US20040063986A1 - Boron chelate complexes - Google Patents

Boron chelate complexes Download PDF

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Publication number
US20040063986A1
US20040063986A1 US10/467,220 US46722003A US2004063986A1 US 20040063986 A1 US20040063986 A1 US 20040063986A1 US 46722003 A US46722003 A US 46722003A US 2004063986 A1 US2004063986 A1 US 2004063986A1
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Prior art keywords
boron
lithium
borate
hydrogen
oxalato
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Abandoned
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US10/467,220
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English (en)
Inventor
Ulrich Wietelmann
Uwe Lischka
Klaus Schade
Jan-Christoph Panitz
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Chemetall GmbH
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Chemetall GmbH
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Assigned to CHEMETALL GMBH reassignment CHEMETALL GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LISCHKA, UWE, PANITZ, JAN-CHRISTOPH, SCHADE, KLAUS, WIETELMANN, ULRICH
Publication of US20040063986A1 publication Critical patent/US20040063986A1/en
Priority to US11/355,863 priority Critical patent/US7709663B2/en
Priority to US12/634,963 priority patent/US8168806B2/en
Abandoned legal-status Critical Current

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/02—Boron compounds
    • C07F5/022—Boron compounds without C-boron linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/02—Boron compounds
    • C07F5/04—Esters of boric acids
    • 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
    • H01M10/056—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
    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the present invention relates to boron chelate complexes, a process for their production as well as their use as electrolytes and as catalysts.
  • LiPF 6 lithium hexafluorophosphate
  • This salt satisfies the necessary preconditions for use in high-energy cells, i.e. it is readily soluble in aprotic solvents, leads to electrolytes with high conductivities, and has a high level of electrochemical stability. Oxidative decomposition occurs only at potential values greater than ca. 4.5 V.
  • LiPF 6 has serious disadvantages however, which can mainly be attributed to a lack of thermal stability (it decomposes above ca. 130° C.). Also, on contact with moisture, corrosive and poisonous hydrogen fluoride is released, which on the one hand complicates handling and on the other hand attacks and damages other battery components, for example the cathode.
  • lithium salts with perfluorinated organic radicals include lithium trifluoromethane sulfonate (“Li-triflate”), lithium imides (lithium-bis(perfluoroalkylsulfonyl)imides) as well as lithium methides (lithium-tris(perfluoroalkylsulfonyl)methides). All these salts require relatively complicated production processes and are therefore relatively expensive, and have other disadvantages such as corrosiveness with respect to aluminium or poor conductivity.
  • Lithium organoborates have been investigated as a further class of compounds for use as conducting salt in rechargeable lithium batteries. On account of their low oxidation stability and safety considerations in the handling of triorganoboranes, their use for commercial systems is excluded however.
  • the lithium complex salts of the type ABL 2 (where A denotes lithium or a quaternary ammonium ion, B denotes boron and L denotes a bidentate ligand that is bound via two oxygen atoms to the boron atom) proposed in EP 698301 for use in galvanic cells represent a considerable step forward.
  • the proposed salts, whose ligands contain at least one aromatic radical however only have a sufficient electrochemical stability if the aromatic radical is substituted by electron-attracting radicals, typically fluorine, or if it contains at least one nitrogen atom in the ring.
  • Such chelate compounds are not commercially available and can be produced only at high cost. The proposed products could therefore not penetrate the market.
  • the compound lithium-bis(oxalato)borate (LOB) described for the first time in DE 19829030 is the first boron-centred complex salt described for use as an electrolyte that employs a dicarboxylic acid (in this case oxalic acid) as chelate component.
  • the compound is simple to produce, non-toxic and electrochemically stable up to about 4.5 V, which permits its use in lithium ion batteries.
  • a disadvantage however is that it can hardly be used in new battery systems with cell voltages of >3 V. For such electrochemical storage units, salts with stabilities of ⁇ ca. 5 V are required.
  • a further disadvantage is that lithium-bis(oxalato)borate does not allow any possible structural variations without destroying the basic chemical framework.
  • R 1 and R 2 are identical or different and are optionally directly bonded to one another by a single or double bond, in each case individually or jointly denote an aromatic or aliphatic carboxylic acid or sulfonic acid, or in each case individually or jointly denote an aromatic ring from the group consisting of phenyl, naphthyl, anthracenyl or phenanthrenyl, which may be unsubstituted or mono to tetra substituted by A or Hal, or in each case individually or jointly denote a heterocyclic aromatic ring from the group comprising pyridyl, pyrazyl or bipyridyl, which may be unsubstituted or mono to tri substituted by A or Hal, or in each case individually or jointly denote an aromatic hydroxy acid from the group consisting of aromatic hydroxycarboxylic acids or aromatic hydroxysulfonic acids, which may be unsubstituted or mono to tetra substituted by A or Hal, and
  • Hal F, Cl or Br
  • A alkyl radical with 1 to 6 C atoms, which may be mono to tri halogenated.
  • Lithium-bis(malonato)borate which is said to have an electrochemical window up to 5 V, has been described by C. Angell as being an electrochemically particularly stable simple lithium-(chelato)borate compound.
  • the compound in question has the disadvantage however that it is practically insoluble in the usual battery solvents (e.g. only 0.08 molar in propylene carbonate), which means that it can be dissolved and characterised only in DMSO and similar prohibitive battery solvents (Wu Xu and C. Austen Angell, Electrochem. Solid-State Lett. 4, E1-E4, 2001).
  • Chelatoborates may furthermore be present in protonated form (i.e. H[BL 2 ]) where L is a bidentate ligand that is bound to the boron atom via two oxygen atoms.
  • L is a bidentate ligand that is bound to the boron atom via two oxygen atoms.
  • Such compounds have an extremely high acidic strength and may therefore be used as so-called super acids in organic synthesis being used as catalysts for cyclisations, aminations, etc.
  • hydrogen-bis(oxalato)borate has been proposed as a catalyst for the production of tocopherol (U.S. Pat. No. 5,886,196).
  • the disadvantage of this catalyst however is the relatively poor hydrolytic stability.
  • the object of the present invention is to obviate the disadvantages of the prior art and in particular to provide substances for conducting salts that can be produced relatively simply and inexpensively from commercially available raw materials, that have a sufficient oxidation stability of at least 4.5 V, and that are readily soluble in conventionally used “battery solvents”. Furthermore the substances should be relatively resistant to decomposition by water or alcohols.
  • X is either —C(R 1 R 2 )— or —C(R 1 R 2 )—C( ⁇ O)—, in which
  • R 1 , R 2 independently of one another denote H, alkyl (with 1 to 5 C atoms), aryl, silyl or a polymer, and one of the alkyl radicals R 1 or R 2 may be bonded to a further chelatoborate radical,
  • S 1 , S 2 independently of one another denote alkyl (with 1 to 5 C atoms), fluorine or a polymer
  • M+ denotes Li + , Na + , K + , Rb + , Cs + or [(R 3 R 4 R 5 R 6 )N] + or H + , where R 3 , R 4 , R 5 , R 6 independently of one another denote H or alkyl with preferably 1 to 4 C atoms.
  • HMOB hydrogen(malonato,oxalato)borate
  • HGOB hydrogen(glycolato,oxalato)borate
  • HLOB hydrogen(lactato,oxalato)borate
  • HOSB hydrogen(oxalato,salicylato)borate
  • BHOTB bis-[hydrogen(oxalato,tartrato)borate]
  • Table 2 shows the hydrolysisability of various chelatoborates. TABLE 2 Degree of hydrolysis of 5% solutions in water after stirring for 2 hours at room temperature LOB LMB LMOB Degree of hydrolysis (%) >50 5 15
  • the metal salts with mixed boron chelate anions according to the invention can dissolve in relatively high concentrations in the typical aprotic solvents such as carbonates, lactones and ethers used for high-performance batteries.
  • Table 3 gives the measured conductivities at room temperature: TABLE 3 Conductivities of non-aqueous electrolytes with mixed chelatoborate salts in ⁇ -BL, 1,2-DME and THF at room temperature ⁇ -BL 1,2-DME THF Concn. 1) Cond. 2) Concn. 1) Cond 2) Concn. 1) Cond. 1) Cond. 1) Cond. 1) Cond. 1) Cond. 1) Cond.
  • the conductivities may be optimised corresponding to the prior art by, for example, combining at least one solvent having a high dielectric constant (for example ethylene carbonate, propylene carbonate) with at least one viscosity-reducing agent (for example dimethyl carbonate, butylacetate, 1,2-dimethoxyethane, 2-methyltetrahydrofuran).
  • a high dielectric constant for example ethylene carbonate, propylene carbonate
  • at least one viscosity-reducing agent for example dimethyl carbonate, butylacetate, 1,2-dimethoxyethane, 2-methyltetrahydrofuran
  • the salts with mixed chelatoborate anions exhibit the desired high degree of electrochemical stability.
  • the boron chelate complexes described above can be fixed to polymer compounds by known techniques. Thus, it is possible to remove the acidic hydrogen atoms in the ⁇ -position to the carbonyl groups by means of suitable bases and to add the carbanionic species obtained in this way to functionalised (e.g. halogenated) polymers.
  • the boron chelate complexes according to the invention can be produced by reacting boric acid or boron oxide with oxalic acid and the other chelate-forming agent, optionally in the presence of an oxidic metal source (e.g. Li 2 CO 3 , NaOH, K 2 O) or an ammonium salt, for example according to the following equations:
  • an oxidic metal source e.g. Li 2 CO 3 , NaOH, K 2 O
  • an ammonium salt for example according to the following equations:
  • L 2 denotes dicarboxylic acid (not oxalic acid), hydroxycarboxylic acid or salicylic acid (which may be at most di-substituted).
  • stoichiometric amounts of the starting substances are used, i.e. the molar ratio boron/oxalic acid/chelate-forming agent L 2 /optional oxidic metal source or ammonium salt is about 1:1:1:1.
  • Small deviations from the theoretical stoichiometry e.g. 10% above or below are possible without having a marked effect on the chelatoborate end product.
  • the ligands is present in excess, the corresponding symmetrical end product will occur to a greater extent in the reaction mixture.
  • chelate-formins agent If the chelate-formins agent is not used in a stoichiometric amount, unreacted boron component or undesirable 1:1-adduct (HO—B(C 2 O 4 ) or HO—BL 2 ) will remain. If more than 2 moles of chelate-forming agent are used, then unreacted chelate-forming agent will remain, which has to be separated in a complicated procedure.
  • the reaction according to the above chemical equations is preferably carried out by suspending the raw material components in a medium suitable for the azeotropic removal of water (e.g. toluene, xylene, methylcyclohexans, perfluorinated hydrocarbons with more than 6 C atoms) and removing the water azeotropically in a known way.
  • a medium suitable for the azeotropic removal of water e.g. toluene, xylene, methylcyclohexans, perfluorinated hydrocarbons with more than 6 C atoms
  • the product can also be produced without adding any solvent, i.e. the commercially available raw materials are mixed and then heated by supplying heat and dehydrated preferably under reduced pressure.
  • the acids H[BC 2 O 4 L 2 ] produced in this way are used in organic synthesis as super acid catalysts, e.g. for condensations, hydroaminations or debenzylations.
  • Lithium salts of the mixed chelatoborates are used as electrolytes in electrolytic cells, preferably lithium batteries.
  • the ammonium and caesium salts may be used in electrolytic double-layer capacitors.
  • reaction mixture was cooled to 40° C. and poured onto a glass frit and filtered.
  • the colourless solids were washed twice with toluene and once with pentane.
  • the finely powdered product was dried first of all at room temperature and then at 100° C. on a rotary evaporator.
  • TGA Thermogravimetry
  • TGA decomposition starts at ca. 210° C.
  • reaction matter was cooled and ground by means of a pestle and mortar.
  • the now white, powdery reaction material was again dried to constant weight on a rotary evaporator at 115° to 125° C. and finally 10 mbar (2 hours).
  • the product was extremely soluble in propylene carbonate, ⁇ -butyrolactone, 1,2-dimethyoxyethane, acetone and dimethylformamide.
US10/467,220 2001-02-22 2002-02-15 Boron chelate complexes Abandoned US20040063986A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US11/355,863 US7709663B2 (en) 2001-02-22 2006-02-16 Boron chelate complexes
US12/634,963 US8168806B2 (en) 2001-02-22 2009-12-10 Boron chelate complexes

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DE10108592A DE10108592C1 (de) 2001-02-22 2001-02-22 Borchelatkomplexe, Verfahren zu deren Herstellung sowie deren Verwendung
PCT/EP2002/001639 WO2002068432A1 (de) 2001-02-22 2002-02-15 Borchelatkomplexe

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US (3) US20040063986A1 (de)
EP (1) EP1379532B1 (de)
JP (1) JP4076141B2 (de)
KR (1) KR100902963B1 (de)
CN (1) CN1275971C (de)
CA (1) CA2438611C (de)
DE (2) DE10108592C1 (de)
TW (1) TWI316518B (de)
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030211383A1 (en) * 2002-05-09 2003-11-13 Lithium Power Technologies, Inc. Primary lithium batteries
US20050274000A1 (en) * 2004-06-14 2005-12-15 The University Of Chicago Methods for fabricating lithium rechargeable batteries
US20080118845A1 (en) * 2006-11-22 2008-05-22 Sony Corporation Ionic compound, electrolytic solution, electrochemical device, and battery
US20090309075A1 (en) * 2006-09-07 2009-12-17 Roeder Jens Usage of borate salts
US20100143806A1 (en) * 2007-07-04 2010-06-10 Rainer Dietz Method for producing low-acid lithium borate salts and mixtures of low-acid lithium borate salts and lithium hydride
US9260456B2 (en) 2011-11-14 2016-02-16 Rockwood Lithium GmbH Process for preparing metal difluorochelatoborates and use as battery electrolytes or additives in electrochemical cells

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DE10108592C1 (de) * 2001-02-22 2002-08-14 Chemetall Gmbh Borchelatkomplexe, Verfahren zu deren Herstellung sowie deren Verwendung
US8524397B1 (en) 2004-11-08 2013-09-03 Quallion Llc Battery having high rate and high capacity capabilities
US7572554B2 (en) 2002-09-03 2009-08-11 Quallion Llc Electrolyte
US6787268B2 (en) 2002-09-03 2004-09-07 Quallion Llc Electrolyte
JP4022889B2 (ja) 2004-02-12 2007-12-19 ソニー株式会社 電解液および電池
DE102004011522A1 (de) 2004-03-08 2005-09-29 Chemetall Gmbh Leitsalze für Lithiumionenbatterien und deren Herstellung
JP5211422B2 (ja) * 2005-01-24 2013-06-12 セントラル硝子株式会社 イオン性錯体の合成法
DE102008041748A1 (de) 2007-08-30 2009-03-05 Chemetall Gmbh Sauerstoffverbindung der Borgruppe
EP2821408B1 (de) 2013-07-02 2018-02-21 Samsung SDI Co., Ltd. Bis(hydroxyacetato)borate als Elektrolyte für Lithiumsekundärbatterien
CN104037452B (zh) * 2014-06-18 2016-05-18 厦门首能科技有限公司 一种锂离子二次电池及含有该电解液的锂离子电池
JPWO2021117721A1 (de) * 2019-12-09 2021-06-17

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JP2611301B2 (ja) 1988-01-29 1997-05-21 三菱化学株式会社 電解コンデンサ用電解液
US5886196A (en) * 1996-01-12 1999-03-23 Roche Vitamins Inc. Method of catalyzing condensation reactions
DE19829030C1 (de) * 1998-06-30 1999-10-07 Metallgesellschaft Ag Lithium-bisoxalatoborat, Verfahren zu dessen Herstellung und dessen Verwendung
DE19932317A1 (de) * 1999-07-10 2001-01-11 Merck Patent Gmbh Verfahren zur Herstellung von Lithiumkomplexsalzen zur Anwendung in elektrochemischen Zellen
JP3824465B2 (ja) * 1999-08-02 2006-09-20 セントラル硝子株式会社 イオン性錯体の合成法
JP2004511879A (ja) * 2000-06-16 2004-04-15 アリゾナ　ボード　オブ　リージェンツ，　ア　ボディ　コーポレイト　アクティング　オン　ビハーフ　オブ　アリゾナ　ステート　ユニバーシティ リチウム電池用伝導性ポリマー組成物
US7527899B2 (en) * 2000-06-16 2009-05-05 Arizona Board Of Regents For And On Behalf Of Arizona State University Electrolytic orthoborate salts for lithium batteries
DE10108592C1 (de) * 2001-02-22 2002-08-14 Chemetall Gmbh Borchelatkomplexe, Verfahren zu deren Herstellung sowie deren Verwendung

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7462424B2 (en) * 2002-05-09 2008-12-09 Lithium Power Technologies, Inc. Primary thermal batteries
US20060073376A1 (en) * 2002-05-09 2006-04-06 Lithium Power Technologies, Inc. Primary lithium batteries
US20030211383A1 (en) * 2002-05-09 2003-11-13 Lithium Power Technologies, Inc. Primary lithium batteries
US20050274000A1 (en) * 2004-06-14 2005-12-15 The University Of Chicago Methods for fabricating lithium rechargeable batteries
WO2005124919A2 (en) * 2004-06-14 2005-12-29 The University Of Chicago Methods for fabricating lithium rechargeable batteries
WO2005124919A3 (en) * 2004-06-14 2006-09-21 Univ Chicago Methods for fabricating lithium rechargeable batteries
US20090309075A1 (en) * 2006-09-07 2009-12-17 Roeder Jens Usage of borate salts
US20080118845A1 (en) * 2006-11-22 2008-05-22 Sony Corporation Ionic compound, electrolytic solution, electrochemical device, and battery
US8652682B2 (en) 2006-11-22 2014-02-18 Sony Corporation Ionic compound, electrolytic solution, electrochemical device, and battery
US20100143806A1 (en) * 2007-07-04 2010-06-10 Rainer Dietz Method for producing low-acid lithium borate salts and mixtures of low-acid lithium borate salts and lithium hydride
US20160028120A1 (en) * 2007-07-04 2016-01-28 Chemetall Gmbh Method for producing low-acid lithium borate salts and mixtures of low-acid lithium borate salts and lithium hydride
US9847552B2 (en) * 2007-07-04 2017-12-19 Albermarle Germany Gmbh Method for producing low-acid lithium borate salts and mixtures of low-acid lithium borate salts and lithium hydride
US9260456B2 (en) 2011-11-14 2016-02-16 Rockwood Lithium GmbH Process for preparing metal difluorochelatoborates and use as battery electrolytes or additives in electrochemical cells

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US20100168476A1 (en) 2010-07-01
KR100902963B1 (ko) 2009-06-15
DE10108592C1 (de) 2002-08-14
US20060142608A1 (en) 2006-06-29
US8168806B2 (en) 2012-05-01
KR20030077642A (ko) 2003-10-01
DE50200970D1 (de) 2004-10-14
EP1379532A1 (de) 2004-01-14
US7709663B2 (en) 2010-05-04
JP4076141B2 (ja) 2008-04-16
EP1379532B1 (de) 2004-09-08
TWI316518B (en) 2009-11-01
JP2004534735A (ja) 2004-11-18
CA2438611C (en) 2010-01-26
CN1275971C (zh) 2006-09-20
WO2002068432A1 (de) 2002-09-06
CA2438611A1 (en) 2002-09-06
CN1516702A (zh) 2004-07-28

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