WO2003020691A1 - Heptafluor-2-propansulfonatsalze und ihre verwendung in der elektrotechnik - Google Patents
Heptafluor-2-propansulfonatsalze und ihre verwendung in der elektrotechnik Download PDFInfo
- Publication number
- WO2003020691A1 WO2003020691A1 PCT/EP2002/009544 EP0209544W WO03020691A1 WO 2003020691 A1 WO2003020691 A1 WO 2003020691A1 EP 0209544 W EP0209544 W EP 0209544W WO 03020691 A1 WO03020691 A1 WO 03020691A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alkali metal
- compounds
- general formula
- tetraalkylammonium
- salt
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/06—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing halogen atoms, or nitro or nitroso groups bound to the carbon skeleton
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
-
- 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
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
- H01M2300/004—Three solvents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- Alkali metal and tetraalkylammonium salts of certain anions are useful in electrical engineering. Tetraalkylammonium salts are e.g. B. used in double-layer capacitors.
- Alkali metal salts in particular the lithium salt of the hexafluorophosphate anion, the tetrafluoroborate anion, the trifluoromethanesulfonate anion or the bis-trifluoromethanesulfonylimide, are used as the conductive salt for lithium ion batteries.
- the conductive salt used is dissolved in an electrolyte solvent.
- Electrolyte solvents which are particularly suitable are, for example, alkylene carbonates, dialkyl carbonates, ethers, formamides, sulfolanes or methylsulfolanes and nitriles, other nitrogen-containing compounds such as nitroethane or pyrrolidinones.
- alkylene carbonates dialkyl carbonates
- ethers formamides
- sulfolanes or methylsulfolanes and nitriles other nitrogen-containing compounds
- other nitrogen-containing compounds such as nitroethane or pyrrolidinones.
- Such compounds are described by Makoto Ue, Kazuhiko, Ida and Shoichiro Mori in J. Electrochem. Soc. 141 (1994), pages 2989 to 2996.
- the usability of fluorinated phosphoric acid esters, e.g. B. of tris (trifluoroethyl) phosphate is disclosed in EP-A 825 664, of esters
- M + stands for Li + , Na + , K + , Cs + , Rb + , R 4 P + or RN + , where the 4 alkyl groups R may be the same or different and stand for Cl-C4-alkyl or at least 2 R. Groups include nitrogen or phosphorus and form a non-aromatic ring system.
- Perfluoroisopropyl sulfonyl fluoride also known as heptafluoro-2-propanesulfonic acid fluoride
- heptafluoro-2-propanesulfonic acid fluoride which may be required as an intermediate product, can be prepared from a corresponding isopropanesulfonyl halide by electrolysis in the presence of anhydrous liquid hydrogen fluoride.
- phosphonium salts can be produced in which all four substituents R are the same, or in which at least one substituent R has a different meaning than the other three substituents.
- the phosphine is reacted with the dialkyl carbonate, the tetraalkylphosphonium alkyl carbonate is first formed, which reacts with the addition of the heptafluoro-2-propanesulfonic acid to form the desired salt.
- This method corresponds to the "Ue-Mori Process" already cited in the publication by Kang Xu and co-workers.
- Another method provides that the tetraalkylammonium halide is first converted into the tetraalkylammonium hydroxide. This is possible by adding KOH and methanol, for example; it is also possible by electrolysis or by ion exchange resins. The tetraalkylammonium hydroxide obtained is then reacted with the heptafluoro-2-propanesulfonic acid to form the desired tetraalkylammonium salt of this acid.
- Ammonium cations in which at least two of the groups R form a ring which contains the nitrogen atom can also be prepared in an analogous manner. These ring systems preferably have five, six or seven atoms in the ring.
- Some tetraalkylammonium cations are a commercial product in the form of the hydroxides. They can then be reacted with the hepta-fluoro-2-propanesulfonic acid to the desired salt.
- M + is preferably Li + or R 4 N + .
- the substituent R preferably has the meaning methyl or ethyl; the four substituents R may be the same or different. Examples of such cations are MeN + , Me 3 EtN + , n-Pr 3 MeN + , i-Pr 2 EtMeN + , n-Bu 3 MeN + , Me 4 P + , Et 4 P + , Et 4 N + , Et 3 MeP + , n-Bu 3 MeP + and N, N-dimethylpiperidinium.
- the compounds of general formula (I) provided are very well suited for use in electrical engineering, for example as a conductive salt dissolved in a solvent (electrolyte).
- the tetraalkylammonium salt and the tetraalkylphosphonium salt of heptafluoropropane sulfonate can be used, for example, in capacitors.
- capacitors These are double-layer capacitors that represent an electrochemical energy store. The electrical charge is stored in the electrical double layer that arises between a polarizable electrode and an electrolyte solution when a DC voltage is applied.
- Such capacitors are used as a "memory back up" device in many electronic devices and where large short current surges of high currents ("high pulse power”) are required, for. B. in electric cars.
- Useful solvents are given in the cited reference by Makoto Ue and co-workers.
- the alkali metal salts are particularly suitable as a conductive salt for rechargeable batteries, especially lithium ion batteries.
- the invention is further explained.
- Lithium ion batteries contain the conductive salt dissolved in a solvent or a solvent mixture.
- the solvents mentioned in the aforementioned publication by Ue and co-workers can also be used in pure or mixed form for the present field of application in lithium-ion batteries.
- Dialkyl carbonates, alkylene carbonates, lactones and formamides, for example, are particularly useful.
- Fluorine-substituted organic compounds are also useful as solvents or as solvent additives; their advantage is that they have a flame-retardant effect. point. Z. B.
- electrolytes which contain a compound of the general formula (I) and an electrolyte solvent or an electrolyte solvent are also part of the invention .
- Electrolytes which contain a compound of the general formula (I) in which M + stands for the sodium, potassium, cesium, rubidium or lithium ion are preferably used for batteries, in particular lithium ion batteries;
- Electrolytes according to the invention with compounds of the formula (I) in which M + represents the tetraalkylamium ion or tetraalkylphosphonium ion are preferably used for capacitors.
- the preferred salts and the preferred solvents or solvent mixtures have already been mentioned above.
- the present invention also relates to batteries, preferably lithium ion batteries, which contain a compound of the general formula (I).
- batteries preferably lithium ion batteries
- the statements made above also apply here with regard to the preferred salts and solvents.
- capacitors which contain a compound of the general formula (I), in particular capacitors with an electrical double layer, as are described, for example, in the above-mentioned publication by Ue and co-workers, are also a subject of the invention.
- Preferred electrolytes (dissolved salts and solvents) have already been mentioned above.
- Advantage of the compounds of general formula (I) according to the invention is their high hydrolytic and thermal stability, for. B. in comparison with the frequently used LiPF 6 .
- Heptafluoro-2-propanesulfonyl fluoride (50.4 g; 0.2 mol; 252 g ol -1 ) was in a closed reaction vessel with a slurry of calcium hydroxide (16.3 g; 0.22 mol; 74 g mol -1 ) in 50 ml of water stirred for 8 h at room temperature. The aqueous solution was filtered off from the CaF 2 formed and evaporated to dryness. The yield of [(CF 3 ) 2 CFS0 3 ] 2 Ca (62.4 g; 0.11 mol; 538 g mol -1 ) was 58.0%.
- (CF 3 ) 2 CFS0 3 H (10.0 g; 0.04 mol; 250 g mol -1 ) from stage b) was in aqueous solution with LiOH (0.96 g; 0.04 mol; 24 g mol - 1 ) neutralized and evaporated to dryness.
- the yield of (CF 3 ) 2 CFS0 3 Li (9.7 g; 0.038 mol; 256 g mol -1 ) was 95.0%.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02767438A EP1427698B1 (de) | 2001-09-04 | 2002-08-27 | Heptafluor-2-propansulfonatsalze und ihre verwendung in der elektrotechnik |
DE50214052T DE50214052D1 (de) | 2001-09-04 | 2002-08-27 | Heptafluor-2-propansulfonatsalze und ihre verwendung in der elektrotechnik |
AT02767438T ATE450500T1 (de) | 2001-09-04 | 2002-08-27 | Heptafluor-2-propansulfonatsalze und ihre verwendung in der elektrotechnik |
KR1020047002958A KR100927069B1 (ko) | 2001-09-04 | 2002-08-27 | 헵타플루오로-2-프로판설포네이트염 및 그것의 전기공업에의 이용 |
JP2003524962A JP4266821B2 (ja) | 2001-09-04 | 2002-08-27 | ヘプタフルオロ−2−プロパンスルホネート塩及び電気工学におけるその使用 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10143172.4 | 2001-09-04 | ||
DE10143172A DE10143172A1 (de) | 2001-09-04 | 2001-09-04 | Sulfonylsalze in der Elektrotechnik |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2003020691A1 true WO2003020691A1 (de) | 2003-03-13 |
Family
ID=7697579
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2002/009544 WO2003020691A1 (de) | 2001-09-04 | 2002-08-27 | Heptafluor-2-propansulfonatsalze und ihre verwendung in der elektrotechnik |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP1427698B1 (de) |
JP (1) | JP4266821B2 (de) |
KR (1) | KR100927069B1 (de) |
CN (1) | CN1279021C (de) |
AT (1) | ATE450500T1 (de) |
DE (2) | DE10143172A1 (de) |
WO (1) | WO2003020691A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007532647A (ja) * | 2004-04-13 | 2007-11-15 | ゼネラル・エレクトリック・カンパニイ | 帯電防止剤の製造方法 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20110060253A (ko) * | 2009-11-30 | 2011-06-08 | 에스케이케미칼주식회사 | 전해질 용액 및 이를 포함하는 초고용량 커패시터 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61252620A (ja) * | 1985-05-02 | 1986-11-10 | 旭硝子株式会社 | 改良された電気二重層コンデンサ |
JPS6290919A (ja) * | 1985-09-20 | 1987-04-25 | 旭硝子株式会社 | 電気二重層コンデンサ |
JPH01207263A (ja) * | 1988-02-10 | 1989-08-21 | Sony Corp | 磁気記録媒体 |
DE3913037A1 (de) * | 1988-04-21 | 1989-11-02 | Central Glass Co Ltd | Verfahren zur herstellung von alkalimetallfluoralkylsulfonaten hoher reinheit |
JP2001322975A (ja) * | 2000-05-16 | 2001-11-20 | Dainippon Ink & Chem Inc | パーフルオロアルキルスルホン酸塩の製造方法 |
-
2001
- 2001-09-04 DE DE10143172A patent/DE10143172A1/de not_active Withdrawn
-
2002
- 2002-08-27 AT AT02767438T patent/ATE450500T1/de not_active IP Right Cessation
- 2002-08-27 JP JP2003524962A patent/JP4266821B2/ja not_active Expired - Fee Related
- 2002-08-27 WO PCT/EP2002/009544 patent/WO2003020691A1/de active Application Filing
- 2002-08-27 KR KR1020047002958A patent/KR100927069B1/ko not_active IP Right Cessation
- 2002-08-27 CN CNB028172337A patent/CN1279021C/zh not_active Expired - Fee Related
- 2002-08-27 DE DE50214052T patent/DE50214052D1/de not_active Expired - Lifetime
- 2002-08-27 EP EP02767438A patent/EP1427698B1/de not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61252620A (ja) * | 1985-05-02 | 1986-11-10 | 旭硝子株式会社 | 改良された電気二重層コンデンサ |
JPS6290919A (ja) * | 1985-09-20 | 1987-04-25 | 旭硝子株式会社 | 電気二重層コンデンサ |
JPH01207263A (ja) * | 1988-02-10 | 1989-08-21 | Sony Corp | 磁気記録媒体 |
DE3913037A1 (de) * | 1988-04-21 | 1989-11-02 | Central Glass Co Ltd | Verfahren zur herstellung von alkalimetallfluoralkylsulfonaten hoher reinheit |
JP2001322975A (ja) * | 2000-05-16 | 2001-11-20 | Dainippon Ink & Chem Inc | パーフルオロアルキルスルホン酸塩の製造方法 |
Non-Patent Citations (4)
Title |
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DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; MORIMOTO, TAKESHI ET AL: "Electric double layer capacitors", XP002226287, retrieved from STN Database accession no. 106:225893 CA * |
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; MORIMOTO, TAKESHI ET AL: "Electric double-layer capacitor", XP002226286, retrieved from STN Database accession no. 107:167115 CA * |
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; YAMAOKA, SEIJI ET AL.: "Preparation of perfluoroalkylsulfonates", XP002226288, retrieved from STN Database accession no. 135:371444 * |
PATENT ABSTRACTS OF JAPAN vol. 013, no. 515 (C - 655) 17 November 1989 (1989-11-17) * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007532647A (ja) * | 2004-04-13 | 2007-11-15 | ゼネラル・エレクトリック・カンパニイ | 帯電防止剤の製造方法 |
JP2011201900A (ja) * | 2004-04-13 | 2011-10-13 | Sabic Innovative Plastics Ip Bv | 帯電防止剤の製造方法 |
JP4932702B2 (ja) * | 2004-04-13 | 2012-05-16 | サビック・イノベーティブ・プラスチックス・アイピー・ベスローテン・フェンノートシャップ | 帯電防止剤の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
DE50214052D1 (de) | 2010-01-14 |
DE10143172A1 (de) | 2003-03-20 |
CN1551867A (zh) | 2004-12-01 |
KR100927069B1 (ko) | 2009-11-13 |
EP1427698B1 (de) | 2009-12-02 |
ATE450500T1 (de) | 2009-12-15 |
JP4266821B2 (ja) | 2009-05-20 |
CN1279021C (zh) | 2006-10-11 |
JP2005501899A (ja) | 2005-01-20 |
KR20040034676A (ko) | 2004-04-28 |
EP1427698A1 (de) | 2004-06-16 |
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