WO2014167035A1 - Procédé pour la préparation de composés fluoro et chloro cyano du 15ème groupe du tableau périodique des éléments - Google Patents

Procédé pour la préparation de composés fluoro et chloro cyano du 15ème groupe du tableau périodique des éléments Download PDF

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WO2014167035A1
WO2014167035A1 PCT/EP2014/057220 EP2014057220W WO2014167035A1 WO 2014167035 A1 WO2014167035 A1 WO 2014167035A1 EP 2014057220 W EP2014057220 W EP 2014057220W WO 2014167035 A1 WO2014167035 A1 WO 2014167035A1
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compound
formula
group
cis
cat
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Katharina SIEVERT
Axel Schulz
Jörg HARLOFF
Alrik STOFFERS
Stefan Ellinger
Lothar Ott
Christiaan RIJKSEN
Patrick Franke
Christoph Taeschler
Cornelia Zur Taeschler
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Lonza Ltd
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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
    • H01M10/056—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
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • 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
    • H01M2300/0045—Room temperature molten salts comprising at least one organic ion
    • 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 discloses a method for preparation of fluoro and chloro cyano compounds of the 15th group of the periodic table with 1 to 5 cyano residues, represented by formula (I), by a reaction using trimethylsilylcyanide, certain fluoro and chloro cyano compounds of the 15th group of the periodic table,the compounds are used as ionic liquids;
  • Cat is a cation
  • Z is P, As, Sb or Bi
  • Q is fluoro or chloro
  • m is an integer from 1 to 5 and n is i, 2, 3 or 4.
  • ionic liquid is usually used to refer to a salt which is liquid at temperatures below 100°C, in particular at room temperature.
  • Such liquid salts typically comprise organic cations and organic or inorganic anions, and are described inter alia in P. Wasserscheid et al., Angew. Chem., 2000, 112, 3926-3945.
  • Ionic liquids have a series of interesting properties: Usually, they are thermally stable, relatively non-flammable and have a low vapor pressure. They show good solvability for numerous organic and inorganic substances. In addition, ionic liquids have interesting electrochemical properties, for example electrical conductivity which is often accompanied by a high electrochemical stability.
  • ionic liquids can be used foremost as solvent in synthesis, as electrolyte, as lubricant and as hydraulic fluid. Moreover they serve as phase-transfer catalyst, as extraction medium, as heat-transfer medium, as surface-active substance, as plasticizer, as conductive salt, organic salt or additive in electrochemical cells, as electrolyte, as component in electrolyte formulations, wherein such electrolyte formulation comprising an ionic liquid is preferably used in electrochemical and/or optoelectronic device such as a photovoltaic cell, a light emitting device, an electrochromic or photo-electrochromic device, an electrochemical sensor and/or biosensor, particularly preferred in a dye sensitized solar cell.
  • electrochemical and/or optoelectronic device such as a photovoltaic cell, a light emitting device, an electrochromic or photo-electrochromic device, an electrochemical sensor and/or biosensor, particularly preferred in a dye sensitized solar cell.
  • US 2013/0089777 Al disclose a material for use as an electrolyte comprising a lithium salt which comprises the following components (Al) and (B), or which comprises the following components (Al), (A2) and (B):
  • n is an integer of 1 to 5.
  • Li P(CN) 3 F 3 is the only compound disclosed as substance. Its preparation starts with AgCN and PC1 3 providing P(CN) 3 , which is converted with LiCl and gaseous Cl 2 to Li P(CN) 3 (C1) 3 , which is converted with AgBF 4 to Ag P(CN) 3 (F) 3 , which is converted with Lil to the desired Li P(CN) 3 (C1) 3 .
  • the only two electrolytes disclosed comprise a Li + cation, a trifluorotricyanophosphate anion and optionally a l-ethyl-3-methylimidazolium cation.
  • JP 2012 009158 A discloses an electrolyte useful in a lithium secondary battery comprising components (Al), (A2) and (B), with (Al) being a Lithium cation, (A2) being an organic cation and (B) being a cyanofluorophosphate -based anion represented by the general formula
  • n is an integer of 1 to 5.
  • l-ethyl-3-methylimidazolium trifluorotricyanophosphate is the only compound disclosed as substance. Its preparation is identical with the preparation disclosed in EP 2 410 601 Al and starts with PC1 5 and l-ethyl-3-methylimidazolium chloride, then reaction with AgCN providing l-ethyl-3-methylimidazolium P(CN)3Cl3.
  • a third step is necessary, that is reaction with AgBF 4 as fluorinating agent, then a fourth step follows, addition of l-ethyl-3-methylimidazolium chloride.
  • JP 2012 248515 A discloses a metal salt useful for an electrode protective film forming agent, the metal salt comprises a component (Al) or a component (A2), and a component (B), (Al) being a monovalent metal cation (excluding a lithium cation), (A2) being a divalent metal cation and (B) being a cyanofluorophosphate type anion represented by the
  • EP 2 587 580 Al discloses an electrolyte material containing a lithium salt comprising the components (Al-580) and (B-580), or containing the components (Al-580), (A2-580) and (B- 580):
  • n is an integer of 1 to 5.
  • n 3 in form of the cyanofluorophosphates AgP(CN) 3 F 3 and LiP(CN) 3 F 3 and in form of the electrolyte material containing a lithium cation, a l-ethyl-3- methylimidazolium cation and a trifluorotricyanophosphate anion.
  • the anion having the general formula [(Z 1 (Q 1 ) 6 _ m (CN) m ) ] with Z 1 being P, As, Sb or Bi, Q 1 being
  • CI or F and m being 1 , 2, 3, 4 or 5.
  • the method should require as few steps as possible.
  • the method should allow also the preparation of compounds with m being 1 , 2, 4 or 5 and not only of compound with m being 3.
  • the method should avoid the use of Cl 2 , AgCN of AgBF 4 .
  • the method should provide stable compounds of said formula which can be used as ionic liquids or as precursors of ionic liquids and can be used e.g. in electrolyte formulations and in electrochemical or optoelectronic devices. These compounds should be able to be disposed of in an environmentally friendly manner after use.
  • This object is achieved by a method using trimethylsilylcyanide as CN source. No Cl 2 , AgCN or AgBF 4 is required. Another advantage is that the reaction does not require an extra solvent.
  • the compounds obtained show good performance such as high thermal stability, low melting points, high stability against acids or bases or good electrochemical properties.
  • alkyl linear or branched alkyl
  • Ci_ q alkyl refers to any alkyl residue which contains from 1 to q carbon atoms
  • Ci_ 6 alkyl encompasses inter alia methyl, ethyl, propyl, isopropyl, n- butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl (3-methylbutyl), neopentyl (2,2-dimethylpropyl), n-hexyl and isohexyl (4-methylpentyl);
  • C 2 - q alkenyl refers to an alkenyl residue which contains from 2 to q carbon atoms and contains at least one double bond, the carbon chain can be linear or branched; for example C 2 _ 4 alkenyl encompasses inter alia ethenyl, 1-methylethenyl, prop-l-enyl, prop-2-enyl, 2-methylprop-2-enyl and buta-l ,3-dienyl;
  • C 2 _ q alkynyl refers to an alkynyl residue which contains from 2 to q carbon atoms and contains at least one triple bond, the carbon chain can be linear or branched; for example C 2 _ 4 alkynyl encompasses inter alia ethynyl, prop-l-ynyl and prop-2-ynyl;
  • C 6 -io aryl refers to an aryl residue which has from 6 to 10 carbon atoms and is
  • Ci_ 4 alkyl and Ci_ 4 alkoxy for example C 6-10 aryl encompasses inter alia phenyl, methylphenyl, methoxyphenyl, dimethylphenyl, ethylmethylphenyl, diethylphenyl and naphthyl;
  • cyclic alkyl or cycloalkyl include cyclo and polycyclo, such as bicyclo or tricyclo,
  • C3_ q cycloalkyl refers to a cycloalkyl group having from 3 to q carbon atoms
  • C3-10 cycloalkyl encompasses inter alia cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl;
  • Ci_ q alkoxy refers to an linear or branched alkoxy group having from 1 to q carbon atoms; for example Ci_ 2 o alkoxy encompasses inter alia methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, 1 ,4- dimethylpentyloxy, hexyloxy, heptyloxy, octyloxy, 1 ,5-dimethylhexyloxy, nonyloxy, decyloxy, 4-ethyl- 1 ,5-dimethylhexyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy and eicosyloxy;
  • alkylene means a linear or branched alkylene group; e.g. propylene, and e.g. propylene can be connected via its C I and C2 carbon atoms (a branched alkylene group), or via its C I and C3 carbon atoms (linear alkylene group);
  • halide F , CI , Br or I preferably F , CI or Br , more preferably CI
  • halogen F CI, Br or I; preferably F, CI or Br;
  • TMSCN (CH 3 ) 3 SiCN i.e. trimethylsilylcyanide
  • Subject of the invention is a method for the preparation of compound of formula (I); the method comprises a step (Stl) or a step (St3);
  • step (Stl) comprises a reaction (Real), wherein compound of formula (Al)
  • step (St3) comprises a reaction (Rea3), wherein compound formula (A3) is reacted with trimethylsilylcyanide in the presence of compound of formula (I-Cat-n);
  • (Cat n ) tl (AnINORG q" ) t2 Z 1 is selected from the group consisting of P, As, Sb and Bi;
  • Cat is selected from the group consisting of inorganic cation CatlNORG and organic n+
  • Q 1 is F or CI
  • n 1, 2, 3, 4 or 5;
  • n 1, 2, 3 or 4;
  • q 1 or 2;
  • tl is 1 or 2;
  • t2 is 1, 2, 3 or 4;
  • AnINORG is an anion selected from the group consisting of halide, OH “ , CN , OCN , SC , N 3 ⁇ , sulfate, hydrogensulfate, nitrate, C0 3 2" , HC0 3 “ , BF 4 " , PF 6 “ , SbF 6 " , CF 3 S0 3 “ , (CF 3 S0 2 ) 2 N ⁇ , (FS0 2 ) 2 N ⁇ , d_ 6 alkyl-S0 3 " , d_ 6 alkyl-0-S0 3 " ,
  • CatlNORG is a cation selected from the 1., 2., 3., 4., 5., 6., 7., 8., 9., 10., 1 1., 12., 13., 14.,
  • group of the periodic table or is a cation from the lanthanides, a cation from the actinides, NH 4 + , H 3 0 + or H 5 0 2 + ;
  • CatORG n+ is selected from the group consisting of CatORG-A + , CatORG-B + , CatORG- C + , CatORG-D + , CatORG-E + , guanidinium and (H 2 (R18)N-R16-N(R19)H 2 ) 2+ ;
  • CatORG-A + is (WR2R3R4R5) + ,
  • W is a nitrogen or phosphorus
  • R2, R3, R4 and R5 are identical or different and independently from each other selected from the group consisting of H, Ci_ 2 o alkyl, Ci_ 2 o
  • R2 and R3 together are a hydrocarbon chain and form together with W a 5- to
  • R4 and R5 are identical or different and independently from each other selected from the group consisting of H, Ci_ 2 o alkyl, Ci_ 20 perfluoroalkyl, C 3 _i 0 cycloalkyl and C 6-1 o aryl; or
  • R2 and R3 together are a hydrocarbon chain and form together with W
  • R4 and R5 together are a hydrocarbon chain and form together with W, independently from each other, 5- to 7-membered saturated or unsaturated heterocyclic rings
  • CatORG-B + is (XR6R7R8) + ,
  • R6 and R7 together are a hydrocarbon chain and form together with X a 5- to 7-membered unsaturated heterocyclic ring in which X is connected by a single bond and a double bond to R6 and R7 respectively,
  • R8 is selected from the group consisting of H, Ci_ 2 o alkyl, C 2 _s alkenyl, Ci_ 2 o
  • CatORG-C + is (YR9R10R1 1) + ,
  • Y is sulphur
  • R9, RIO and Rl 1 are identical or different and independently from each other selected from the group consisting of H, Ci_ 2 o alkyl, Ci_ 2 o
  • R9 and RIO together are a hydrocarbon chain and form together with Y a 5- to
  • Rl 1 is selected from the group consisting of H, Ci_ 2 o alkyl, Ci_ 2 o perfluoroalkyl, C 3 _io cycloalkyl and C 6 -io aryl;
  • CatORG-D + is (ZR12R13) + ,
  • Z is oxygen or sulphur
  • R12 and R13 together are a hydrocarbon chain and form together with Z a 5- to 7-membered heterocyclic ring in which Z is connected by a single bond and a double bond to R12 and R13 respectively;
  • CatORG-E is a cyclic C nx alkane or a cyclic C nx alkene bearing a positive charge, wherein
  • nx 3, 5, 7 or 9
  • said cyclic C nx alkene has 1 double bond in case of nx being 3, 2 double bonds in case of nx being 5, 3 double bonds in case of nx being 7, and 4 double bonds in case of nx being 9,
  • cyclic C nx alkane and cyclic C nx alkene are unsubstituted or substituted by 1 to nx
  • R14 and R15 are identical or different and independently from each other selected from the group consisting of H and Ci_ 6 alkyl; the residues R2, R3, R4, R5, R6, R7, R8, R9, RIO, Rl 1, R12 and R13 are, independently from each other, unsubstituted or, where applicable, substituted by 1, 2, 3, 4, 5 or 6 substituents selected from the group consisting of Ci_ 4 alkyl, C 3 _i 0 cycloalkyl, C 2 _8 alkenyl, phenyl, benzyl, halogen, cyano and Ci_ 4 alkoxy; in any of said hydrocarbon chains formed by R2 and R3, by R4 and R5, by R6 and R7, by R9 and R10, and by R12 and R13, 1 or 2 carbon atoms of said hydrocarbon chains can be exchanged for 1 or 2 heteroatoms respectively, said one or two heteroatoms being selected from the group consisting of O, N and S; in case of an exchange for N, this N
  • R16 is selected from the group consisting of C 2 _s alkylen, C 3 _s cycloalkylen, phenylen,
  • R17 is selected from the group consisting of CH 2 -CH 2 , CH 2 -CH 2 -CH 2 , CH 2 -C(H)(CH 3 )-
  • R18 and R19 are identical or different and independently from each other selected from the group consisting of H, Ci_s alkyl, C 3 _s cycloalkyl, phenyl and benzyl;
  • nl is an integer from 1 to 20.
  • Z 1 is P with any of the embodiments disclosed in the specification.
  • n is 1 or 2.
  • Q 1 is F.
  • Q 1 is CI
  • Q 1 is F and compound of formula (I) is prepared by step (Stl). In another preferred embodiment, Q 1 is CI and compound of formula (I) is prepared by step (St3).
  • m is 2, 3, 4 or 5.
  • n is 4 or 5;
  • n is 2, 3 or 4.
  • m is 4:
  • m is 2 or 3.
  • n 4 or 5 and Q 1 is F.
  • reaction (Real) in case of reaction (Real), m is 4 and Q 1 is F.
  • anion [(Z ! (Q Vm(CN) m ) " ] in formula (I) is preferably [(cis-P(Q 1 ) 2 (CN) 4 ) " ].
  • anion ] in formula (I) is preferably [(cis-PF 2 (CN) 4 ) " ].
  • CatINORG n+ is a cation selected from the 1., 2., 3., 4., 5., 6., 7., 8., 9., 10., 11.,
  • CatINORG n+ is a cation selected from the 1., 2., 4., 5., 6., 7., 8., 9., 10., 11., 12., 13., 14. or 15. group of the periodic table or is a cation from the lanthanides, NH 4 + ,
  • CatINORG n+ is selected from the group consisting of Li + , Na + , K + ,
  • CatINORG n+ is selected from the group consisting of Li + , Na + , K + , Mg 2+ , Ca 2+ ,
  • CatINORG n+ is selected from the group consisting of Li + , Na + , K + , Mg 2+ ,
  • CatINORG n+ is selected from the group consisting of Li + , Na + , K + ,
  • CatINORG n+ is selected from the group consisting of Li + , Na + , K + , Rb + , Cs + , NH 4 + , Ag + , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Zn 2+ , Cu 2+ , H 3 0 + and H 5 0 2 + ; preferably, CatINORG n+ is selected from the group consisting of Li + , Na + , K + , Rb + , Cs + ,
  • CatINORG n+ is selected from the group consisting of Li + , Na + , K + , NH 4 + ,
  • CatINORG n+ is selected from the group consisting of Li + , Na + , K + ,
  • CatINORG n is selected from the group consisting of Li + , Na + , K + , Ag + , H 3 0 + and
  • CatINORG n+ is selected from the group consisting of Li + , K + , Ag + , H 3 0 + and H 5 0 2 + ;
  • CatINORG n is selected from the group consisting of
  • CatlNORG is selected from the group consisting of Li , K , Mg , Ca , Zn ,
  • CatINORG n+ is selected from the group consisting of Li + , K + , Mg 2+ , Ca 2+ , H 3 0 + and H 5 0 2 + .
  • CatINORG n+ is selected from the group consisting of Li + , Na + , K + , NH 4 + , Ag + , Mg 2+ , Ca 2+ , Zn 2+ , Cu 2+ , H 3 0 + and H 5 0 2 + ;
  • CatINORG n+ is selected from the group consisting of Li + , Na + , K + , NH 4 + ,
  • CatINORG n+ is selected from the group consisting of Li + , Na + , K + , Ag + , Mg 2+ , Zn 2+ , H 3 0 + and H 5 0 2 + ;
  • CatINORG n+ is selected from the group consisting of Li + , K + , Ag + , Mg 2+ , Zn 2+ , H 3 0 + and H 5 0 2 + .
  • n in CatlnORG is a heteroatom selected from the group consisting of nitrogen, phosphorus, sulfur and oxygen;
  • CatORG n contains a heteroatom selected from the group consisting of
  • R16 is selected from the group consisting of C 2 _6 alkylen, C 5 _ 6 cycloalkylen, phenylen,
  • R17 is selected from the group consisting of CH 2 -CH 2 , CH 2 -CH 2 -CH 2 and
  • R18 and R19 are identical or different and independently from each other selected from the group consisting of H, Ci_ 4 alkyl, C 5 -6 cycloalkyl, phenyl and benzyl; nl is an integer from 1 to 10;
  • R16 is selected from the group consisting of C 2 _ 4 alkylen, C 6 cycloalkylen, phenylen, C(H)(phenyl), R17(-0-R17) tenui;
  • R17 is selected from the group consisting of CH 2 -CH 2 and CH 2 -CH 2 -CH 2 ;
  • R18 and R19 are identical and selected from the group consisting of H, Ci_ 4 alkyl,
  • nl is an integer from 1 to 6;
  • n is (H 2 (R18)N-R16-N(Rl 9)H 2 ) 2+ ;
  • R16 is selected from the group consisting of C 2 _ 4 alkylen, phenylen and C(H)(phenyl); R18 and R19 are identical and selected from the group consisting of H, Ci_ 4 alkyl, C 5 -6 cycloalkyl, phenyl and benzyl;
  • CatORG is (H 3 N-CH 2 -CH 2 -NH 3 ) 2+ .
  • CatORG is selected from the group consisting of cation CatORG- A + , CatORG-B + , CatORG-C + , CatORG-D + and CatORG-E + ;
  • CatORG-A is (WR2R3R4R5) ,
  • W is a nitrogen or phosphorus
  • R2, R3, R4 and R5 are identical or different and independently from each other selected from the group consisting of H, Ci_ 2 o alkyl, Ci_ 2 o
  • R4 and R5 are identical or different and independently from each other selected from the group consisting of H, Ci_ 20 alkyl, Ci_ 20 perfluoroalkyl, C 3 _i 0 cycloalkyl and C 6-10 aryl; or
  • CatORG-B + is (XR6R7R8) + ,
  • R6 and R7 together with X form a 5- to 7-membered unsaturated ring in which X formally has one single bond and one double bond to R6 and R7 respectively,
  • R8 is selected from the group consisting of Ci_ 20 alkyl, Ci_ 20 perfluoroalkyl, C 3 _i 0
  • CatORG-C + is (YR9R10R11) + ,
  • Y is sulphur
  • R9, RIO and Rl 1 are identical or different and independently from each other selected from the group consisting of Ci_ 2 o alkyl, Ci_ 2 o perfluoroalkyl, C3-10 cycloalkyl and C 6 -io aryl; or
  • R9 and RIO together with Y form a 5- to 7-membered saturated or unsaturated ring
  • Rl 1 is selected from the group consisting of Ci_ 2 o alkyl, Ci_ 2 o perfluoroalkyl, C 3-10 cycloalkyl and C 6 -io aryl;
  • CatORG-D is (ZR12R13) + , wherein
  • Z is oxygen or sulphur
  • R12 and R13 together with Z form a 5- to 7-membered ring in which Z formally has one
  • CatORG-E + is a cyclic C 3 _9 alkane or a cyclic C 3 _9 alkene bearing a positive charge; in case of a cyclic C 3 _ 9 alkene, CatORG-E + has 1 , 2 or 3 double bonds; the residues R2, R3, R4, R5, R6, R7, R8, R9, RIO, Rl 1 , R12 and R13 are, independently from each other, unsubstituted or, where applicable, substituted by 1 , 2 or 3 substituents selected from the group consisting of halogen, cyano and Ci_ 4 alkoxy; the rings formed by R2 and R3 together with W, R4 and R5 together with W, R6 and R7
  • X, R9 and RIO together with Y and R12 and R13 together with Z contain no, 1 or 2 further heteroatoms, the heteroatoms being selected from the group consisting of O, N and S; and wherein any further heteroatom N can be substituted by Ci_ 8 alkyl or Ci_8 perfluoroalkyl.
  • n in CatORG n+ is 1.
  • CatORG n is selected from the group consisting of
  • CatORG n is selected from the group consisting of
  • CatORG-E + is selected from the group consisting of
  • CatORG is selected from the group consisting of
  • CatORG is selected from the group consisting of
  • R20 is Ci_2o alkyl or C3-10 cycloalkyl
  • R21 , R22 and R23 are identical or different and independently selected from the group
  • R20 is Ci_i4 alkyl or C5-8 cycloalkyl
  • R21 , R22 and R23 are identical or different and independently selected from the group
  • R20 is Ci_8 alkyl or C 5 _ 7 cycloalkyl
  • Pv21 , R22 and R23 are identical or different and independently selected from the group consisting of H and Ci_s alkyl.
  • CatORG n+ is selected from the group consisting of
  • CatORG is selected from the group consisting of
  • R20, R22 is Ci_ 2 o alkyl or C 3 _io cycloalkyl
  • R21 is H and Ci_ 2 o alkyl
  • R20, R22 is C 1-14 alkyl or C 5 _s cycloalkyl
  • R21 is H and C i_i 4 alkyl
  • R20, R22 is Ci_s alkyl or C5-7 cycloalkyl
  • R21 is H and Ci_8 alkyl; even more preferably,
  • R20 and R22 are independently from each other methyl, ethyl, butyl or cyclohexyl, and
  • R21 is H, methyl or ethyl.
  • Cat is a cation (Cat-Part 1); cation (Cat-Parti) is CatINORG n+ or CatORG n+ ,
  • I 2 2 2 2 2 with CatlNORG selected from the group consisting of Li , Na , K , Mg , Ca , Zn , Cu , Ag + , H 3 0 + and H 5 0 2 + , preferably of Li + , K + , Ag + , H 3 0 + and H 5 0 2 + ; and
  • R20 is methyl, ethyl, propyl, butyl or cyclohexyl
  • R21 is H, methyl or ethyl
  • R22 is H or methyl; more in particular, Cat is a cation (Cat-Part2); cation (Cat-Part2) is CatINORG n+ or CatORG n+ , with CatlNORG selected from the group consisting of Li , Na , K , Mg , Ca , Zn , Cu , Ag + , H 3 0 + and H 5 0 2 + , preferably of Li + , K + , Ag + , H 3 0 + and H 5 0 2 + ; and with CatORG n+ selected from the group consisting of
  • Cat is a cation (Cat-Part3); cation (Cat-Part3) is CatINORG n+ or CatORG n+ ,
  • I 2 2 2 with CatlNORG selected from the group consisting of Li , Na , K , Mg , Ca , Zn , Cu ,
  • CatORG selected from the roup consisting of
  • Cat is a cation (Cat-Part4); cation (Cat-Part4) is CatINORG n+ or CatORG n+ , with CatlNORG selected from the group consisting of Li , Na , K , Mg , Ca , Zn , Cu Ag + , H 3 0 + and H 5 0 2 + , preferably of Li + , K + , Ag + , H 3 0 + and H 5 0 2 + ; and
  • CatORG n+ selected from the group consisting of , [NH(C 2 H 5 ) 3 f and [N(n-Bu) 4 ] and optionally [P(n-Bu) 4 ] very, very more in particular, Cat is a cation (Cat-Part5);
  • Cat-Part5 is CatINORG n+ or CatORG n+ ,
  • CatlNORG selected from the group consisting of Li , Na , K , Mg , Ca , Zn , Cu
  • CatORG selected from the roup consisting of .
  • Cat-Part6 Another particular preferred embodiment of Cat is a cation (Cat-Part6)
  • Cat-Part6 is selected from the group consisting of Li , Na , K , Mg , Ca , Zn ,
  • Cat-Part7 Another particular preferred embodiment of Cat is a cation (Cat-Part7)
  • cation (Cat-Part7) is selected from the group consisting of Li , Na , K , Mg , Ca , Zn , Cu 2+ , Ag + , H 3 0 + , H 5 0 2 + , [N(n-Bu) 4 ] + , [P(n-Bu) 4 ] + , [N(n-Octyl) 4 ] + , [P(n-Octyl) 4 ] + ,
  • Cat-Part8 Another particular preferred embodiment of Cat is a cation (Cat-Part8)
  • Cat-Part8 is selected from the group consisting of Li + , K + , Mg 2+ , Ca 2+ , [N(n-Bu) 4 ]
  • Cat-Part9 Another particular preferred embodiment of Cat is a cation (Cat-Part9)
  • I cation is selected from the group consisting of Na , Mg , Ca , Zn , Cu , [N(n-
  • Cat-PartlO a cation (Cat-PartlO), catio -PartlO) is selected from the group consisting of Li , K ,
  • compound of formula (I) is a compound (COMP-Neg-I), with compound (COMP-Neg-I) having the definition of compound of formula (I) as defined above, also with all the embodiments of compound of formula (I), and with the proviso, that compound (COMP-Neg-I) is none of the compounds selected from the group consisting of [Et 4 N + ] [trans-PF 2 (CN) 4 ] and [Ag + ] [trans-PF 2 (CN) 4 ] and optionally compound of formula (NIPP);
  • compound of formula (NIPP) is selected from the group consisting of
  • compound of formula (I) is a compound (COMP-Neg-II), with compound (COMP-Neg-II) having the definition of compound (COMP-Neg-I) as defined above, and
  • compound (COMP-Neg-II) is none of the compounds selected from the group consisting of [Et N + ] [PF 2 (CN) 4 ] and [Ag + ] [PF 2 (CN) 4 ] and optionally compound of formula (NIPP).
  • compound of formula (I) is a compound (COMP-
  • compound of formula (I) is a compound (COMP- Neg-IV), with compound (COMP-Neg-IV) having the definition of compound (COMP- Neg-I) or of compound (COMP-Neg-II) or of compound (COMP-Neg-III) as defined above, and
  • optionally compound of formula (I) is also not compound of formula (NIPP).
  • compound of formula (I) is compound (COMP-Pos-I),
  • compound (COMP-Pos-I) is selected from the group consisting of compound of formula (la), compound of formula (lb), compound of formula (Ic), compound of formula (Id), compound of formula (Ie), compound of formula (If) and compound of formula (Ig);
  • compound (COMP-Pos-I) is selected from the group consisting of compound of formula (la) and compound of formula (lb); in another preferred embodiment, compound (COMP-Pos-I) is selected from the group
  • compound (COMP-Pos-I) is compound of formula (la);
  • Cat and n are as defined above, also with all their embodiments,
  • Cat-Parti preferably Cat is cation (Cat-Parti);
  • Cat-Part2 More preferably Cat is cation (Cat-Part2);
  • Cat-Part3 is cation (Cat-Part3);
  • Cat-Part4 especially Cat is cation (Cat-Part4)
  • Cat is cation (Cat-Part5).
  • compound of formula (I) is compound (COMP-Pos-I), also with all the
  • compound (COMP-Pos-I) and with one or more of the provisos defined with respect of compound (COMP-Neg-I), compound (COMP-Neg-II), compound (COMP-Neg-III) and compound (COMP-Neg-IV).
  • compound of formula (I) is compound (COMP-Pos-II),
  • compound (COMP-Pos-II) is compound of formula (la), wherein
  • Cat is selected from the group consisting of cation cation (Cat-Part6), cation (Cat-Part7), cation (Cat-Part8), cation (Cat-Part9) and cation (Cat-PartlO),
  • compound of formula (I) is compound (COMP-Pos-III)
  • compound (COMP-Pos-III) is compound of formula (lb), wherein
  • Cat is selected from the group consisting of cation (Cat-Part6), cation (Cat-Part7), cation (Cat-Part8), cation (Cat-Part9) and cation (Cat-Parti 0),
  • (GPvOUP-II) is selected from the group consisting of Li [(cis-PF 2 (CN) 4 ) ], Mg [(cis-PF 2 (CN) 4 ) " ] 2 , Zn 2+ [(cis-PF 2 (CN) 4 ) " ] 2 , Ca 2+ [(cis-PF 2 (CN) 4 ) " ] 2 , [H 3 0][cis- PF 2 (CN) 4 ], [H 5 0 2 ][cis-PF 2 (CN) 4 ], [N(n-Bu) 4 ] + [(cis-PF 2 (CN) 4 ) " ], [P(n-Bu) 4 ] + [(cis-
  • compound of formula (I) is compound (GROUP), compound (GROUP), compound (GROUP), compound (GROUP), compound (GROUP), compound (GROUP), compound (GROUP), compound (GROUP), compound (GROUP), compound (GROUP), compound (GROUP), compound (GROUP), compound (GROUP), compound (GROUP), compound (GROUP), compound (
  • (GROUP) is selected from the group consisting of compound of formula (1), compound of formula (la), compound of formula (lb), compound of formula (2), compound of formula (3), compound of formula (4), compound of formula (5), compound of formula (6), compound of formula (7), compound of formula (8), compound of formula (9), compound of formula (10), compound of formula (11), compound of formula (12), compound of formula (13), compound of formula (14), compound of formula (14a), compound of formula (14b), compound of formula (15), compound of formula (15a), compound of formula (15b), compound of formula (17), compound of formula (18), compound of formula (18a), compound of formula (18b), compound of formula (19), compound of formula (20), compound of formula (21), compound of formula (22), compound of formula (23), compound of formula (24), compound of formula (25), and mixtures thereof.
  • compound of formula (I) is any of the above defined compounds or groups of compounds, preferably selected from the group consisting of compound (COMP-Pos-I), compound (COMP-Pos-II), compound (COMP-Pos-III), compound (Group-II), compound (Group-Ill) and compound
  • compound (COMP-Pos-I), compound (COMP-Pos-II), compound (COMP-Pos- III), compound (Group-II), compound (Group-Ill) and compound (GROUP) have been prepared according to the method as defined above, also with all the embodiments of the method.
  • reaction (Real) from 1 to 20 mol equivalents, more preferably 4 to 20 mol equivalents, even more preferably from 6 to 15 mol equivalents, of trimethylsilylcyanide are used in reaction (Real), the mol equivalents being based on the molar amount of compound of formula (Al).
  • reaction temperatures of reaction (Real) is preferably from 80 to 250°C, more preferably from 150 to 250°C, more preferably from 175 to 225°C, even more preferably 180 to 210°C.
  • Reaction (Real) can be done in a closed system and at the pressure caused by the chosen temperature.
  • reaction time of reaction (Real) is preferably from 30 min to 96 h, more preferably from 1 h to 72 h, even more preferably from 2 h to 48 h.
  • reaction (Real) is done under inert atmosphere.
  • the inert atmosphere is achieved by the use if an inert gas preferably selected from the group consisting of argon, another noble gas, lower boiling alkane, nitrogen and mixtures thereof.
  • the lower boiling alkane is preferably a Ci_ 3 alkane, i.e. methane, ethane or propane.
  • compound of formula (I) can be isolated by standard methods such as evaporation of volatile components, extraction, washing, drying, concentration,
  • the reaction product is treated with hydrogen peroxide, preferably with aqueous hydrogen peroxide. More preferably for isolation, the reaction product is mixed with aqueous hydrogen peroxide to provide a mixture (M).
  • the concentration of the aqueous hydrogen peroxide is from 10 to 40 wt% hydrogen peroxide, the wt% based on the total weight of the aqueous hydrogen peroxide.
  • the concentration of the aqueous hydrogen peroxide is from 10 to 40 wt% hydrogen peroxide, the wt% based on the total weight of the aqueous hydrogen peroxide.
  • from 1 to 30 mol equivalents, more preferably from 1 to 20 mol equivalents, of hydrogen peroxide are used, the mol equivalents being based on the molar amount of compound of formula (Al).
  • mixture (M) is stirred for 5 min to 12 h, more preferably for 10 min to 6 h.
  • mixture (M) is stirred at a temperature (M), temperature (M) is preferably from ambient temperature to 100°C. After treatment with hydrogen peroxide, mixture (M) is preferably filtrated.
  • the residue of the filtration is preferably washed with a solvent (WASH), solvent (WASH) is preferably water.
  • the residue is preferably extracted with a solvent (EXTRACT); solvent (EXTRACT) is preferably acetonitrile, to provide a solution (EXTRACT).
  • Any drying of an organic phase e.g. the solution (EXTRACT) obtained after extraction with solvent (EXTRACT), is preferably done with Na 2 S0 4 , K 2 C0 3 , CaCl 2 or MgS0 4 .
  • Any isolation from a solution is preferably done by evaporation of the solvent.
  • the method for the preparation of compound of formula (I) comprises a step (St2), step (St2) is done after step (Stl) or after step (St3);
  • step (St2) comprises a reaction (Rea2), reaction (Rea2) is a metathesis reaction wherein cation n+ n+
  • Cat in compound of formula (I) is exchanged for a cation different from Cat ;
  • reaction (Rea2) provides for the preparation of a compound of formula (I-Cat-r);
  • Cat-r is selected from the group consisting of CatlNORG and CatORG and is
  • r is 1, 2, 3 or 4; j j n+ n+
  • Reaction (Rea2) is a metathesis reaction, also called a salt-exchange reaction.
  • a metathesis reaction such as reaction (Rea2) a first cation in a first salt is exchanged for a second cation, said second cation coming from a second salt.
  • AnINORG q is an anion selected from the group consisting of halide, OH “ , CN ⁇ , sulfate, hydrogensulfate, nitrate, C0 3 2" , HC0 3 “ , BF 4 " , PF 6 " , CF 3 S0 3 " , (CF 3 S0 2 ) 2 N ⁇ , (FS0 2 ) 2 N ⁇ , H 3 C-S0 3 ⁇ , H 3 C-CH 2 -S0 3 ⁇ , H 3 C-0-S0 3 ⁇ , H 3 C-CH 2 -0-S0 3 ⁇ , acetate, oleate, fumarate, maleate, oxalate, benzoate, N(CN) 2 , and mixtures thereof; more preferably, AnINORG q is an anion selected from the group consisting of Br , CI , OH " , GST, sulfate, hydrogensulfate, C0
  • AnINORG ⁇ is an anion selected from the group consisting of halide, OH “ , CN ⁇ , OCN , SCN ⁇ , N 3 ⁇ , sulfate, hydrogensulfate, nitrate, C0 3 2" , HC0 3 “ , BF 4 " , PF 6 “ , SbF 6 " , CF 3 S0 3 “ , (CF 3 S0 2 ) 2 N ⁇ , (FS0 2 ) 2 N ⁇ , Ci_ 6 alkyl-S0 3 " , Ci_ 6 alkyl-0-S0 3 " ,
  • Ci_ 2 o monocarboxylic aliphatic acids anions of Ci_ 2 o monocarboxylic aliphatic acids, anions of C 2 _ 6 dicarboxylic aliphatic acids, benzoate, phthalates, N(CN) 2 , C(CN) 3 B(CN) 4 " , P(CN) 6 “ , Sb(CN) 6 “ , and mixtures thereof.
  • r is 1 or 2.
  • reaction (Rea2) preferably a compound of formula (I-Cat-r) with Cat-r being CatORG n is prepared by exchange of a Cat n being a CatINORG n in compound of formula (I) for a CatORG n+ .
  • Said CatORG n is provided in reaction (Rea2) preferably in form of a compound of formula (I-CatORG)
  • n+ r+ Preferably, in reaction (Rea2) the cation different from Cat , that is preferably Cat-r , is n+
  • compound of formula (I) and compound of formula (I-Cat-n-r) are present in n+
  • the molar amount of compound of formula (I-Cat-n-r) is such, that
  • reaction temperatures of reaction (Rea2) is preferably from 0 to 250 °C, more preferably from 10 to 200 °C, even more preferably from 10 to 150 °C, especially from 10 to 100°C, more especially from 10 to 50°C.
  • the reaction (Rea2) is preferably carried out in a solvent (Sol2)
  • solvent (Sol2) is preferably selected from the group consisting of water, DCM, ethyl acetate, C 5 _i 0 alkane, and mixtures thereof.
  • C 5 _io alkane is preferably pentane, hexane or heptane.
  • reaction (Rea2) is done in DCM or in a biphasic solvent system of water and DCM.
  • reaction can also be carried out in the absence of a solvent or in a solvent in which the inorganic salt formed as side product is sparingly soluble or insoluble.
  • reaction it is also possible to carry out the reaction in an aqueous solution using an ion exchanger loaded with the desired cation Cat n .
  • the amount of solvent is preferably from 2 to 40 fold, more preferably from 3 to 20 fold, of the weight of compound of formula (I).
  • Reaction (Rea2) can be done in a closed system and at the pressure caused by the chosen temperature.
  • reaction time of reaction (Rea2) is preferably from 15 min to 96 h, more preferably from 15 min to 48 h, even more preferably from 15 min to 24 h.
  • reaction (Rea2) is done under inert atmosphere.
  • the inert atmosphere is achieved by the use if an inert gas preferably selected from the group consisting of argon, another noble gas, lower boiling alkane, nitrogen and mixtures thereof.
  • the lower boiling alkane is preferably a Ci_ 3 alkane, i.e. methane, ethane or propane.
  • reaction (Rea2) there can be a further metathesis reaction or further metathesis reactions.
  • reaction (Rea2) compound of formula (I) can be isolated from the reaction mixture by standard methods such as filtration, evaporation of volatile components, extraction, washing, drying, concentration, crystallization, chromatography and any combination thereof, which are known per se to the person skilled in the art.
  • reaction (Rea2) when reaction (Rea2) was done in a biphasic solvent system of water and DCM, the aqueous and organic phases are separated, the organic phase is preferably washed, preferably with water, then preferably dried, preferably with Na 2 S0 4 , K 2 C0 3 , CaCl 2 or MgS0 4 , and finally evaporated.
  • reaction (Rea2) when reaction (Rea2) was done in DCM and a suspension was formed, filtration and evaporation of the solvent will isolate the product.
  • reaction (Rea3) from 1 to 20 mol equivalents, more preferably from 4 to 20 mol equivalents, even more preferably from 6 to 15 mol equivalents, of trimethylsilylcyanide are used in reaction (Rea3), the mol equivalents being based on the molar amount of compound of formula (A3).
  • reaction temperatures of reaction (Rea3) is preferably from -50 to 80°C, more preferably from -40 to 60°C, more preferably from -30 to 40°C.
  • Reaction (Rea3) can be done in a closed system and at the pressure caused by the chosen temperature.
  • reaction time of reaction (Rea3) is preferably from 30 min to 96 h, more preferably from 1 h to 72 h, even more preferably from 2 h to 48 h.
  • reaction (Rea3) is done under inert atmosphere.
  • the inert atmosphere is achieved by the use if an inert gas preferably selected from the group consisting of argon, another noble gas, lower boiling alkane, nitrogen and mixtures thereof.
  • the lower boiling alkane is preferably a Ci_ 3 alkane, i.e. methane, ethane or propane.
  • compound of formula (I) can be isolated by standard methods such as evaporation of volatile components, extraction, washing, drying, concentration, crystallization, chromatography and any combination thereof, which are known per se to the person skilled in the art.
  • reaction product after the reaction with hydrogen peroxide, preferably with aqueous hydrogen peroxide.
  • the reaction product is mixed with aqueous hydrogen peroxide to provide a mixture (M3).
  • the concentration of the aqueous hydrogen peroxide is from 10 to 40 wt% hydrogen peroxide, the wt% based on the total weight of the aqueous hydrogen peroxide.
  • mol equivalents from 1 to 30 mol equivalents, more preferably from 1 to 20 mol equivalents, of hydrogen peroxide are used, the mol equivalents being based on the molar amount of compound of formula (A3).
  • mixture (M3) is stirred for 5 min to 12 h, more preferably for 10 min to 6 h.
  • mixture (M3) is stirred at a temperature (M3), temperature (M3) is preferably from ambient temperature to 100°C.
  • mixture (M3) is preferably filtrated.
  • the residue of the filtration is preferably washed with a solvent (WASH3), solvent (WASH3) is preferably water.
  • the residue is preferably extracted with a solvent (EXTRACT3); solvent (EXTRACT3) is preferably acetonitrile, to provide a solution (EXTRACT3).
  • solvent (EXTRACT3) is preferably acetonitrile, to provide a solution (EXTRACT3).
  • Any drying of an organic phase e.g. the solution (EXTRACT3) obtained after extraction with solvent (EXTRACT3), is preferably done with Na 2 S0 4 , K 2 C0 3 , CaCl 2 or MgS0 4 .
  • Any isolation from a solution e.g. from solution (EXTRACT3), is preferably done by evaporation of the solvent.
  • step (St2) is done after step (St3), and compound of formula (I-Cat-r) of step (St2) is a compound of formula (I), which has been prepared in step (St3).
  • compound of formula (I) is any of the above defined compounds or groups of compounds, preferably selected from the group consisting of compound (COMP-Pos-I), compound (COMP-Pos- II), compound (COMP-Pos-III), compound (Group-II), compound (Group-Ill) and compound (GROUP),
  • compound (COMP-Pos-I), compound (COMP-Pos-II), compound (COMP-Pos- III), compound (Group-II), compound (Group-Ill) and compound (GROUP) have been prepared according to the method as defined above, also with all the embodiments of the method; preferably the use of compound of formula (I) with Cat n being CatORG n , with CatORG n as defined above, also with all its embodiments;
  • phase-transfer catalyst as extractant, as heat-transfer medium, as surface-active substance, as plasticizer, as conductive salt, organic salt or additive in electrochemical cells, further as electrolyte; as lubricant, as hydraulic fluid or as component in electrolyte formulations;
  • electrochemical and/or optoelectronic devices especially in electrolytres or electrolyte formulations which are used in electrochemical and/or optoelectronic devices.
  • Said electrolyte formulations comprising a compound of formula (I), preferably a compound of formula (I) with Cat n being CatORG n , with CatORG n as defined above, also with all its embodiments, are preferably used in electrochemical and/or optoelectronic devices; wherein the electrochemical and/or optoelectronic devices are preferably selected from the group consisting of batteries, capacitors, supercapacitors, electrochemical cells, photovoltaic cell, light emitting device, electrochromic or photo-electrochromic device, electrochemical sensor and/or biosensor, and dye sensitized solar cell, particularly preferred compound of formula (I) is used in battareies and in dye sensitized solar cells; preferably any of these compounds of formula (I) have been prepared according to the method as defined above, also with all the embodiments of the method.
  • compound of formula (I) When used as extractant, compound of formula (I) can be employed to separate off reaction products, but also to separate off impurities, depending on the solubility of the respective component in the ionic liquid.
  • the ionic liquids may also serve as separation media in the separation of a plurality of components, for example in the distillative separation of a plurality of components of a mixture.
  • Further possible applications for compounds of formula (I) are the use as plasticizer in polymer materials and as conductive salt or additive in various electrochemical cells and applications, for example in galvanic cells, in capacitors or in fuel cells.
  • Further fields of applications of compounds of formula (I), according to this invention are their use as solvents for carbohydrate containing solids, in particular biopolymers and derivatives or degradation products thereof.
  • compound of formula (I) can be used as lubricants or hydraulic fluids, preferably in machines such as compressors, pumps or hydraulic devices.
  • Electrolyte formulations comprising a compound of formula (I), preferably a compound of formula (I) with Cat n being CatORG n , can be preferably used in electrochemical and/or optoelectronic devices such as batteries, preferably primary batteries and secondary batteries, further capacitors, supercapacitors or electrochemical cells, optionally also in combination with further conductive salts, additives and/or solvents.
  • Preferred batteries are lithium batteries or lithium-ion batteries.
  • a preferred capacitor is a lithium-ion capacitor.
  • Electrolyte formulations comprising a compound of formula (I), preferably a compound of formula (I) with Cat n being CatORG n , can be preferably used in electrochemical and/or optoelectronic devices such as a photovoltaic cell, a light emitting device, an electrochromic or photo-electrochromic device, an electrochemical sensor and/or biosensor, and a dye sensitized solar cell, particularly preferred in a dye sensitized solar cell.
  • electrochemical and/or optoelectronic devices such as a photovoltaic cell, a light emitting device, an electrochromic or photo-electrochromic device, an electrochemical sensor and/or biosensor, and a dye sensitized solar cell, particularly preferred in a dye sensitized solar cell.
  • Electrolyte formulations comprising a compound of formula (I), preferably a compound of formula (I) with Cat n being CatORG n , can used in addition or as an alternatives to already known electrolyte formulations. They show especially in the field of electrolyte formulations of dye sensitized solar cells increased power conversion efficiency particularly under low temperature.
  • the advantage of the use of compounds of formula (I) is their low viscosity, and subsequently the smaller Nernst diffusion resistance of the oxidant species, especially at lower temperature.
  • Compound of formula (I) exhibit interesting melting points, thermal and electrochemical stability, viscosity, polarity and solubility in water or in organic solvents.
  • compound of formula (I) is any of the above defined compounds or groups of
  • compounds preferably selected from the group consisting of compound (COMP-Pos-I), compound (COMP-Pos-II), compound (COMP-Pos-III), compound (Group-II), compound (Group-Ill) and compound (GROUP),
  • compound (COMP-Pos-I), compound (COMP-Pos-II), compound (COMP-Pos- III), compound (Group-II), compound (Group-Ill) and compound (GROUP) have been prepared according to the method as defined above, also with all the embodiments of the method.
  • An electrolyte formulation (ElFormul) can comprise in addition to compound of formula (I) a solvent (ElSolv).
  • Solvent is preferably an organic solvent, which can reduce the viscosity, can increase the ionic conductivity and the electric pemittivity.
  • Solvent (ElSolv) is, for example, selected from the group consisting of
  • ester carbonates preferably ethylene carbonate and propylene carbonate
  • lactones preferably gamma-butyrolactone, gamma-valerolactone and delta-valerolactone, ethers, preferably 1 ,2-dimethoxyethane, diethoxyethane, ethylene glycol dimethyl ether, polyethylene glycol dimethyl ether and 1,4-dioxane,
  • alcohols preferably ethanol, ethylene glycol monomethyl ether and polyethylene glycol monoalkyl ether,
  • glycols preferably ethylene glycol, propylene glycol and polyethylene glycol
  • tetrahydrofurans preferably tetrahydrofuran and 2-methyltetrahydrofuran
  • nitriles preferably acetonitrile, glutarodinitrile, propionitrile, valeronitrile,
  • carboxylic esters preferably methyl acetate, ethyl acetate and ethyl propionate
  • phosphate triesters preferably trimethyl phosphate and triethyl phosphate
  • heterocyclic compounds preferably N-methylpyrrolidone, 2-methyl-l,3-dioxolane, N- butylbenzimidazole and sulfolane,
  • nonprotonic organic solvents preferably dimethyl sulfoxide, formamide, N,N- dimethylformamide and nitromethane,
  • solvent is selected from the group consisting of ethylene carbonate, propylene carbonate, tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile,
  • solvent is selected from the group consisting of propylene carbonate, acetonitrile, propionitrile, N-methylpyrrolidone, 2-methyl-l,3-dioxolane, N- butylbenzimidazole, sulfolane, dimethyl sulfoxide, ⁇ , ⁇ -dimethylformamide, and mixtures thereof;
  • solvent is selected from group consisting of sulfolane,
  • An electrolyte formulation (ElFormul) can also comprise water.
  • An electrolyte formulation (ElFormul) containing water can further enhance the energy conversion efficiency of a photosensitized solar cell.
  • An electrolyte formulation can also comprise electrically insulating particles, semiconductor particles, and electroconductive particles.
  • An electrolyte formulation (ElFormul) can also comprise a salt (ElSalt), salt (ElSalt) is preferably not an ionic liquid.
  • Salt (ElSalt) is more preferably an inorganic iodide, even more preferably an iodide of a metal ion of the first main group of the periodic table, especially salt (ElSalt) is selected from the group consisting of Lil, Nal and KI.
  • electrolyte formulation (ElFormulMix-la) comprising the electrolyte formulation (ElFormul) and a compound (IonLiqu),
  • compound (IonLiqu) is a salt or an ionic liquid which is not a compound of formula (I);
  • electrolyte formulation (ElFormul) as defined above, also with all its embodiments; preferably electrolyte formulation (ElFormulMix-la) comprises also a salt (ElSalt), with salt (ElSalt) as defined above, also with its embodiments.
  • compound (IonLiqu) in the electrolyte formulation in one more preferable embodiment, compound (IonLiqu) in the electrolyte formulation
  • CatORG , AnINORG, n, q, tl and t2 are as defined above, also with all their embodiments; even more preferably, compound (IonLiqu) is a compound of formula (I-IonLiqu), wherein AnINORG q is an anion selected from the group consisting of halide, GST, OCN , SCN ⁇ ,
  • compound (IonLiqu) is a compound of formula (I-IonLiqu), wherein AnINORG q is an anion selected from the group consisting of Br , I , SCN ⁇ , BF 4 , PF 6 , CF 3 SO 3 , (CF 3 S0 2 ) 2 N , (FS0 2 ) 2 N , anions of Ci_ 2 o monocarboxylic aliphatic acids, N(CN) 2 " , C(CN) 3 " , B(CN) 4 " , and mixtures thereof and
  • CatORG is selected from the group consisting of s l ? 3- dimethylimidazolium, 1 -ethyl-3-methylimidazolium, 1 -propyl-3-methylimidazolium, 1 -allyl-3 -methylimidazolium, 1 -methyl-3 -hexylimidazolium, 1 -ethylimidazolium, l-butyl-2,3-dimethylimidazolium and mixture thereof;
  • compound (IonLiqu) is a compound of formula (I-IonLiqu), wherein
  • AnINORG q is an anion selected from the group consisting of I , SCN ⁇ , (CF 3 S0 2 ) 2 N , (FS0 2 ) 2 N ⁇ , N(CN) 2 " , C(CN) 3 " , B(CN) 4 " , and mixtures thereof; and
  • CatORG " is selected from the group consisting of ⁇ 13 n- ⁇ tig ⁇
  • compound (IonLiqu) is a compound of formula (I-IonLiqu), wherein
  • AnINORG q is an anion selected from the group consisting of I , SCN ⁇ , (CF 3 S0 2 ) 2 N , (FS0 2 ) 2 N ⁇ , N(CN) 2 " , C(CN) 3 " , B(CN) 4 " , and mixtures thereof; and
  • CatORG is selected from the group consisting of 3 4 9 , ⁇ ,3- dimethylimidazolium, 1 -ethyl-3 -methylimidazolium, 1 -propyl-3 -methylimidazolium, 1 -allyl-3 -methylimidazolium, 1 -methyl-3 -hexyl imidazolium and mixture thereof; in one particular embodiment, compound (IonLiqu) is a compound of formula (I-IonLiqu), wherein AnINORG q is an anion selected from the group consisting of I , SCN ⁇ , (CF 3 S0 2 ) 2 N , (FS0 2 ) 2 N ⁇ , N(CN) 2 " , C(CN) 3 " , B(CN) 4 " , and mixtures thereof; and
  • CatORG is 3 11 4 H 9 ? l-ethyl-3-methylimidazolium or l-propyl-3- methylimidazolium;
  • compound (IonLiqu) is selected from the group consisting of
  • compound (IonLiqu) in the electrolyte formulation (ElFormulMix-la) is compound of formula (II-IonLiqu);
  • CatlNORG , AnINORG, q, tl and t2 are as defined above, also with all their
  • compound (IonLiqu) is a compound of formula (I-IonLiqu), wherein AnINORG q is an anion selected from the group consisting of halide, GST, OCN , N 3 ⁇ , sulfate, hydrogensulfate, BF 4 " , PF 6 " , SbF 6 " , CF 3 S0 3 ⁇ , (CF 3 S0 2 ) 2 N ⁇ , (FS0 2 ) 2 N ⁇ , anions of Ci_ 20 monocarboxylic aliphatic acids, N(CN) 2 , C(CN) 3 , B(CN) 4 , P(CN) 6
  • compound (IonLiqu) is a compound of formula (I-IonLiqu), wherein AnINORG q is an anion selected from the group consisting of BF 4 , PF 6 , CF 3 SO 3 , (CF 3 S02)2N , (FSC ⁇ N , anions of Ci_2o monocarboxylic aliphatic acids, N(CN)2 , C(CN)3 , B(CN) 4 , and mixtures thereof; and
  • CatINORG n+ is selected from the group consisting of Li + , Na + , K + , Ag + , Mg 2+ , Zn 2+ , Ca 2+ , Ba 2+ , H 3 0 + and H 5 0 2 + ;
  • compound (IonLiqu) is a compound of formula (I-IonLiqu), wherein
  • AnINORG q is an anion selected from the group consisting of BF 4 , PF 6 , (CF 3 S0 2 ) 2 N , (FS0 2 ) 2 N “ , N(CN) 2 “ , C(CN) 3 " , B(CN) 4 " , and mixtures thereof; and
  • CatlNORG is selected from the group consisting of Li , Na , K , Mg , Zn , Ca , H 3 0 + and H 5 0 2 + ;
  • compound (IonLiqu) is a compound of formula (I-IonLiqu), wherein
  • AnINORG q is an anion selected from the group consisting of PF 6 , (CF 3 S0 2 ) 2 N ,
  • CatINORG n is selected from the group consisting of Li + , Na + , K + , Mg 2+ , Zn 2+ , H 3 0 + and H 5 0 2 + .
  • compound (IonLiqu) in the electrolyte in yet another more preferable embodiment, compound (IonLiqu) in the electrolyte
  • Cat is selected from the group consisting of CatORG-B + , , Li + , Na + , K + , Mg 2+ and Zn 2+ ;
  • AnINORG q is selected from the group consisting of PF 6 " , (CF 3 S0 2 ) 2 N " , (FS0 2 ) 2 N ⁇ and
  • tl 1;
  • t2 is 1 or 2;
  • CatORG-B is selected from the group consisting of 1,3-dimethylimidazolium, 1- ethy -methylimidazolium, 1 -propyl-3 -methylimidazolium, 1 -allyl-3 -methylimidazolium, l-methyl-3-hexyl imidazolium, 1-ethylimidazolium, l-butyl-2,3-dimethylimidazolium and mixture thereof;
  • CatORG-B being l-ethyl-3 -methylimidazolium or
  • electrolyte formulation (ElFormulMix-lb) comprising the electrolyte formulation (ElFormul) and a redox couple (RedOxCoup),
  • redox couple (RedOxCoup) is selected from the group consisting of Br /Br 2 , 1 /I 3 ,
  • electrolyte formulation (ElFormulMix-2) comprising the electrolyte formulation (ElFormul), a compound (IonLiqu) and a redox couple
  • compound (IonLiqu) is compound of formula (I-IonLiqu);
  • electrolyte formulation comprises also salt (ElSalt);
  • electrolyte formulation comprises also solvent (ElSolv);
  • electrolyte formulation (ElFormulMix-2) comprises also salt (ElSalt) and solvent (ElSolv);
  • IR-spectra were recorded on a Nicolet 380 FT-IR spectrometer. Measurements were done at room temperature.
  • RAMAN-spectra were recorded on a LabRAM HR 800 Horiba Jobin YVON. Measurements were done at room temperature.
  • Melting points and temperature of decomposition Td ec were measured on a DSC 823e from Mettler-Toledo. The calibration was carried out with the melting points of In (156.6 ⁇ 0.3°C) and Zn (419.6 ⁇ 0.7°C) with an heating rate of 5 K per min.
  • TGA/DSC measurements were conducted on a Setaram Labsys TGA / DSC 1600. The measurements were carried out under argon atmosphare with a heating rate of 5 K per min, corrected via a blank measurement.
  • IR ATR, 32 scans, v in cm “1 ): 2966 (m), 2937 (w), 2879 (w), 1472 (m), 1404 (w), 1386 (w), 1360 (w), 1350 (w), 1319 (w), 1260 (w), 1242 (w), 1165 (w), 1109 (w), 1070 (w), 1035 (w), 931 (w), 880 (m), 829 (s), 738 (m), 555 (s)
  • the autoclave was placed inside a muffle furnace and heated to 200°C within 30 minutes. The temperature was held for 16.5 h.
  • RAMAN 100 mW, 25°C, 4 scans, cm “1 ): 2974 (w), 2942 (m), 2880 (w), 2216 (m) 2205 (vs), 2197 (m), 1483 (w), 1473 (m), 1462 (m), 1454 (s), 1326 (m), 1313 (w), 1155 (w), 1136 (m), 1112 (w), 1056 (m), 1040 (w), 1005 (w), 914 (s), 904 (w), 883 (w), 798 (w), 597 (w), 574 (vs), 545 (vw), 524 (w), 473 (m), 436 (w), 402 (w), 393 (m), 305 (vw), 255 (vs), 219 (s)
  • Compound of formula (1) was obtained from the described evaporation of the CH 3 CN on a rotary evaporator and subsequent drying in vacuum at 50°C in form of a powder.
  • a small amount of the powder was dissolved in a small amount of acetonitrile and the solvent was evaporated by letting the solution stand in an open container without lid overnight.
  • the crystals formed were suitable for x-ray crystal structure determination.
  • the x-ray crystal structure determination revealed cis-configuration of the two fluorine atoms.
  • Example 2 was repeated with the difference that [(n-Bu) 4 N][PF 6 ] (9.521 g, 24.57 mmol) and (CH 3 ) 3 SiCN (22 g, 222 mmol) were used. After extracting the product with CH 3 CN and drying the product in vacuum the light brown solid substance was recrystallized from ethanol to give a white solid. After drying in vacuum at 50°C 5.929 g (58%, 14.27 mmol) of compound of formula (1) were isolated.
  • Example 8 was repeated with the difference that compound of formula (3) (0.423 g, 2.00 mmol), prepared according to example 5, and Et 3 HNCl (0.275 g, 2.00 mmol) were used.
  • Compound of formula (6) was obtained as a white solid (0.355 g, 65 %, 1.29 mmol).
  • Example 8 was repeated with the difference that compound of formula (3) (0.208 g, 0.98 mmol), prepared according to example 5, and l-butyl-3-methylpyridinium bromide (0.226 g, 0.98 mmol) were used.
  • Compound of formula (7) was obtained as a light yellow liquid (0.311 g, 98 %, 0.96 mmol). The liquid showed low viscosity.
  • Example 11 Synthesis of compound of formula (8)
  • Example 8 was repeated with the difference that compound of formula (3) (0.203 g, 0.96 mmol), prepared according to example 5, and 1 -butyl- 1-methylpyrrolidinium bromide (0.216 g, 0.97 mmol) were used.
  • a colourless liquid of compound of formula (8) was obtained (0.296 g, 98 %, 0.94 mmol). The liquid showed low viscosity.
  • Example 8 was repeated with the difference that compound of formula (3) (0.218 g, 1.03 mmol), prepared according to example 5, and 1 -butyl- 1-methylpiperidinium bromide (0.243 g, 1.03 mmol) were used.
  • Compound of formula (9) was obtained as a colourless liquid (0.297 g, 87 %, 0.90 mmol). The liquid showed low viscosity.
  • Example 8 was repeated with the difference that compound of formula (3) (0.316 g, 1.49 mmol), prepared according to example 5, and 1-ethylimidazolium bromide (0.264 g, 1.49 mmol) were used.
  • Compound of formula (10) was obtained as a white solid (0.201 g, 50 %, 0.74 mmol).
  • Example 8 was repeated with the difference that compound of formula (3) (0.216 g, 1.02 mmol), prepared according to example 5, and l-butyl-2,3-dimethylimidazolium bromide (0.238 g, 1.02 mmol) were used.
  • Compound of formula (11) was obtained as a light yellow liquid (0.316 g, 95 %, 0.97 mmol). The liquid showed low viscosity.
  • reaction mixture prepared according to example 15a was refluxed for eight hours. After cooling to ambient temperatures a sample of the resulting reaction was analyzed by 19 F NMR: the reaction mixture contained a mixture of about less than 1 % of compound of formula (13), 95 % of compound of formula (14a) and 4 % of compound of formula (15).
  • Compound of formula (14a) is a mixture of 52 % (14b) and 48 % (14).
  • reaction mixture contained a mixture of about less than 1 % of compound of formula (14b), 93 % of compound of formula (15a) and 6 % of compound of formula (la).
  • Compound of formula 15a is a mixture of 60 % (15) and 40 % (15b).
  • Compound of formula (la) is a mixture of 91 % (1) and 9 % (lb).
  • Example 16 was repeated with the differences:
  • reaction mixture contained a mixture of about 90 % of compound of formula (1) and 10 % of compound of formula (21).
  • aqueous MgCl 2 solution (1 g MgCl 2 in 10 ml H 2 0) aqueous NH 3 solution (0.5 ml, 25 wt%) was added.
  • the resulting suspension of Mg(OH) 2 was filtered and washed 3 times with water.
  • prepared Mg(OH) 2 was added to 10 ml of an aqueous solution of
  • Example 21 was repeated with the difference that [H 3 0][PF 2 (CN)4] (0.17 g, 0.89 mmol), prepared according to example 20, were used, and ZnO (0.16 g, 2 mmol) instead of Mg(OH) 2 were used.
  • Compound of formula (24) was obtained as a white solid (0.19 g, 95 %, 0.42 mmol).
  • Comparative Compound EMIm[PF3(CN)3] , which is available according to example 4 of EP 2 410 601 Al .
  • Photo anodes used to make the devices consisted of a screen-printed nanoparticulate mesoporous Ti0 2 layers.
  • a 8 ⁇ thick transparent layer of 20 nm sized Ti0 2 particles was first printed on the fluorine doped Sn0 2 (FTO) conducting glass (purchased from NSG with 10 ⁇ /cm 2 , 4 mm thick) and subsequently coated with a 5 ⁇ thick second layer of 400 nm light-scattering anatase particles (CCIC, Japan).
  • FTO fluorine doped Sn0 2
  • CCIC light-scattering anatase particles
  • composition of the electrolyte B, which was used, is:
  • electrolyte A DMII/EMII/compound TEST /I 2 /NBB/GITC (12/12/16/1.67/3.33/0.67)
  • electrolyte B electrolyte A + sulfolane (50:50 v/v).
  • Electrodes were completed by filling the space between the electrodes with electrolyte through pre-drilled holes in the counter electrodes and the holes were sealed with a Surlyn sheet and a thin glass cover by heating. Finally, metal contacts were placed on both electrodes.
  • Photovoltaic measurements were performed under simulated sun irradiance (100 mW cm “2 , equivalent of 1 sun at air mass global, AM 1.5 G, at the surface of the device) provided by a 450 W Xenon light source (Oriel, USA).
  • a Schott Kl 13 Tempax sunlight filter (Prazisions Glas & Optik GmbH, Germany) was used to correct the spectral output of the lamp in the region 350 to 750 nm.
  • Current to voltage characteristics were obtained by applying a forward potential bias and measuring resulting current with a Keithley 2400 digital sourcemeter (Keithley, USA).
  • a metal mask was used to precisely define the irradiated surface area (0.159 cm 2 ).
  • Quantum efficiencies of the cells were measured by using a SR830 lock in amplifier, however the incident light (300 W xenon lamp, ILC Technology) was focused through a Gemini- 180 double monochromator (Jobin-Yvon Ltd.). The cells were measured with an external light bias (100% Sun) provided by LED array. A black metal mask defined the cell active area to be 0.159 cm 2 .
  • the tables show the photovoltaic parameters of CI 06 dye based devices measured under irradiation of 100 mW cm "2 AM 1.5 G Sunlight.
  • the melting points were determined with the aid of DSC measurements with a heating rate of 10 K per min.
  • the melting point of compound of formula (5), prepared according to example 7, is -32 °C, that is 16 °C below the melting point of EMIm[PF 3 (CN) 3 ], which is available according to example 4 of EP 2 410 601 Al, with -16 °C. This shows that compound of formula (5) has a wider range of application at low temperatures.

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Abstract

L'invention porte sur un procédé pour la préparation de composés fluoro et chloro cyano représentés par la formule (I) indiquée ci-dessous, par une réaction utilisant du cyanure de triméthylsilyle. Lesdits composés s'utilisent comme ligands ioniques dans des dispositifs électrochimiques ou opto-électroniques comme des batteries ou des cellules solaires. [Cat n+] [(Z 1(Q 1) 6-m(CN) m) -] n (I) L'invention concerne également des formulations et des composés électrolytiques du sous-groupe de formule (I), représentés par la formule (Ia) [Cat n+] [(cis-PF 2(CN) 4) ] n(la). Des exemples types de formule (Ia) sont [(n-Bu)4N] [cis-PF2(CN)4], Ag[cis-PF 2(CN) 4], K[cis-PF 2(CN) 4], Li[cis- PF 2(CN) 4], [Et 3HN][ [cis-PF 2(CN) 4], [(n-Bu) 4P][cis-PF 2(CN) 4], [H30] [cis-PF2(CN)4], Mg[cis-PF 2(CN) 4]2 *4H 20, Zn[cis-PF 2(CN) 4]2 *2H 20, [H 50 2] [Cis-PF 2(CN) 4]
PCT/EP2014/057220 2013-04-12 2014-04-10 Procédé pour la préparation de composés fluoro et chloro cyano du 15ème groupe du tableau périodique des éléments WO2014167035A1 (fr)

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US201361811363P 2013-04-12 2013-04-12
EP13163571 2013-04-12
EP13163571.6 2013-04-12
US61/811,363 2013-04-12
EP13177694 2013-07-23
EP13177694.0 2013-07-23
EP13179302 2013-08-05
EP13179302.8 2013-08-05
EP13179538 2013-08-07
EP13179538.7 2013-08-07
EP13181616 2013-08-23
EP13181616.7 2013-08-23
EP13188615.2 2013-10-15
EP13188615 2013-10-15
EP13188614 2013-10-15
EP13188614.5 2013-10-15
EP13193096 2013-11-15
EP13193096.8 2013-11-15
EP14155418.8 2014-02-17
EP14155418 2014-02-17
EP14156459 2014-02-25
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EP3078668A1 (fr) * 2015-04-09 2016-10-12 Lonza Ltd Procédé de préparation de composés de cyano fluoro du groupe 15 avec un acide de brönstedt
CN106848400A (zh) * 2017-01-11 2017-06-13 长兴天晟能源科技有限公司 一种高安全锂离子电池用电解液及锂离子电池
CN106848401A (zh) * 2017-01-11 2017-06-13 长兴天晟能源科技有限公司 一种锂离子电池用高温自阻断电解液的制备方法
CN113937391A (zh) * 2021-10-15 2022-01-14 中国科学院长春应用化学研究所 一种用于锂氧气电池的金属有机配合物、锂氧气电池及抑制锂氧气电池氧化还原穿梭的方法
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EP4321505A1 (fr) * 2022-06-17 2024-02-14 Contemporary Amperex Technology Co., Ltd. Composé ionique et son utilisation, solution de précurseur de pérovskite, matériau de pérovskite, cellule solaire et dispositif électrique

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EP3078668A1 (fr) * 2015-04-09 2016-10-12 Lonza Ltd Procédé de préparation de composés de cyano fluoro du groupe 15 avec un acide de brönstedt
CN106848400A (zh) * 2017-01-11 2017-06-13 长兴天晟能源科技有限公司 一种高安全锂离子电池用电解液及锂离子电池
CN106848401A (zh) * 2017-01-11 2017-06-13 长兴天晟能源科技有限公司 一种锂离子电池用高温自阻断电解液的制备方法
CN113937391A (zh) * 2021-10-15 2022-01-14 中国科学院长春应用化学研究所 一种用于锂氧气电池的金属有机配合物、锂氧气电池及抑制锂氧气电池氧化还原穿梭的方法
CN113937391B (zh) * 2021-10-15 2024-02-13 中国科学院长春应用化学研究所 一种用于锂氧气电池的金属有机配合物、锂氧气电池及抑制锂氧气电池氧化还原穿梭的方法
EP4321505A1 (fr) * 2022-06-17 2024-02-14 Contemporary Amperex Technology Co., Ltd. Composé ionique et son utilisation, solution de précurseur de pérovskite, matériau de pérovskite, cellule solaire et dispositif électrique
CN116960466A (zh) * 2023-09-15 2023-10-27 宁德时代新能源科技股份有限公司 电解液、二次电池及用电装置
CN116960466B (zh) * 2023-09-15 2024-04-02 宁德时代新能源科技股份有限公司 电解液、二次电池及用电装置

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