cold. Typically, a solid oxide fuel cell may have an operating temperature of -1,0000C, although so-called low-temperature SOFC's may operate at 700-800"C, and the solid oxide electrolytes, eg yttria stabilised zirconia, suffer thermal shock rather readily, and shatter or crack. Additionally, conventional
SOFC's use solid oxide electrolytes such as yttria stabilised zirconia, which break easily during fabrication.
The present invention provides a method of manufacturing an electrolyte/electrode assembly for SOFC's, which method comprises applying to a substrate which is capable of acting as an electrode in a SOFC or carries an electrode layer, a flexible transfer comprising an oxide electrolyte component together with organic components, and firing the combination of substrate and transfer to burn off the organic components and to adhere the electrolyte component layer to said substrate to form a solid oxide electrolyte/electrode assembly.
The present invention should be understood as being applicable to solid oxide sensors, which are a type of fuel cell.
Although the invention has particular application to the production of non-planar electrode-electrolyte combinations especially tubular SOFC's, the invention may offer technical advantages for manufacturing planar SOFC's particularly where multi-layers or intricate patterns are required.
The substrate for application of the transfer will normally be a solid electrode in the pre-fired or fired state, an example of such an electrode is nickel/yttria stabilised zirconia cermet. The electrolyte or substrate itself does not form part of the present invention, nor does the material chosen for the electrode(s).
Descriptions of such materials given herein are to be regarded as exemplary and not in any way limiting.
The flexible transfer sheet may be prepared by methods analogous to the preparation of ceramic transfers for the tile or tableware industry, except that instead of decorative colours, the inorganic component of the transfer is functional as an electrolyte layer after firing. Hereinafter, the transfer will be described as being prepared by screen printing, but other printing methods, including lithographic printing, or combination methods, may be used if desired.
In general, the selected electrolyte component, for example an yttria stabilised zirconia powder, is dispersed in an organic screen printing medium, eg by triple roll milling, to form an ink. The electrolyte powder content of the ink is suitably 20-250 parts by wt to 100 parts by wt of medium, typically 40-100 parts by wt of solids to 100 parts by wt of medium. The medium is suitably 30-50 parts by wt of an acrylic resin in a hydrocarbon solvent (eg Solvesso (Trade Mark) 100) together with 2-5% of a plasticiser such as dioctyl phthalate.The ink is printed through a screen incorporating the desired pattern(s), for example using an appropriate synthetic fibre screen or stainless steel mesh, onto a release sheet, especially commercial transfer paper (a paper coated with a water soluble gum), allowed to air-dry or dry under an air jet and, if required, the printing process is repeated to form a multi-layer structure. If it is desired to produce a multi-layer structure, any second or subsequent layer may be identical in composition and design to the first printed layer, or may be different.
Each dried printed transfer is over-printed by a "covercoat" which gives integrity to the printed material and facilitates handling whilst being removed from the release sheet and being applied to the substrate. Suitable covercoats are known in the decorative ceramic transfer industry and may be an acrylic resin solution compatible with the organic components of the medium.
Each layer of dried ink may be up to 10 microns thick, although thicknesses of up to 50 microns may be used if required, and this depends upon the screen mesh used, eg from 10-160 apertures per linear cm. In general, for small diameter tubes it is necessary that the inorganic ink layer does not exceed 10 microns to ensure good contact. Also, ;. is technically advantageous to have as thin an electrolyte layer as possible, providing that the layer is substantially ( > 95%) impervious to gas. The appropriate rheology of the ink can be determined by the skilled printer in combination with a rheological examination of the inks.
During application to the substrate, the transfer should retain sufficient flexibility from the organic components, to "drape" or cover the shape of the substrate, eg in tubular form, and to cover undulations or dimples in the substrate.
It will be understood that the method of the invention cannot provide satisfactory even deposition if the substrate has sudden step-like changes in surface section, but is ideal for smooth transformations.
The dried covercoated transfer may be stocked until required, then soaked in water to provide a film carrying the electrolyte layer and remnants of gum, which may be positioned on the desired substrate, and the water squeezed out using an appropriate method deteremined by the tube diameter or other substrate configuration.
While the method of the invention has been particularly described herein with reference to water-slide transfers, alternative transfer constructions may be used, depending upon the shape of the substrate. The transfer/substrate combination may then be fired as described below.
Firing the transfer/substrate combination in excess of 5000C is sufficient to cause all organic components to decompose and to burn off. To produce a satisfactory bond between electrode and substrate, it is necessary to continue the firing to typically 1300"C-1500"C. The time/temperature firing curve should be determined experimentally for each electrode/electrolyte combination in order to optimise the electrochemical properties required.
Where the substrate is a solid oxide electrode, the method of the invention provides a simple method of depositing a thin, uniform electrolyte onto the electrode which may be of complex shape, thus offering improved design options.
The other electrode may be applied using similar technology (see UK Patent
Application No 9415150.3).
The invention will now be described by way of example only.
An ink was prepared by triple roll milling 54 parts by wt of commercial yttria-stabilised zirconia powder (Tosoh T8Y) with 100 parts by wt of an organic medium. The organic medium was a pre-mixed acrylic resin solution of 40% by wt of butyl methacrylate in 60% aromatic hydrocarbon solvent. The ink was screen printed through a 150S-X (150 apertures/linear cm) "estal mono" mesh carrying the required electrolyte image, onto a commercial water-slide transfer paper.
After drying, the printed pattern was covercoated by overprinting with an acrylic resin system of 45% butyVmethyl methacrylate copolymer, 5% butyl benzyl phthalate in 50% aromatic hydrocarbon solvent, screen printed through a 80# (80 apertures/linear inch, 31.5 apertures/linear cm) stainless steel mesh. The completed transfers were allowed to dry.
The transfer sheet was soaked in water to release the transfer then applied to the exterior surface of a 2mm outside diameter tube extruded from a 50% nickel oxide 50% yttria stabilised zirconia mixture, the tube wall having a thickness of approximately 0.25mm, and fired at 1500"C. The electrolyte layer applied by transfer sintered well onto the tube and SEM studies indicate that there is a continuous layer of electrolyte over the surface, the layer having a thickness of
1-2 microns.
Platinum wire was wound around the electrolyte layer, connected with platinum paste and fired at 10000C. A nickel wire made contact with the inner electrode substrate.
The assembly was heated to 1000"C in a furnace and fuel (hydrogen/5% by vol water) was passed into the tube via a rubber connector.
A voltage of 0.95 volts was observed at open circuit, demonstrating density and integrity of the thin uniform layer of electrolyte.
Claims (10)
1. A method of manufacturing an electrolyte/electrode for SOFC's, which method comprises applying to a substrate which is capable of acting as an electrode in a SOFC or carries an electrode layer, a flexible transfer comprising an oxide electrolyte component together with organic components, and firing the combination of substrate and transfer to burn off the organic components and to adhere the electrolyte component layer to said substrate to form a solid oxide electrolyte/electrode assembly.
2. A method according to claim 1, wherein the substrate is in tubular form.
3. A method according to claim 1 or 2, wherein the oxide electrolyte component is an yttria stabilised zirconia.
4. A method according to claim 1, 2 or 3, wherein the combination of substrate and transfer is fired at 1300-1500 C.
5. A method according to any one of the preceding claims, wherein the electrolyte component layer after firing has a thickness of up to 10 microns.
6. A method according to claim 5, wherein the electrolyte component layer after firing has a thickness of 1-2 microns.
7. A method according to any one of the preceding claims, wherein an electrode layer is applied by transfer to the electrolyte layer before or after firing, and is fired to adhere the electrode layer to the electrolyte layer.
8. A method according to claim 1, substantially as hereinbefore described.
9. A fuel cell comprising an electrolyte/electrode assembly manufactured according to any one of the preceding claims.
10. A fuel cell stack comprising fuel cells according to claim 9.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9420030A GB2293916B (en) | 1994-10-05 | 1994-10-05 | Fuel cell production |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9420030A GB2293916B (en) | 1994-10-05 | 1994-10-05 | Fuel cell production |
Publications (3)
Publication Number | Publication Date |
---|---|
GB9420030D0 GB9420030D0 (en) | 1994-11-16 |
GB2293916A true GB2293916A (en) | 1996-04-10 |
GB2293916B GB2293916B (en) | 1997-04-02 |
Family
ID=10762349
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB9420030A Expired - Fee Related GB2293916B (en) | 1994-10-05 | 1994-10-05 | Fuel cell production |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB2293916B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2407204A (en) * | 2003-10-15 | 2005-04-20 | Sunplus Technology Co Ltd | Electronic musical score device |
US7195832B2 (en) | 2000-10-19 | 2007-03-27 | British Nuclear Fuels Plc | Fuel cells |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1322959A (en) * | 1969-10-27 | 1973-07-11 | Hitachi Ltd | Solid electrolyte |
US4421797A (en) * | 1980-09-16 | 1983-12-20 | Pressbau Gmbh | Method and device for the dry-spray application of concrete to a substrate |
GB2148586A (en) * | 1983-10-19 | 1985-05-30 | Atomic Energy Authority Uk | Solid state cell manufacture |
US4738741A (en) * | 1986-12-19 | 1988-04-19 | The Dow Chemical Company | Method for forming an improved membrane/electrode combination having interconnected roadways of catalytically active particles |
US5085742A (en) * | 1990-10-15 | 1992-02-04 | Westinghouse Electric Corp. | Solid oxide electrochemical cell fabrication process |
US5211984A (en) * | 1991-02-19 | 1993-05-18 | The Regents Of The University Of California | Membrane catalyst layer for fuel cells |
US5279624A (en) * | 1992-11-27 | 1994-01-18 | Gould Inc. | Solder sealed solid electrolyte cell housed within a ceramic frame and the method for producing it |
-
1994
- 1994-10-05 GB GB9420030A patent/GB2293916B/en not_active Expired - Fee Related
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1322959A (en) * | 1969-10-27 | 1973-07-11 | Hitachi Ltd | Solid electrolyte |
US4421797A (en) * | 1980-09-16 | 1983-12-20 | Pressbau Gmbh | Method and device for the dry-spray application of concrete to a substrate |
GB2148586A (en) * | 1983-10-19 | 1985-05-30 | Atomic Energy Authority Uk | Solid state cell manufacture |
US4738741A (en) * | 1986-12-19 | 1988-04-19 | The Dow Chemical Company | Method for forming an improved membrane/electrode combination having interconnected roadways of catalytically active particles |
US5085742A (en) * | 1990-10-15 | 1992-02-04 | Westinghouse Electric Corp. | Solid oxide electrochemical cell fabrication process |
US5211984A (en) * | 1991-02-19 | 1993-05-18 | The Regents Of The University Of California | Membrane catalyst layer for fuel cells |
US5279624A (en) * | 1992-11-27 | 1994-01-18 | Gould Inc. | Solder sealed solid electrolyte cell housed within a ceramic frame and the method for producing it |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7195832B2 (en) | 2000-10-19 | 2007-03-27 | British Nuclear Fuels Plc | Fuel cells |
GB2407204A (en) * | 2003-10-15 | 2005-04-20 | Sunplus Technology Co Ltd | Electronic musical score device |
GB2407204B (en) * | 2003-10-15 | 2006-09-06 | Sunplus Technology Co Ltd | Electronic musical score device |
Also Published As
Publication number | Publication date |
---|---|
GB9420030D0 (en) | 1994-11-16 |
GB2293916B (en) | 1997-04-02 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19981005 |