WO2001057947A1 - Utilisation d'amidines - Google Patents

Utilisation d'amidines Download PDF

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Publication number
WO2001057947A1
WO2001057947A1 PCT/EP2001/000886 EP0100886W WO0157947A1 WO 2001057947 A1 WO2001057947 A1 WO 2001057947A1 EP 0100886 W EP0100886 W EP 0100886W WO 0157947 A1 WO0157947 A1 WO 0157947A1
Authority
WO
WIPO (PCT)
Prior art keywords
amidines
ppm
mol
solvents
use according
Prior art date
Application number
PCT/EP2001/000886
Other languages
German (de)
English (en)
Inventor
Olaf BÖSE
Matthias Rieland
Dirk Seffer
Wolfgang Kalbreyer
Original Assignee
Solvay Fluor Und Derivate 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 Solvay Fluor Und Derivate Gmbh filed Critical Solvay Fluor Und Derivate Gmbh
Priority to AU37349/01A priority Critical patent/AU3734901A/en
Publication of WO2001057947A1 publication Critical patent/WO2001057947A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
    • C07D295/195—Radicals derived from nitrogen analogues of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
    • C07C257/14—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to acyclic carbon atoms
    • 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
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
    • 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
    • H01M2300/0034—Fluorinated 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

  • the invention relates to a new application for certain amidines and some new amidines.
  • Electrolytes from solvents or solvent mixtures and dissolved conductive salts are used, for example, in rechargeable batteries. Many different conductive salts and many different organic solvents for the production of electrolytes are known. Some useful classes of compounds are, for example, in J. Elektrochem. Soc. Vol. 141 (1994), pages 2989-296. Alkyl carbonates or alkylene carbonates are frequently used, see EP-A-0 643 433. Pyrocarbonates can also be used, see US Pat. No. 5,427,874.
  • the object of the present invention is to enlarge the range of usable solvents for conductive salts. This object is achieved by the present invention.
  • the invention is based on the knowledge that amidines of certain carboxylic acids are very useful as solvents for conductive salts for the formation of electrolytes.
  • amidines of perfluorinated C2-C5 carboxylic acids are used as solvents or solvent components for conductive salts in electrolytes.
  • the electrolytes are used in particular for the production of rechargeable batteries.
  • amidines of perfluorinated C2-C5 carboxylic acids have a very good dissolving power for conductive salts.
  • concentrations of around 1 mol / l of the conductive salt in the solvent are usually aimed for.
  • N, N-dimethyltrifluoroacetamidine for example, easily dissolves so much lithium bis (trifluoromethanesulfonyl) imide that its concentration is greater than 2 mol / l, and this is not even the saturation concentration at 20 ° C.
  • the advantage is that even at lower temperatures, which are achieved in practice when using batteries, there is no fear of the conductive salt failing.
  • R 1 represents CF 3 , C 2 F 5 , C 3 F 7 or C 4 F 9 ; the latter two can be linear or branched.
  • R 2 and R 3 may be the same or different. They stand for H, alkyl with 1 to 4 carbon atoms.
  • R 1 has the meaning given above.
  • R 4 is a saturated cyclic 5-ring amino group or a saturated 6-ring amino group. These ring systems can optionally have 1 or 2 heteroatoms such as oxygen or nitrogen exhibit. The nitrogen atom through which the bond to
  • R 4 is preferably the morpholino, piperidino or pyrrolidino group.
  • Preferred conductive salts are lithium salts.
  • Lithium hexafluorophosphate, lithium tetrafluoroborate and lithium salts of sulfonylimides, for example the lithium salt of bis (trifluoromethanesulfonyl) imide, are particularly useful.
  • the conductive salts are expediently present in the solvent in a concentration of at least 0.5 mol / l. Usually concentrations of about 1 mol / 1 of conductive salt are aimed for in the finished electrolytes. The upper limit is of course the saturation concentration.
  • LiAsF 6 , LiSbF 6 , LiC10 4 and LiN (C 2 F 5 S0 2 ) are also very useful.
  • amidines described here can be used in pure form, as a mixture of amidines or as a mixture with other, known to be useful solvents for the production of electrolytes.
  • the solvent described in the publications cited above as useful can be used as a further solvent.
  • the usable solvents are not limited to the classes of compounds mentioned there. Other commonly used solvents can also be used.
  • Usable as pure solvents are, for example, the dialkylamides of perfluorinated carboxylic acids described in the unpublished German patent application ... (199 42 021.1).
  • the compounds described there are C1-C3 dialkylamides, especially trifluoroacetic acid. These compounds in particular have a stabilizing effect on lithium hexafluorophosphate.
  • aprotic solvents can also be used, for example lactones, nitriles, formamides, acetamides, pyrrolidinones, oxazolidinones, nitroalkanes, N, N-substituted uretanes, sulfolanes, dialkyl sulfoxides, dialkyl sulfites and trialkyl phosphates.
  • R 1 and R 4 have the meaning given above.
  • the invention further relates to electrolytes which contain amidines of the general formula (I) and / or (II) and conductive salts and, if appropriate, further aprotic solvents for conductive salts.
  • the amidines are compounds which can be derived from perfluorinated C2-C5 carboxylic acids.
  • the amidines of the formula (I) and (II) are preferred.
  • amidines increases the range of solvents available for conductive salts; the compounds have the advantage that they have a very good dissolving power for conductive salts.
  • the preparation of the amidines is very simple.
  • the carboxylic acid nitrile of the respective carboxylic acid is reacted with the desired amine.
  • the amidines are formed in an addition reaction and are isolated in a conventional manner, e.g. B. by distillation.
  • amidines are therefore also recommended for use in a mixture with other solvents, which may not have as good a solvent power, but other application advantages. They also have application-related advantages at lower temperatures.

Landscapes

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

Abstract

Selon l'invention, des amidines d'acides carboxyliques C2-C5 perfluorés peuvent être utilisées comme solvant ou composant de solvant pour les sels conducteurs contenus dans des électrolytes. Quelques nouvelles amidines sont également décrites.
PCT/EP2001/000886 2000-02-04 2001-01-27 Utilisation d'amidines WO2001057947A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU37349/01A AU3734901A (en) 2000-02-04 2001-01-27 Use of amidines

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10004928A DE10004928A1 (de) 2000-02-04 2000-02-04 Verwendung von Amidinen
DE10004928.1 2000-02-04

Publications (1)

Publication Number Publication Date
WO2001057947A1 true WO2001057947A1 (fr) 2001-08-09

Family

ID=7629818

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2001/000886 WO2001057947A1 (fr) 2000-02-04 2001-01-27 Utilisation d'amidines

Country Status (3)

Country Link
AU (1) AU3734901A (fr)
DE (1) DE10004928A1 (fr)
WO (1) WO2001057947A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10056647B2 (en) * 2013-11-20 2018-08-21 Samsung Sdi Co., Ltd. Electrolyte for rechargeable lithium battery and rechargeable lithium battery including same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015225286A1 (de) 2015-12-15 2017-06-22 Volkswagen Aktiengesellschaft Perfluorierte Elektrolytlösungsmittel in Lithium-Schwefel-Batterien

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2676985A (en) * 1952-05-02 1954-04-27 Minnesota Mining & Mfg Perfluoroalkyl amidines and salts thereof
EP0550200A2 (fr) * 1991-12-31 1993-07-07 Minnesota Mining And Manufacturing Company Procédé de déshydratation
WO1998029877A1 (fr) * 1996-12-30 1998-07-09 Hydro-Quebec Conducteurs protoniques sous forme liquide
US5866612A (en) * 1994-12-20 1999-02-02 Glaxo Wellcome Inc. Acetamidine derivatives and their use as inhibitors for the nitric oxide synthase

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2676985A (en) * 1952-05-02 1954-04-27 Minnesota Mining & Mfg Perfluoroalkyl amidines and salts thereof
EP0550200A2 (fr) * 1991-12-31 1993-07-07 Minnesota Mining And Manufacturing Company Procédé de déshydratation
US5866612A (en) * 1994-12-20 1999-02-02 Glaxo Wellcome Inc. Acetamidine derivatives and their use as inhibitors for the nitric oxide synthase
WO1998029877A1 (fr) * 1996-12-30 1998-07-09 Hydro-Quebec Conducteurs protoniques sous forme liquide

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BURGER K.: "Eine einfache Synthese für trifluoromethyl-substituierte Pyrimidine", SYNTHESIS, vol. 11, 1981, pages 904 - 905, XP002170653 *
JOHNSON R.N.: "The reaction of trifluoroacetonitrile with aliphatic diamines", J.ORG.CHEM., vol. 27, 1962, pages 3958 - 3962, XP002170652 *
KLAUS BURGER: "Trifluomethyl-substituierte Pyrimidine aus Enaminen und Trifluoracetonitril", LACHDL, 1984, pages 991 - 1002, XP002169965 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10056647B2 (en) * 2013-11-20 2018-08-21 Samsung Sdi Co., Ltd. Electrolyte for rechargeable lithium battery and rechargeable lithium battery including same

Also Published As

Publication number Publication date
AU3734901A (en) 2001-08-14
DE10004928A1 (de) 2001-08-09

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