WO2002011229A1 - Novel use of difluoromalonic acid esters - Google Patents

Novel use of difluoromalonic acid esters Download PDF

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Publication number
WO2002011229A1
WO2002011229A1 PCT/EP2001/008478 EP0108478W WO0211229A1 WO 2002011229 A1 WO2002011229 A1 WO 2002011229A1 EP 0108478 W EP0108478 W EP 0108478W WO 0211229 A1 WO0211229 A1 WO 0211229A1
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compounds
formula
solvent
electrolyte
general formula
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PCT/EP2001/008478
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German (de)
French (fr)
Inventor
Olaf BÖSE
Matthias Rieland
Dirk Seffer
Wolfgang Kalbreyer
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Solvay Fluor Und Derivative Gmbh
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Priority to AU2001289723A priority Critical patent/AU2001289723A1/en
Publication of WO2002011229A1 publication Critical patent/WO2002011229A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/62—Halogen-containing esters
    • C07C69/63—Halogen-containing esters of saturated acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen 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
    • 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
    • H01M10/0569—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
    • 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
    • H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
    • 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 novel use for difluoronic acid esters and a new compound.
  • the object of the present invention was to provide further compounds which can be used as solvents for electrolytes and which, for increased security, can be of the lithium ion battery.
  • This object is achieved by the invention.
  • compounds of the general formula (I) E -OC (O) -CF 2 -C (O) -OR 2 wherein R 1 and R 2 are the same or different and for Cl-C4-alkyl or for by at least 1 fluorine atom
  • Substituted Cl-C4-alkyl are available as solvents in electrolytes, especially lithium ion batteries.
  • R 1 and R 2 are preferably the same. They particularly preferably mean methyl, ethyl, n-propyl, i-propyl or 2,2,2-trifluoroethyl.

Abstract

Difluoromalonic acid dialkyl esters can be used as solvents in electrolytes for lithium-ion batteries. The invention also relates to novel compounds of difluoromalonic acid.

Description

Neuartige Verwendung von Difluormalonsäureestern Novel use of difluoronic acid esters
Beschreibungdescription
Die Erfindung bezieht sich auf eine neuartige Verwendungsmöglichkeit für Difluormalonsäureester und eine neue Verbindung.The invention relates to a novel use for difluoronic acid esters and a new compound.
Lithiumionen-Batterien weisen einen Elektrolyten auf, der ein Leitsalz umfaßt sowie ein oder mehrere polare, apro- tische Lösungsmittel . Ein sehr gutes Leitsalz ist LiPF6. Andere brauchbare Lithiumsalze sind LiBF4, das Lithiumsalz der Trifluormethansulfonsäure, die Lithiumsalze von Bis-tri- fluormethansulfonyl) imiden oder Lithiumsalze von Verbindungen des sechsfach koordinierten Phosphors mit F und CF3-Gruppen als Substituent, wie in der WO 98/15562 angegeben. Als Lösungsmittel werden beispielsweise Alkylencarbonate, acycli- sche Carbonate, Ether, Formamide, Sulfolane oder Methylsul- folane eingesetzt. Brauchbar sind auch bestimmte Nitrile oder stickstoffhaltige Verbindungen, wie Nitromethan, Pyrrolidi- none etc. siehe z. B. Macoto Ue, Kazuhiko Ida, und Shoichiro Mori in J. Electroche . Soc . 141 (1994), Seiten 2989 - 2996.Lithium ion batteries have an electrolyte which comprises a conductive salt and one or more polar, aprotic solvents. A very good conductive salt is LiPF 6 . Other useful lithium salts are LiBF 4 , the lithium salt of trifluoromethanesulfonic acid, the lithium salts of bis-trifluoromethanesulfonyl) imides or lithium salts of compounds of six-coordinate phosphorus with F and CF 3 groups as a substituent, as indicated in WO 98/15562. Examples of solvents used are alkylene carbonates, acyclic carbonates, ethers, formamides, sulfolanes or methylsulfolanes. Certain nitriles or nitrogen-containing compounds, such as nitromethane, pyrrolidinone, etc., can also be used. B. Macoto Ue, Kazuhiko Ida, and Shoichiro Mori in J. Electroche. Soc. 141 (1994), pages 2989-296.
Aufgabe der vorliegenden Erfindung war es, weitere, als Lösungsmittel für Elektrolyte verwendbare Verbindungen anzugeben, die zu einer erhöhten Sicherheit der Lithiumionenbatterie betragen können. Diese Aufgabe wird durch die Erfindung gelöst. Erfindungsgemäß werden Verbindungen der allgemeinen Formel (I) E -O-C (O) -CF2-C (O) -O-R2, worin R1 und R2 gleich oder verschieden sind und für Cl-C4-Alkyl oder für durch mindestens 1 Fluoratom substituiertes Cl-C4-Alkyl stehen, als Lösungsmittel in Elektrolyten, insbesondere von Lithiumionen-Batterien. Bevorzugt sind R1 und R2 gleich. Besonders bevorzugt bedeuten sie Methyl, Ethyl, n-Propyl, i-Propyl oder 2,2,2-Tri- fluorethyl.The object of the present invention was to provide further compounds which can be used as solvents for electrolytes and which, for increased security, can be of the lithium ion battery. This object is achieved by the invention. According to the invention compounds of the general formula (I) E -OC (O) -CF 2 -C (O) -OR 2 , wherein R 1 and R 2 are the same or different and for Cl-C4-alkyl or for by at least 1 fluorine atom Substituted Cl-C4-alkyl are available as solvents in electrolytes, especially lithium ion batteries. R 1 and R 2 are preferably the same. They particularly preferably mean methyl, ethyl, n-propyl, i-propyl or 2,2,2-trifluoroethyl.
Die Verbindungen der Formel (I) können als alleiniges Lösungsmittel in Elektrolyten verwendet werden. Bevorzugt wird eine Verbindung der Formel (I) zusammen mit mindestens einem weiteren polaren, aprotischen organischen Lösungsmittel eingesetzt. Als weiteres Lösungsmittel können die bereits bekannten Lösungsmittel für Elektrolyte verwendet werden. Brauchbare Lösungsmitteltypen sind beispielsweise in der angegebenen Literaturstelle von Ue et al. erwähnt. Besonders gut brauchbar sind Dialkylcarbonate, Alkylencarbonate, Lactone, Nitrile und Formamide. Gut brauchbar sind Gemische mit den, in der WO 00/38264 offenbarten, alkylenverbrückten Diestern. Sehr vorteilhaft sind auch Gemische mit Dialkyl- a iden von fluorierten Carbonsäuren, beispielsweise von N,N-Dialkylamiden der Trifluoressigsäure, die z. B. in der WO 00/38259 offenbart sind. "Alkyl" steht hier vorzugsweise für Cl-C4-Alkyl. Das Mol-Verhältnis der Verbindung der Formel (I) und des anderen Lösungsmittels liegt bevorzugt im Bereich von 1:0,5 bis 1:10. Neben solchen Lösungsmittelgemischen sind Elektrolyte, die eine Verbindung der allgemeinen Formel (I) und ein Leitsalz sowie gegebenenfalls weitere bekannte Elek- trolytlösungsmittel enthalten, ebenfalls Gegenstand der Erfindung. Bevorzugte Leitsalze umfassen als Kation das Lithium-Kation. Bevorzugtes Anion des Leitsalzes ist das einfach negativ geladene Anion PF5, brauchbar sind aber auch die einfach negativ geladenen Anionen BF , CF3S03, C104, [N(S02CF3)2] oder PFx(CF3)y, worin x + y = 6 gilt und x = 1 bis 5 und y = 1 bis 5 ist. Bevorzugt ist im erfindungsgemäßen Elektroyten zusätzlich zu einer oder mehreren Verbindungen der Formel (I) ein weiteres Elektrolytlösungsmittel enthalten, vorzugsweise ein Dialkylcarbonat, ein Alkylencarbonat oder ein N,N-Dialkylamid der Trifluoressigsäure, wobei Alkyl für Cl-C4-Alkyl, steht. Brauchbar sind als weiteres Elektrolytlösungsmittel auch Amide der Trifluoressigsäure, in wel- chen der Amid-Stickstoff in ein 5- oder 6-Ringsystem eingebaut ist, welches auch Heteroatome wie Sauerstoff enthalten kann. Beispiele sind Amide der Trifluoressigsäure, in welchen die Amidgruppe durch die Pyrrolidinyl-, Morpholinyl- oder Piperidinyl-Gruppe gebildet ist.The compounds of formula (I) can be used as the sole solvent in electrolytes. A compound of the formula (I) is preferably used together with at least one other polar, aprotic organic solvent. The known solvents for electrolytes can be used as a further solvent. Usable types of solvents are described, for example, in the literature reference by Ue et al. mentioned. Dialkyl carbonates, alkylene carbonates, lactones, nitriles and formamides are particularly useful. Mixtures with the alkylene-bridged diesters disclosed in WO 00/38264 are very useful. Mixtures with dialkyl aids of fluorinated carboxylic acids, for example of N, N-dialkylamides of trifluoroacetic acid, which, for. B. are disclosed in WO 00/38259. "Alkyl" here preferably stands for C1-C4-alkyl. The molar ratio of the compound of formula (I) and the other solvent is preferably in the range from 1: 0.5 to 1:10. In addition to such solvent mixtures, electrolytes which contain a compound of the general formula (I) and a conductive salt and, if appropriate, further known electrolyte solvents are also a subject of the invention. Preferred conductive salts include the lithium cation as the cation. The preferred anion of the conducting salt is the simply negatively charged anion PF 5 , but the simply negatively charged anions BF, CF 3 S0 3 , C10 4 , [N (S0 2 CF 3 ) 2 ] or PF x (CF 3 ) y are also useful , where x + y = 6 and x = 1 to 5 and y = 1 to 5. In addition to one or more compounds of the formula (I), the electrolyte according to the invention preferably contains a further electrolyte solvent, preferably a dialkyl carbonate, an alkylene carbonate or an N, N-dialkylamide of trifluoroacetic acid, alkyl being C1-C4-alkyl. Amides of trifluoroacetic acid can also be used as a further electrolyte solvent, in which Chen the amide nitrogen is built into a 5- or 6-ring system, which can also contain heteroatoms such as oxygen. Examples are amides of trifluoroacetic acid, in which the amide group is formed by the pyrrolidinyl, morpholinyl or piperidinyl group.
CF3CH2-0-C(0)CF2C(0)-0-CH2CF3 ist neu und ebenfalls Gegenstand der Erfindung.CF 3 CH 2 -0-C (0) CF 2 C (0) -0-CH 2 CF 3 is new and also the subject of the invention.
Die Herstellung von Difluormalonestern aus den entsprechenden Chlorverbindungen und Aminfluorid-HF-Addukten offenbart die EP-A 597 329.EP-A 597 329 discloses the preparation of difluoromalone esters from the corresponding chlorine compounds and amine fluoride-HF adducts.
Zur Herstellung der Verbindungen der Formel (I) kann man ausgehen von analogen Verbindungen der Formel R^-O-C (O) -CBr2- C{0)-0-R2. Ester mit R1, R2 = Methyl oder Ethyl sind z. B. im Handel erhältlich. Andere Ester erhält man durch Umesterung (vor oder nach der Fluorierung) . Die Ausgangsverbindung setzt man mit einem Fluorierungsmittel wie KF um. Ein geeignetes Lösungsmittel wie Sulfolan kann eingesetzt werden. Dieses Verfahren ist neu und ebenfalls Gegenstand der Erfindung.The compounds of the formula (I) can be prepared from analogous compounds of the formula R ^ -OC (O) -CBr 2 - C {0) -0-R 2 . Esters with R 1 , R 2 = methyl or ethyl are e.g. B. commercially available. Other esters are obtained by transesterification (before or after fluorination). The starting compound is reacted with a fluorinating agent such as KF. A suitable solvent such as sulfolane can be used. This method is new and also the subject of the invention.
Ein anderes Herstellungsverfahren durch alkalische Per- manganat-Oxidation von Polyfluorocyclohexenen offenbaren E. J. P. Fear et al. in J. Appl. Che . 5 (1955), Seiten 589 - 594. Eine weitere Herstellungsmethode umfaßt die Fluorierung des Monobromderivates der jeweiligen Malonester, siehe E. D. Bergmann et al . in J. Chem. Soc. 1959, Seiten 3286 - 3289.Another manufacturing process by alkaline permanganate oxidation of polyfluorocyclohexenes is disclosed by E. J. P. Fear et al. in J. Appl. Che. 5 (1955), pages 589-594. Another production method comprises the fluorination of the monobromo derivative of the respective malonic ester, see E. D. Bergmann et al. in J. Chem. Soc. 1959, pages 3286-3289.
Die Technik, insbesondere im Hinblick auf die Palette der verfügbaren Lösungsmittel, besonders bei Elektrolyten für Batterien wird durch die Erfindung bereichert. Die Verbindungen weisen durch ihren Fluorierungsg ad einen erhöhten Flammpunkt auf und tragen dadurch zu einer erhöhten Sicherheit der Lithiumionenbatterie bei. Die folgenden Beispiele sollen die Erfindung weiter erläutern, ohne sie in ihrem Umfang einzuschränken.The technology, in particular with regard to the range of available solvents, particularly in the case of electrolytes for batteries, is enriched by the invention. The compounds have an increased flash point due to their fluorination thread and thus contribute to increased safety of the lithium ion battery. The following examples are intended to illustrate the invention without restricting its scope.
BeispieleExamples
Beispiel 1;Example 1;
Herstellung von DifluormalonsäurediethylesterProduction of difluoromonic acid diethyl ester
+KF C2H5OOCCBr2COOC2H5 i ;>- C2H5OOCCF2COOC2H5 + KF C 2 H 5 OOCCBr 2 COOC 2 H 5 i;> - C 2 H 5 OOCCF 2 COOC 2 H 5
-KBr In einem 2 1 Kolben mit Rückflußkühler und Rührer wurden Di- brom alonsäurediethylester (318 g; 1 mol; 318 g mol-1) , Kali- umfluorid (232 g; 4 mol; 58 g mol-1) und 250 ml Sulfolan vorgelegt. Das Reaktionsgemisch wurde auf 80 bis 150 °C erwärmt. Nach dem Abkühlen wurde dreimal mit je 40 ml Dichlormethan extrahiert. Das erhaltene Rohprodukt wurde destillativ gereinigt.-KBr In a 2 1 flask with reflux condenser and stirrer were diethyl dibromononate (318 g; 1 mol; 318 g mol -1 ), potassium fluoride (232 g; 4 mol; 58 g mol -1 ) and 250 ml sulfolane submitted. The reaction mixture was heated to 80 to 150 ° C. After cooling, the mixture was extracted three times with 40 ml of dichloromethane each time. The crude product obtained was purified by distillation.
Ausbeute: 81,2 g (0,472 mol, 172 g mol-1; 47,2 %) Kp. : 66 - 68 °C bei 10 barYield: 81.2 g (0.472 mol, 172 g mol -1 ; 47.2%) bp: 66 - 68 ° C at 10 bar
^- MR: 1,36 ppm (Triplett, CH3 ) ; 4,39 ppm (Quartett, CH2) 12C-NMR: 13,79 ppm (Singulett, CH3 ) ; 63,91 ppm (Singulett,^ - MR: 1.36 ppm (triplet, CH 3 ); 4.39 ppm (quartet, CH 2 ) 12 C-NMR: 13.79 ppm (singlet, CH 3 ); 63.91 ppm (singlet,
CH2); 106,24 ppm (Triplett, CF2) ; 160,85 ppmCH 2 ); 106.24 ppm (triplet, CF 2 ); 160.85 ppm
(Triplett, CO) 19F-NMR: Singulett, CF2 (Triplet, CO) 19 F-NMR: singlet, CF 2
Die Lδslichkeit an Li [N(S02CF3) 2] betrug mehr als 2 mol/1. The solubility in Li [N (S0 2 CF 3 ) 2 ] was more than 2 mol / 1.

Claims

Patentansprüche claims
1. Verwendung von Verbindungen der allgemeinen Formel (I)1. Use of compounds of the general formula (I)
RI-O-C (O) -CF2C (0) -0-R2 RI-OC (O) -CF 2 C (0) -0-R 2
worin R1 und R2 gleich oder verschieden sind und für C1-C4- Alkyl oder für durch mindestens 1 Fluoratom substituiertes Cl-C4-Alkyl stehen, als Lösungsmittel in Elektrolyten, insbesondere von Lithium-Batterien mit erhöhter Sicherheit.wherein R 1 and R 2 are the same or different and stand for C1-C4-alkyl or for Cl-C4-alkyl substituted by at least 1 fluorine atom, as a solvent in electrolytes, in particular of lithium batteries, with increased security.
2. Verwendung nach Anspruch 1, wobei R1 und R2 gleich sind und Methyl, Ethyl, i-Propyl, n-Propyl oder 2,2,2-Tri- fluorethyl bedeuten.2. Use according to claim 1, wherein R 1 and R 2 are the same and are methyl, ethyl, i-propyl, n-propyl or 2,2,2-tri-fluoroethyl.
3. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß mindestens ein weiteres, aprotisches, nichtwäßriges Elektrolytlösungsmittel eingesetzt wird.3. Use according to claim 1, characterized in that at least one other, aprotic, non-aqueous electrolyte solvent is used.
4. Verbindung der allgemeinen Formel (I), worin R und4. Compound of general formula (I), wherein R and
22
R 2, 2, 2-Trifluorethyl bedeuten.R 2, 2, 2-trifluoroethyl mean.
5. Elektrolyt, umfassend eine Verbindung der allgemeinen Formel (I) und ein Leitsalz, vorzugsweise LiPF6.5. Electrolyte comprising a compound of general formula (I) and a conductive salt, preferably LiPF 6 .
6. Elektrolyt, weiterhin umfassend mindestens ein weiteres aprotisches, nichtwäßriges Elektrolytlösungsmittel .6. electrolyte, further comprising at least one other aprotic, non-aqueous electrolyte solvent.
7. Gemische, umfassend Verbindungen der Formel (I) und mindestens ein weiteres Elektrolytlösungsmittel.7. Mixtures comprising compounds of the formula (I) and at least one further electrolyte solvent.
8. Verfahren zur Herstellung von Verbindungen der Formel (I) Ri-O-C (O ) -CF2-C (0 ) -O-R2 8. Process for the preparation of compounds of formula (I) Ri-OC (O) -CF 2 -C (0) -OR 2
worin R1 und R2 die oben angegebene Bedeutung besitzen, durch Umsetzung von Verbindungen der Formel (la)wherein R 1 and R 2 have the meaning given above, by reacting compounds of the formula (Ia)
Ri-O-C (0) -CBr2-C (O) -O-R2 R i -OC (0) -CBr 2 -C (O) -OR 2
mit Fluorierungsmitteln, insbesondere KF. with fluorinating agents, especially KF.
PCT/EP2001/008478 2000-08-02 2001-07-23 Novel use of difluoromalonic acid esters WO2002011229A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2667444A1 (en) * 2012-05-21 2013-11-27 Solvay Sa Use of fluorinated 2-methoxymalonic acid esters in electrolyte or solvent compositions
WO2018181856A1 (en) * 2017-03-31 2018-10-04 Murata Manufacturing Co., Ltd. Non-aqueous electrolytes and electrolytic solutions comprising electrolyte stabilizing materials, secondary batteries comprising the same, and uses thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0005810A1 (en) * 1978-06-01 1979-12-12 Hoechst Aktiengesellschaft Method for the preparation of organic fluoro compounds
JPH05301844A (en) * 1992-04-22 1993-11-16 Idemitsu Kosan Co Ltd Production of 2-fluoroisobutyric ester
EP0597329A2 (en) * 1992-11-10 1994-05-18 Bayer Ag Process for the preparation of alpha-fluor-beta dicarbonyle compounds
JPH08190932A (en) * 1995-01-06 1996-07-23 Nippon Telegr & Teleph Corp <Ntt> Secondary battery having nonaqueous solvent electrolyte
EP0948073A1 (en) * 1997-06-13 1999-10-06 Daikin Industries, Ltd. Electrolytic solution and device for generating electric energy therewith
WO2000001027A1 (en) * 1998-06-26 2000-01-06 Duracell Inc. Solvent for electrolytic solutions

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0005810A1 (en) * 1978-06-01 1979-12-12 Hoechst Aktiengesellschaft Method for the preparation of organic fluoro compounds
JPH05301844A (en) * 1992-04-22 1993-11-16 Idemitsu Kosan Co Ltd Production of 2-fluoroisobutyric ester
EP0597329A2 (en) * 1992-11-10 1994-05-18 Bayer Ag Process for the preparation of alpha-fluor-beta dicarbonyle compounds
JPH08190932A (en) * 1995-01-06 1996-07-23 Nippon Telegr & Teleph Corp <Ntt> Secondary battery having nonaqueous solvent electrolyte
EP0948073A1 (en) * 1997-06-13 1999-10-06 Daikin Industries, Ltd. Electrolytic solution and device for generating electric energy therewith
WO2000001027A1 (en) * 1998-06-26 2000-01-06 Duracell Inc. Solvent for electrolytic solutions

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199350, Derwent World Patents Index; Class C03, AN 1993-400364, XP002185482 *
PATENT ABSTRACTS OF JAPAN vol. 1996, no. 11 29 November 1996 (1996-11-29) *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2667444A1 (en) * 2012-05-21 2013-11-27 Solvay Sa Use of fluorinated 2-methoxymalonic acid esters in electrolyte or solvent compositions
WO2013174697A1 (en) * 2012-05-21 2013-11-28 Solvay Sa Use of fluorinated 2 -methoxymalonic acid esters in electrolyte or solvent compositions
WO2018181856A1 (en) * 2017-03-31 2018-10-04 Murata Manufacturing Co., Ltd. Non-aqueous electrolytes and electrolytic solutions comprising electrolyte stabilizing materials, secondary batteries comprising the same, and uses thereof
CN110800150A (en) * 2017-03-31 2020-02-14 株式会社村田制作所 Non-aqueous electrolyte and electrolytic solution containing electrolyte stabilizing material, secondary battery containing the same, and use thereof

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