WO2004019436A1 - 固体高分子形燃料電池 - Google Patents
固体高分子形燃料電池 Download PDFInfo
- Publication number
- WO2004019436A1 WO2004019436A1 PCT/JP2003/010478 JP0310478W WO2004019436A1 WO 2004019436 A1 WO2004019436 A1 WO 2004019436A1 JP 0310478 W JP0310478 W JP 0310478W WO 2004019436 A1 WO2004019436 A1 WO 2004019436A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- fuel cell
- fuel
- polymer electrolyte
- catalyst
- Prior art date
Links
Classifications
-
- 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
- H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
-
- 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
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
-
- 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
- H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
- H01M8/222—Fuel cells in which the fuel is based on compounds containing nitrogen, e.g. hydrazine, ammonia
-
- 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
Definitions
- the present invention relates to a polymer electrolyte fuel cell.
- Polymer electrolyte fuel cells can be used for power supplies for electric vehicles, aerospace equipment, and other transport equipment, and for portable use, because of their high current density at low temperatures and the possibility of miniaturization. Research and development are progressing as power sources.
- As the fuel supplied to the polymer electrolyte fuel cell natural gas, hydrogen gas produced by reforming methanol, gasoline, or the like is generally used.
- polymer electrolyte fuel cells that directly supply methanol as fuel have attracted attention in recent years because of their convenience as liquid fuels for storage and transportation.
- direct current fuel cells are the mainstream for small power supplies and chargers for mobile devices.
- wearable information terminals, implantable biosensors, and medical devices are also being developed, and these microelectronic devices can be powered only by supplying fuel without charging them.
- the application of time-operated direct fuel cells is being considered.
- the direct methanol fuel cell has a structure in which electrodes are attached to both sides of a solid polymer electrolyte membrane, similarly to a solid polymer fuel cell using pure hydrogen or reformed hydrogen as a fuel.
- a platinum-ruthenium catalyst is used for the anode (fuel electrode)
- a platinum catalyst is used for the power source (air electrode).
- the present inventor has been studying a polymer electrolyte direct fuel cell that supplies another compound as a fuel instead of methanol while paying attention to the problems of the conventional technology.
- a group of compounds such as ascorbic acid, which is used as a reducing agent in a reaction process such as catalyst preparation, synthesis reaction, and electroless plating, is used as a fuel, solids that can reduce the problems of the prior art
- a polymer type direct fuel cell can be obtained.
- the present invention provides the following polymer electrolyte direct fuel cell.
- At least one member selected from the group consisting of ascorbic acid, isoascorbic acid, sulfurous acid, bisulfite, dithionous acid and salts thereof is used as a fuel, and a current collector composed of a power pad or carbon cloth is used as a solid.
- the direct fuel cell of the present invention comprises a solution of a compound selected from ascorbic acid, isoascorbic acid, citric acid, tartaric acid, sulfurous acid, thiosulfuric acid, hydrogensulfite, dithionous acid, phosphorous acid, hypophosphorous acid, and salts thereof. Is supplied as fuel to generate electricity.
- Fig. 1 shows cyclic poles measured in a 0.5 M sulfuric acid solution on a platinum-ruthenium electrode using ascorbic acid, sodium sulfite, sodium bisulfite, sodium dithionite and hypophosphorous acid, respectively. Evening gram. Figure 1 also shows the results for methanol for comparison.
- ascorbic acid, isoascorbic acid, citric acid, tartaric acid and their salts sodium, potassium, magnesium, calcium
- ascorbic acid, isoascorbic acid, citric acid, tartaric acid and their salts are used as fuel, only the C-OH is oxidized to a ketone group and no dangerous compounds are produced.
- sulfurous acid, thiosulfuric acid, hydrogen sulfite, dithionous acid, phosphorous acid, hypophosphorous acid and their salts are corrosive and irritating. Although it is known to have properties and requires careful handling, it is not a designated compound such as methanol.
- Sulfurous acid, hydrogen sulfite, thiosulfuric acid, dithionous acid and their salts may produce sulfuric acid, and phosphorous acid, hypophosphorous acid and their salts may produce phosphoric acid. By collecting in the reservoir, release to the outside of the device can be prevented, so that practical problems can be avoided.
- a known polymer electrolyte membrane, an electrode catalyst, a membrane-electrode assembly, and a cell structure used in an ordinary polymer electrolyte fuel cell can be applied to the fuel cell according to the present invention.
- electrode catalyst various kinds of conventionally known metals and metal alloys can be used as the electrode catalyst.
- Various types of metal catalysts, or supported catalysts in which fine particles of these catalysts are dispersed on a carrier such as carbon can be used.
- a carbon such as carbon black can be used without using a noble metal.
- the material can be used as it is as the anode electrode.
- carbon black having a high specific surface area (50 m 2 / g or more) is more preferable.
- a current collector such as carbon paper or carbon cloth is used as a solid.
- polymer electrolyte membrane various ion-exchange resin membranes such as perfluorocarbon-based, styrene-dipinylbenzene-based copolymer, and polybenzimidazole-based can be used.
- a joined body of the solid polymer electrolyte membrane and the electrode catalyst is produced in the same manner as a generally known joined body.
- a method is used in which a catalyst ink prepared by mixing a catalyst powder and an electrolyte solution is thinned and then hot-pressed on the electrolyte membrane or directly coated on the polymer membrane and dried.
- a catalyst can be directly attached to the solid polymer membrane by a method such as adsorption reduction, electroless plating, sputtering, or CVD.
- electrodes are fabricated by applying a catalyst ink directly to a gas diffusion layer such as a carbon vapor or a carbon cloth or a current collector and drying it, or impregnating and reducing a metal complex as a precursor. May be.
- a carbon material such as carbon black can be used as the anode catalyst.
- the current collector itself made of carbon paper, carbon cloth, or the like can also function as an anode catalyst.
- Both sides of the obtained membrane-electrode assembly are made of carbon paper or carbon cloth T / JP2003 / 010478
- At least one of the above compounds is supplied as a fuel to the anode side in the form of a solution of about 10 to 5 M (more preferably, about 10 to 3 M), and air or oxygen is supplied to the power source side. Disperse naturally.
- the operating temperature of the fuel cell of the present invention varies depending on the electrolyte membrane used, but is usually about 0 to 150 ° C, more preferably about 10 to 100 ° C.
- the direct fuel cell which uses the compound instead of methanol designated as a deleterious substance as a fuel of a polymer electrolyte fuel cell is obtained.
- each compound used in the present invention does not generate harmful substances such as formaldehyde and formic acid as oxidation products.
- the direct fuel cell according to the present invention can reduce the crossover that degrades the performance of the direct methanol fuel cell.
- some of the compounds used in the present invention can realize a high-performance polymer electrolyte fuel cell even when a carbon material is used as a catalyst on the anode side instead of an expensive noble metal. .
- the effect is remarkable when a power pump rack having a large specific surface area is used as an anode catalyst.
- FIG. 1 is a cyclic portogram of each fuel used in the present invention in a 0.5 M sulfuric acid solution.
- FIG. 2 is a graph showing current-voltage characteristics of the fuel cell according to Example 1.
- FIG. 3 is a graph showing current-voltage characteristics of the fuel cell according to Example 2.
- FIG. 4 is a graph showing the cathode potentials of the fuel cells according to Example 3 and Comparative Example 2.
- FIG. 5 is a graph showing current-voltage characteristics of the fuel cell according to Example 4.
- FIG. 6 is a graph showing a current-voltage characteristic of the fuel cell according to the fifth embodiment.
- FIG. 7 is a graph showing current-voltage characteristics of the fuel cell according to Example 6.
- FIG. 8 is a graph showing current-voltage characteristics of the fuel cell according to Embodiment 7.
- FIG. 9 is a graph showing current-voltage characteristics of the fuel cell according to Example 8.
- FIG. 10 is a graph showing current-voltage characteristics of the fuel cell according to Embodiment 9.
- FIG. 11 is a graph showing current-voltage characteristics of the fuel cell according to Example 10;
- Example 1 Example 1
- Platinum-ruthenium black was used as the anode catalyst, and platinum black treated with water repellency with polytetrafluoroethylene was used as the power sword catalyst.
- Each catalyst was mixed with a polymer electrolyte solution to form a catalyst ink, and a thin film was formed to form an electrode sheet. Then, hot pressing was performed on both sides of a polymer electrolyte membrane (trade name of “Nafion-117”, manufactured by DuPont). Thus, a membrane-electrode assembly was obtained.
- a fuel cell is assembled by sandwiching both sides of the obtained membrane-electrode assembly with a force cloth, an aqueous solution of a predetermined fuel is supplied to the anode, and air is naturally diffused to the force sword, thereby at room temperature.
- the power generation performance of the fuel cell was evaluated.
- Table 1 shows the values of the open circuit voltage when using various fuels.
- Fig. 2 shows the current-voltage characteristics when ascorbic acid, sodium dithionite, phosphorous acid, and hypophosphorous acid each having an aqueous solution concentration of 0.5M were used as fuel.
- Example 2 Fuel cells were produced in the same manner as in Example 1, except that platinum, ruthenium, palladium, iridium, and rhodium were used as anode catalysts instead of platinum-ruthenium black in Example 1.
- a fuel cell was manufactured according to Example 1 by directly contacting the carbon cloth with the polymer electrolyte membrane without using a catalyst on the anode side.
- FIG. 3 shows the current-voltage characteristics of these fuel cells.
- FIG. 3 also shows the current-voltage characteristics of the cell using ascorbic acid as a fuel according to the first embodiment.
- Fig. 3 shows that the oxidation reaction of ascorbic acid proceeded on all anodes, including the case where no catalyst was used for the anodes, and the fuel cell was operated.
- the types of anode catalysts that can be used are increased, and even if a platinum-ruthenium catalyst is not used on the anode side, or even if a catalyst is not used, the fuel cell can be used. It is clear that power generation is possible.
- a 1 M methanol solution was supplied to the anode side of the fuel cell prepared in Example 2, and the power generation performance was evaluated.
- a 1 M methanol solution was placed on the anode side of the fuel cell fabricated in the same manner as in Example 3. The solution was supplied and the force sword potential was measured at room temperature.
- Example 3 using ascorbic acid as a fuel according to the present invention shows a higher force sword potential than Comparative Example 2 using methanol as a fuel. It is known that methanol has a large membrane permeability from the anode to the force sword, and the cathodic potential decreases as a hybrid potential. On the other hand, the crossover is considered to be small in the fuel used in the present invention since the force sword potential is high.
- Fuel cells were fabricated in the same manner as in Example 1 using various blacks of platinum, ruthenium, palladium, iridium, rhodium and platinum-ruthenium as anode catalysts.
- Example 1 a fuel cell was fabricated according to Example 1 by directly contacting a carbon cloth as a current collector with the polymer electrolyte membrane without using a catalyst on the anode side.
- Fuel cells were fabricated in the same manner as in Example 1 using various blacks of platinum, ruthenium, palladium, iridium, rhodium and platinum-ruthenium as anode catalysts.
- a fuel cell was manufactured according to Example 1. Next, a 0.05 M aqueous solution of sulfurous acid was supplied to the anode, and air was spontaneously diffused into the power sword to evaluate the power generation characteristics of each fuel cell at room temperature.
- Figure 6 shows the current-voltage characteristics of these fuel cells.
- Example 1 without using platinum-ruthenium black used as an anode catalyst, only one side of the polymer electrolyte membrane was hot-pressed with platinum black as a force sword to form did. Then, a carbon cloth attached with carbon black by the above-described method is applied to the film surface on the opposite side of the force sode of the obtained membrane one-sided force bonded body, and a normal carbon cloth is pressed to the cathode side film surface, and the fuel cell is pressed. The cell was assembled.
- FIG. 11 shows current-voltage characteristics of these fuel cells.
- FIG. 11 shows only the carbon cloth (force
- Fig. 11 shows that the performance of the ascorbic acid fuel cell is improved by attaching various carbon blacks with a large specific surface area to the carbon cloth arranged on the anode side.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003257581A AU2003257581A1 (en) | 2002-08-21 | 2003-08-20 | Solid polymer type fuel cell |
JP2004530570A JP4238364B2 (ja) | 2002-08-21 | 2003-08-20 | 固体高分子形燃料電池 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002240086 | 2002-08-21 | ||
JP2002-240086 | 2002-08-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004019436A1 true WO2004019436A1 (ja) | 2004-03-04 |
Family
ID=31943924
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2003/010478 WO2004019436A1 (ja) | 2002-08-21 | 2003-08-20 | 固体高分子形燃料電池 |
Country Status (3)
Country | Link |
---|---|
JP (1) | JP4238364B2 (ja) |
AU (1) | AU2003257581A1 (ja) |
WO (1) | WO2004019436A1 (ja) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100388553C (zh) * | 2005-09-28 | 2008-05-14 | 浙江大学 | 微型生物燃料电池及其制造方法 |
JP2011060531A (ja) * | 2009-09-09 | 2011-03-24 | National Institute Of Advanced Industrial Science & Technology | 直接型燃料電池 |
WO2014098171A1 (ja) * | 2012-12-20 | 2014-06-26 | トヨタ自動車株式会社 | 燃料電池 |
JP2016096156A (ja) * | 2005-02-11 | 2016-05-26 | ダブリュ.エル.ゴア アンド アソシエイツ,インコーポレイティドW.L. Gore & Associates, Incorporated | 燃料電池の劣化を低減する方法 |
CN109952677A (zh) * | 2016-08-05 | 2019-06-28 | 罗地亚经营管理公司 | 无膜直接型燃料电池 |
JP2020053261A (ja) * | 2018-09-27 | 2020-04-02 | 東洋インキScホールディングス株式会社 | 燃料電池正極用触媒、燃料電池正極用ペースト組成物、燃料電池用正極、燃料電池、および水分センサー |
JP2020098725A (ja) * | 2018-12-18 | 2020-06-25 | 東洋インキScホールディングス株式会社 | バイオ燃料電池アノード用触媒インキ材料、バイオ燃料電池アノード用触媒インキ組成物、バイオ燃料電池アノード、バイオ燃料電池デバイス |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002151132A (ja) * | 2000-11-07 | 2002-05-24 | Japan Storage Battery Co Ltd | グリコールを燃料にした燃料電池 |
-
2003
- 2003-08-20 AU AU2003257581A patent/AU2003257581A1/en not_active Abandoned
- 2003-08-20 JP JP2004530570A patent/JP4238364B2/ja not_active Expired - Lifetime
- 2003-08-20 WO PCT/JP2003/010478 patent/WO2004019436A1/ja active Application Filing
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002151132A (ja) * | 2000-11-07 | 2002-05-24 | Japan Storage Battery Co Ltd | グリコールを燃料にした燃料電池 |
Non-Patent Citations (2)
Title |
---|
"Sangyo gijutsu sogo ken seikatsu kenkyokei", THE ELECTROCHEMICAL SOCIETY OF JAPAN TAIKAI KOEN YOSHISHU, vol. 70, 25 March 2003 (2003-03-25), pages 299, XP002974990 * |
"Sangyo hijutsu sougo ken seikatsu kankyokei", DENKI KAGAKU SHUKI TAIKAI KOEN YOSHISHU, vol. 2002, 5 September 2002 (2002-09-05), pages 92, XP002974989 * |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016096156A (ja) * | 2005-02-11 | 2016-05-26 | ダブリュ.エル.ゴア アンド アソシエイツ,インコーポレイティドW.L. Gore & Associates, Incorporated | 燃料電池の劣化を低減する方法 |
CN100388553C (zh) * | 2005-09-28 | 2008-05-14 | 浙江大学 | 微型生物燃料电池及其制造方法 |
JP2011060531A (ja) * | 2009-09-09 | 2011-03-24 | National Institute Of Advanced Industrial Science & Technology | 直接型燃料電池 |
WO2014098171A1 (ja) * | 2012-12-20 | 2014-06-26 | トヨタ自動車株式会社 | 燃料電池 |
CN104854748A (zh) * | 2012-12-20 | 2015-08-19 | 丰田自动车株式会社 | 燃料电池 |
JP5888438B2 (ja) * | 2012-12-20 | 2016-03-22 | トヨタ自動車株式会社 | 燃料電池 |
US9742020B2 (en) | 2012-12-20 | 2017-08-22 | Toyota Jidosha Kabushiki Kaisha | Fuel cell |
CN109952677A (zh) * | 2016-08-05 | 2019-06-28 | 罗地亚经营管理公司 | 无膜直接型燃料电池 |
JP2020053261A (ja) * | 2018-09-27 | 2020-04-02 | 東洋インキScホールディングス株式会社 | 燃料電池正極用触媒、燃料電池正極用ペースト組成物、燃料電池用正極、燃料電池、および水分センサー |
JP7155814B2 (ja) | 2018-09-27 | 2022-10-19 | 東洋インキScホールディングス株式会社 | 燃料電池正極用触媒、燃料電池正極用ペースト組成物、燃料電池用正極、燃料電池、および水分センサー |
JP2020098725A (ja) * | 2018-12-18 | 2020-06-25 | 東洋インキScホールディングス株式会社 | バイオ燃料電池アノード用触媒インキ材料、バイオ燃料電池アノード用触媒インキ組成物、バイオ燃料電池アノード、バイオ燃料電池デバイス |
JP7205209B2 (ja) | 2018-12-18 | 2023-01-17 | 東洋インキScホールディングス株式会社 | バイオ燃料電池アノード用触媒インキ材料、バイオ燃料電池アノード用触媒インキ組成物、バイオ燃料電池アノード、バイオ燃料電池デバイス |
Also Published As
Publication number | Publication date |
---|---|
AU2003257581A1 (en) | 2004-03-11 |
JPWO2004019436A1 (ja) | 2005-12-15 |
JP4238364B2 (ja) | 2009-03-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5523177A (en) | Membrane-electrode assembly for a direct methanol fuel cell | |
Vigier et al. | Development of anode catalysts for a direct ethanol fuel cell | |
JP4083721B2 (ja) | 高濃度炭素担持触媒、その製造方法、該触媒を利用した触媒電極及びそれを利用した燃料電池 | |
US6670301B2 (en) | Carbon monoxide tolerant electrocatalyst with low platinum loading and a process for its preparation | |
US20090068505A1 (en) | Electrocatalyst for Alcohol Oxidation at Fuel Cell Anodes | |
EP2847814B1 (en) | Anode electro-catalysts for alkaline membrane fuel cells | |
WO2005048379A2 (en) | Improved palladium-based electrocatalysts and fuel cells employing such electrocatalysts | |
JP2006260909A (ja) | 膜電極接合体およびこれを用いた固体高分子型燃料電池 | |
CN110416553B (zh) | 质子膜燃料电池催化剂及其制备方法和燃料电池*** | |
US5916702A (en) | CO tolerant platinum-zinc fuel cell electrode | |
US7740974B2 (en) | Formic acid fuel cells and catalysts | |
JP4238364B2 (ja) | 固体高分子形燃料電池 | |
JP2002343403A (ja) | 燃料電池の運転方法 | |
JP2008210581A (ja) | 燃料電池 | |
JP6998797B2 (ja) | 有機ハイドライド製造装置、有機ハイドライドの製造方法およびエネルギー輸送方法 | |
WO2012102715A1 (en) | A membrane electrode assembly for fuel cells | |
JP3844022B2 (ja) | 固体高分子電解質を備えた直接型メタノ−ル燃料電池 | |
JP2001256982A (ja) | 燃料電池用電極および燃料電池 | |
JP3788491B2 (ja) | 固体高分子電解質を備えた直接型メタノ−ル燃料電池およびその製造方法 | |
JP2001126738A (ja) | 燃料電池用電極の製造方法およびそれを用いた直接メタノール燃料電池 | |
JP5375623B2 (ja) | 固体高分子型燃料電池用触媒及びこれを用いた固体高分子型燃料電池用電極 | |
JP3788490B2 (ja) | 固体高分子電解質を備えた直接型メタノ−ル燃料電池およびその製造方法 | |
JP4478009B2 (ja) | 燃料電池 | |
US20240136540A1 (en) | Method for producing catalyst layers for fuel cells | |
JP4392823B2 (ja) | 固体電解質型燃料電池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2004530570 Country of ref document: JP |
|
122 | Ep: pct application non-entry in european phase |