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WO2003001623A2 - Sels conducteurs comprenant du niobium ou du tantale - Google Patents

Sels conducteurs comprenant du niobium ou du tantale Download PDF

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Publication number
WO2003001623A2
WO2003001623A2 PCT/EP2002/005892 EP0205892W WO03001623A2 WO 2003001623 A2 WO2003001623 A2 WO 2003001623A2 EP 0205892 W EP0205892 W EP 0205892W WO 03001623 A2 WO03001623 A2 WO 03001623A2
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
salts
aryl
general formula
compound
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.)
Ceased
Application number
PCT/EP2002/005892
Other languages
English (en)
Other versions
WO2003001623A3 (fr
Inventor
Michael Schmidt
Andreas Kühner
Karl. O. Christe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Priority to AU2002310749A priority Critical patent/AU2002310749A1/en
Publication of WO2003001623A2 publication Critical patent/WO2003001623A2/fr
Publication of WO2003001623A3 publication Critical patent/WO2003001623A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G35/00—Compounds of tantalum
    • C01G35/006—Compounds containing tantalum, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
    • C01G33/006—Compounds containing niobium, with or without oxygen or hydrogen, and containing two or more other elements
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
    • 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

  • Conducting salts comprising niobium or tantalum
  • the present invention relates to salts comprising niobium or tantalum, methods for their preparation, and their use in primary batteries, secondary batteries, condensators, supercondensators and/or galvanic cells.
  • the present invention relates to electrolytes, primary batteries, secondary batteries, condensators, superconductors and/or galvanic cells comprising niobium or tantalum salts.
  • Weakly associated salts are the basis of many electrolytes. They are useful in electrochemical cells such as batteries, electronic parts such as condensators, double layer condensators, super or ultra capacitators as well as for organic synthesis, especially catalysis mecanicionic liquids"). For non-aquous electrolytes fluorine containg salts are generally used as conducting salts.
  • Hydrogenfluoride can result when these salts are brought in contact with water or even with humidity. Next to its toxic properties hydrogen fluoride also has a very negative impact on the cyclic behavior and performance of electrical cells.
  • lithium salts such as imides, for example bis(trifluoromethylsulfonyl)imide as taught in US 4,505,997) or methanides, for example tris(trifluoromethylsulfonyl)-methanide as taught in US 5,273,840.
  • imides for example bis(trifluoromethylsulfonyl)imide as taught in US 4,505,997) or methanides, for example tris(trifluoromethylsulfonyl)-methanide as taught in US 5,273,840.
  • methanides demonstrate a strong anionic stability and provide solutions of high conductivity in aprotic organic solvents.
  • aluminum which is generally used as a cathodic divertant is not rendered passive sufficiently, at least not with imides.
  • methanides require an elaborous preparation and purification procedure.
  • electrochemical properties such as stability against oxidation and passivation of aluminum depend largely on the purity of the methanide.
  • lithium spiroborates as taught in EP 0 698 301 B1 or lithium spirophosphates as described in Electrochemical and Solid State Letters, 2(2) 60-62 (1999). Due to the divalent ligands, many of these salts have decomposition temperatures of more than 200 °C. But their oxidation potential of 4,3 V at maximum against Li/Li + does not provide a sufficient electrochemical stability for use in lithium batteries with highly oxidizing electrode materials, such as, for example, LiMn 2 0 4 or LiCo . x Ni x 0 2 (0 ⁇ x ⁇ 1).
  • a further problem underlying the present invention is the provision of more powerful and more stable primary and secondary batteries, condensators, supercondensators and galvanic cells.
  • This problem is solved according to the present invention by providing new salts comprising niobium or tantalum of the general formula I:
  • M n+ is a mono-, di- or trivalent cation, or a mixture of monovalent cations or a divalent and a monovalent cation
  • Y " denotes a TaF 6 " or NbF 6 " anion
  • R 1 , R 2 , R 3 , R 4 are, in each case independently of one another, C 1-10 alkyl or C 1-10 alkyl and aryl or C 1-10 aryl, wherein C ⁇ o alkyl and/or aryl may be further substituted and wherein carbons of C 1-10 alkyl and/or aryl may be substituted by any of the heteroatoms O, N, or S.
  • Another preferred embodiment relates to salts of the present invention, wherein a cation M n+ is or comprises at least one aromatic heterocyclic cation.
  • salts or a mixture of salts comprising at least one aromatic heterocyclic cation, wherein said cation is or comprises at least one of the following cations:
  • R-i, R 2l R 3 , R 4 , R 5 , R 6 are, in each case independently of one another, a hydrogen or a halogen or a fluoride or a C 1 t08 alkyl,
  • R ⁇ R 2 , R 3 , R 4 , R 5 , R 6 may be bonded to each other by single or double bonds
  • carbons of C 1-8 alkyl and/or aryl may be substituted by any of the heteroatoms O, N, or S wherein the C-i to 8 alkyl may be partially or completely substituted by further functional groups such as
  • the salts of the present invention provide a number of advantages. They are not sensitive to hydrolysis. Their tendency to decompose is very small. They have a high thermal stability and they are soluble in most standard aprotic solvents. They are useful as salts for electrolytes. Electrolytes comprising said salts are electrochemically stable, temperature and humidity resistent. Also, such electrolytes demonstrate an excellent cyclic behavior and performance in electrical cells.
  • a further aspect of the present invention relates to a method for the preparation of salts comprising niobium or tantalum of the general formula I:
  • M n+ r n I wherein M ⁇ + is a mono-, di- or trivalent cation, or a mixture of monovalent cations or a divalent and a monovalent cation
  • Y denotes a TaF 6 " or NbF 6 " anion, and 1 ⁇ n ⁇ 3,
  • TaF 5 or NbF 5 react with a compound M n+ F " n in the presence of a suitable anhydrous solvent.
  • said reaction is performed in a suitable anhydrous solvent such as hydrogen fluoride or acetonitrile or an organic carbonate, preferably ethylenecarbonate, propylenecarbonate, butylenecarbonate, dimethylcarbonate, diethylcarbonate, ethylmethylcarbonate, methylpropylcarbonate or a mixture of at least two of these solvents.
  • a suitable anhydrous solvent such as hydrogen fluoride or acetonitrile or an organic carbonate, preferably ethylenecarbonate, propylenecarbonate, butylenecarbonate, dimethylcarbonate, diethylcarbonate, ethylmethylcarbonate, methylpropylcarbonate or a mixture of at least two of these solvents.
  • Anhydrous organic solvents such as ethers, esters, carbamates or amides are also suitable solvents.
  • Preferred esters are methylformiate, ethylformiate, methylacetate, Ethylacetate, methylpropionate, ethylpropionate, methylbutyrate, ethyl buty rate, ⁇ -butyrolactone.
  • Preferred ethers are diethylether, dimethoxyethane, diethoxyethane, tetrahydrofurane, dioxolane and dioxane.
  • Preferred amides are dimethylformamide and dimethylacetamide.
  • Preferred carbamates are methyl- or ethyl-N,N- dimethylcarbamate, methyl- or ethyl-N,N-diethylcarbamate, 2,2,2-trifluoroethyl- N,N-dimethylcarbamate or 2,2,2-trifluoroethyl-N,N-diethylcarbamate.
  • TaF 5 or NbF 5 are commercially available products.
  • the present invention relates to a method, wherein the cation M n+ is or comprises at least one of the following cations:
  • R 1 , R 2 , R 3 , R 4 are, in each case independently of one another, C 1-10 alkyl, C ⁇ _ ⁇ o alkyl and aryl or C ⁇ oaryl, that may be further substituted and wherein carbons may be substituted by any of the heteroatoms O, N, or S.
  • the cation M n+ is or comprises at least one aromatic heterocyclic cation.
  • the cation M n+ is or comprises at least one of the following aromatic heterocyclic cations:
  • R ⁇ R 2 , R 3 , R 4 , R 5 , R 6 may be bonded to each other by single or double bonds
  • carbons of C- ⁇ -8 alkyl and/or aryl may be substituted by any of the heteroatoms O, N, or S wherein the C-i t0 ⁇ alkyl may be partially or completely substituted by further functional groups such as
  • the reaction between TaF 5 or NbF 5 with a compound M n+ F " n preferably takes place at a temperature of -50 to 50°C, more preferably at a temperature of 15 to 25 °C.
  • Preferred solvents that are directly suitable for use in a secondary or primary battery, a condensator or a galvanic cell are organic carbonates, more preferably ethylenecarbonate, propylenecarbonate, butylenecarbonate, dimethylcarbonate, diethylcarbonate, ethylmethylcarbonate, methylpropylcarbonate or a mixture of at least two of these solvents.
  • the method according to the present invention provides almost pure salts in high yield with little impurities. Often the reaction proceeds to give quantitative yields and only traces of impurities. If necessary, the salts may be further purified according to standard methods, for example, by recrystallisation in a suitable solvent or solvent mixture. A suitable solvent or solvent mixture can easily be selected by preliminary experiments. The method for preparing the salts according to the invention is simply, efficient and without any complicated or dangerous steps.
  • the present invention relates to the use of at least one of the salts according to the invention alone or in combination with further salts and/or additives in primary batteries, secondary batteries, condensators, supercondensators and/or galvanic cells.
  • the salts are suitable for preparing electrolytes, preferably electrolytes for primary batteries, secondary batteries, condensators, supercondensators and/or galvanic cells.
  • Such an electrolyte comprises at least one compound of the present invention.
  • the preparation of soluble or solid electrolytes is well known to the average expert in the field of electrochmistry (for example: D. Linden, Handbook of Batteries, Second Edition, McGraw-Hill Inc., New York 1995; J. Barthel and H.- J. Gores, Solution Chemistry: A Cutting Edge in Modern Electrochemical Technology in G. Mamantov and A.I. Popov (publishers) Chemistry of Nonaquous Solutions, Current Progress, VCH Verlagstician, Weinheim 1994).
  • Electrolytes can be prepared as a solution or a solid material.
  • a solid electrolyte may be a polymer electrolyte optionally comprising a cross-linked polymer and at least one conducting salt or a gel electrolyte that comprises at least one solvent in addition to at least one conducting salt and an optional cross-linked polymer.
  • these electrolytes have a salt concentration of the elektrolyte of 0,01 - 3 mol/l, preferably of 0,01 - 2 mol/l, most preferably of 0,1 - 1 ,5 mol/l.
  • Electrolytes according to the present invention provide excellent electrochemical properties for most uses in batteries, conductors and galvanic cells. These electrolytes provide excellent conductivity as well as stability and safety.
  • a further aspect of the present invention relates to primary batteries, secondary batteries, condensators, superconductors and/or galvanic cells comprising at least one of the niobium or tantalum salts of the present invention.
  • Primary batteries, secondary batteries, condensators, superconductors and/or galvanic cells according to the present invention are suitable to be employed under extreme conditions such as high temperatures or high humidity without an effect on the performance or life span of the device.
  • FEP fluoroethylene polymer
  • N(CH 3 ) 4 F (0.442 g, 4.75 mmol) was added to this solution and the mixture was agitated, resulting in a clear colorless solution.
  • the HF solvent was pumped off at room temperature leaving behind N(CH 3 ) 4 TaF 6 (1.752 g, 4.75 mmol) in quantitative yield.
  • the product was identified by its Raman spectrum.
  • TaF 5 (1.460 g, 5.29 mmol) and N(CH 3 ) 4 F (0. 493 g, 5.29 mmol) were placed in a drybox into separate baked-out Schlenk ampules that were closed by Teflon-glass valves.
  • On a glass vacuum line about 6 ml of liquid dry CH 3 CN were added to each ampule and the mixtures were agitated at room temperature.
  • the resulting suspensions were combined producing a clear yellow solution. All volatile material was pumped off at room temperature leaving behind yellow N(CH 3 ) 4 TaF 6 (1.953 g, 5.29 mmol) in quantitative yield.
  • the yellow color was removed by washing the product several times with 150 ml of hexane.
  • the product was identified by its Raman spectrum and exhibited only traces
  • reaction mixtures were filtered under vacuum using a glas frit to completely remove LiCI.
  • the solvents were removed by vaccum destination and the resulting MTaF 6 and MNbF 6 , wherein M is N(C 2 H 5 ) were dried under vacuum.
  • Lithium hexafluorotantalate was prepared according to example 1 , solved in acetonitrile and an equimolar amount of 1 -Ethyl, 3-methyl imidazoliumchloride was added. This reaction mixture was filtered under vacuum using a glas frit to completely remove LiCI. The solvent was removed by vaccum destination and the resulting of 1 -ethyl, 3-methyl imidazolium hexafluorotantalate was dried under vacuum.
  • EC stands for ethylenecarbonate
  • DMC dimethylcarbonate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Primary Cells (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne des sels comprenant du niobium ou du tantale, des procédés de préparation de ceux-ci et leur utilisation dans des batteries primaires, des accumulateurs, des condensateurs, des supraconducteurs et/ou des piles galvaniques. De plus, l'invention concerne des électrolytes, des batteries primaires, des accumulateurs, des condensateurs, des supercondensateurs et/ou des piles galvaniques comprenant des sels de niobium ou de tantale.
PCT/EP2002/005892 2001-06-22 2002-05-29 Sels conducteurs comprenant du niobium ou du tantale Ceased WO2003001623A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002310749A AU2002310749A1 (en) 2001-06-22 2002-05-29 Conducting salts comprising niobium or tantalum

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US29972101A 2001-06-22 2001-06-22
US01/299,721 2001-06-22

Publications (2)

Publication Number Publication Date
WO2003001623A2 true WO2003001623A2 (fr) 2003-01-03
WO2003001623A3 WO2003001623A3 (fr) 2003-04-10

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WO (1) WO2003001623A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006066918A3 (fr) * 2004-12-23 2006-09-08 Uni I Oslo Conducteurs de protons

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5734026A (en) * 1980-08-01 1982-02-24 Showa K B I Kk Production of high-purity potassium fluorotantalate
JPS58121569A (ja) * 1982-01-14 1983-07-19 Hitachi Ltd プラスチツク２次電池
JPS617567A (ja) * 1984-06-22 1986-01-14 Hitachi Ltd 二次電池およびその製造法
JPH01262617A (ja) * 1988-04-14 1989-10-19 Hitachi Condenser Co Ltd 電気二重層コンデンサ
FR2659486B1 (fr) * 1990-03-09 1995-10-13 Europ Composants Electron Condensateur electrolytique a electrolyte solide et procede d'impregnation d'un tel condensateur.
DE69934170T2 (de) * 1998-02-03 2007-09-27 Acep Inc., Montreal Neue als elektrolytische solubilisate geeignete werkstoffe
JP2001332454A (ja) * 2000-05-22 2001-11-30 Mitsubishi Chemicals Corp 電気化学キャパシタ用非水電解液及びこれを用いた電気化学キャパシタ
JP2002033246A (ja) * 2000-07-19 2002-01-31 Mitsubishi Chemicals Corp 電気化学キャパシタ用電解液及びそれを用いた電気化学キャパシタ
JP2002047255A (ja) * 2000-07-28 2002-02-12 Mitsubishi Chemicals Corp フルオロ錯塩の精製方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006066918A3 (fr) * 2004-12-23 2006-09-08 Uni I Oslo Conducteurs de protons
US8426077B2 (en) 2004-12-23 2013-04-23 Universitetet I Oslo Proton conductors

Also Published As

Publication number Publication date
AU2002310749A1 (en) 2003-01-08
WO2003001623A3 (fr) 2003-04-10

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