Compounds containing alkyl-cyano-borate or alkyl-cyano-fluoroborate anions

Patent metadata

Field	Value
Publication number	US-9058935-B2
Application number	US-201214131990-A
Country	US
Kind code	B2
Filing date	Jul 6, 2012
Priority date	Jul 15, 2011
Publication date	Jun 16, 2015
Grant date	Jun 16, 2015

Abstract

The invention relates to new compounds containing alkyl/alkenyl-cyano-borate or alkyl/alkenyl-cyano-fluoroborate anions, their preparation and their use, in particular as part of electrolyte formulations for electrochemical or optoelectronic devices.

First claim

The invention claimed is:

1. A compound of formula I
[Kt] z+ z[(R 1 ) 4-x-y-v B(CN) x (NC) y F v ] −   I

in which
R 1 in each case independently denotes a straight-chain or branched alkyl group having 1 to 20 C atoms, which optionally contains at least one Cl, Br or I atom, at least one CN group and/or one or more oxygen or sulphur atoms, a straight-chain or branched alkenyl group having 2 to 20 C atoms having one or more double bonds, which optionally contains at least one Cl, Br or I atom and/or one or more oxygen or sulphur atoms, a straight-chain or branched alkinyl group having 1 to 20 C atoms having one or more triple bonds, which optionally contains at least one Cl, Br or I atom and/or one or more oxygen or sulphur atoms and optionally may have a double bond, or unsubstituted phenyl,
z is 1, 2, 3 or 4,
x is 1, 2 or 3,
y is 0, 1 or 2,
v is 0, 1 or 2,
the sum of x+y+v is 2 or 3,
Kt z+ denotes an inorganic cation selected from NO + , H + , Li + , Na + , K + , Rb + , Cs + , Mg 2+ , Cu + , Cu 2+ , Zn 2+ , Ag + , Ca 2+ , Y +3 , Yb +3 , La +3 , Sc +3 , Ce +3 , Nd +3 , Tb +3 , Sm +3 or complex (ligands containing) metal cations which include rare-earths, transitions or noble metals
or an organic cation selected from
(a) a tritylium cation, in which the phenyl groups may be substituted by straight-chain or branched alkyl groups having 1 to 20 C atoms, straight-chain or branched alkenyl having 2 to 20 C atoms and one or more double bonds or straight-chain or branched alkynyl having 2 to 20 C atoms and one or more triple bonds,
(b) an oxonium cation of formula (1) or a sulfonium cation of formula (2))
[(R o ) 3 O] +   (1)

[(R o ) 3 S] +   (2),

where R o each, independently of one another, denotes a straight-chain or branched alkyl group having 1-8 C atoms, non-substituted phenyl or phenyl which is substituted by R 1 *, OR′, N(R′) 2 , CN or halogen and in case of sulfonium cations of formula (2) additionally denotes each independently (R′″) 2 N,
 R′ is independently of each other H, non-fluorinated, partially fluorinated or perfluorinated straight-chain or branched C 1 - to C 18 -alkyl, saturated C 3 - to C 7 -cycloalkyl, non-substituted or substituted phenyl,
 R 1 * is independently of each other non-fluorinated, partially fluorinated or perfluorinated straight-chain or branched C 1 - to C 18 -alkyl, saturated C 3 - to C 7 -cycloalkyl, non-substituted or substituted phenyl, and
 R′″ is independently of each other straight-chain or branched C 1 to C 6 alkyl,

(c) an ammonium cation, which conforms to the formula (3)
[NR 4 ] +   (3),

where R in each case, independently of one another, denotes H, OR′, N(R′) 2 , with the proviso that a maximum of one R in formula (3) is OR′ or N(R′) 2 ,
 straight-chain or branched alkyl having 1-20 C atoms,
 straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
 straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds, saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be
 substituted by straight-chain or branched alkyl groups having 1-6 C atoms,
where one or two R may be fully substituted by halogens, and one or more of the substituents R may be partially substituted by halogens, and/or by —OH, —OR′, —CN, —N(R′) 2 , —C(O)OH, —C(O)OR′, —C(O)R′, —C(O)N(R′) 2 , —SO 2 N(R′) 2 , —C(O)X, —SO 2 OH, —SO 2 X, —NO 2 , —SR′, —S(O)R′, or —SO 2 R′ and where one or two non-adjacent carbon atoms in R which are not in the α-position may each be replaced by —O—, —S—, —S(O)—, —SO 2 —, —SO 2 O—, —C(O)—, —C(O)O—, —N + (R′) 2 —, —P(O)R′O—, —C(O)NR′—, —SO 2 NR′—, —OP(O)R′O—, —P(O)(N(R′) 2 )NR′—, —P(R′) 2 ═N— or —P(O)R′—,
R′ in each case independently is H, non-fluorinated, partially fluorinated or perfluorinated straight-chain or branched C 1 - to C 18 -alkyl, saturated C 3 - to C 7 -cycloalkyl, non-substituted or substituted phenyl, and
X in each case, independently of one another, is halogen;

(d) a phosphonium cation, which conforms to the formula (4)
[P(R 2 ) 4 ] +   (4),

where R 2 in each case, independently of one another, denotes H, OR′ or N(R′) 2 ,
 straight-chain or branched alkyl having 1-20 C atoms,
 straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
 straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
 saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms,
where one or two R 2 may be fully substituted by halogens, and one or more of the substituents R 2 may be partially substituted by halogens, and/or by —OH, —OR′, —CN, —N(R′) 2 , —C(O)OH, —C(O)OR′, —C(O)R′, —C(O)N(R′) 2 , —SO 2 N(R′) 2 , —C(O)X, —SO 2 OH, —SO 2 X, —NO 2 , —SR′, —S(O)R′, or —SO 2 R′, and where one or two non-adjacent carbon atoms in R 2 which are not in the α-position may each be replaced by —O—, —S—, —S(O)—, —SO 2 —, —SO 2 O—, —C(O)—, —C(O)O—, —N + (R′) 2 —, —P(O)R′O—, —C(O)NR′—, —SO 2 NR′—, —OP(O)R′O—, —P(O)(N(R′) 2 )NR′—, —P(R′) 2 ═N— or —P(O)R′—,
R′ in each case independently is H, non-fluorinated, partially fluorinated or perfluorinated straight-chain or branched C 1 - to C 18 -alkyl, saturated C 3 - to C 7 -cycloalkyl, non-substituted or substituted phenyl, and
X in each case independently is halogen,

(e) a uronium cation, which conforms to the formula (5)
[C(NR 3 R 4 )(OR 5 )(NR 6 R 7 )] +   (5),

where R 3 to R 7 each, independently of one another, denote H, where H is excluded for R 5 ,
 straight-chain or branched alkyl having 1 to 20 C atoms,
 straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
 straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
 saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms,
where one or two of the substituents R 3 to R 7 may be fully substituted by halogens, and one or more of the substituents R 3 to R 7 may be partially substituted by halogens, and/or by —OH, —OR′, —N(R′) 2 , —CN, —C(O)OH, —C(O)OR′, —C(O)R′, —C(O)N(R′) 2 , —SO 2 N(R′) 2 , —C(O)X, —SO 2 OH, —SO 2 X, —SR′, —S(O)R′, —SO 2 R′, or —NO 2 , and where one or two non-adjacent carbon atoms in R 3 to R 7 which are not in the α-position may each be replaced by —O—, —S—, —S(O)—, —SO 2 —, —SO 2 O—, —C(O)—, —C(O)O—, —N + (R′) 2 —, —P(O)R′O—, —C(O)NR′—, —SO 2 NR′—, —OP(O)R′O—, —P(O)(N(R′) 2 )NR′—, —P(R′) 2 ═N— or —P(O)R′—,
R′ in each case independently is H, non-fluorinated, partially fluorinated or perfluorinated straight-chain or branched C 1 - to C 18 -alkyl, saturated C 3 - to C 7 -cycloalkyl, non-substituted or substituted phenyl, and
X in each case independently is halogen,

(f) a thiouronium cation, which conforms to the formula (6)
[C(NR 3 R 4 )(SR 5 )(NR 6 R 7 )] +   (6),

where R 3 to R 7 each, independently of one another, denote H, where H is excluded for R 5 ,
 straight-chain or branched alkyl having 1 to 20 C atoms,
 straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
 straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
 saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms,
where one or two of the substituents R 3 to R 7 may be fully substituted by halogens, and one or more of the substituents R 3 to R 7 may be partially substituted by halogens, and/or by —OH, —OR′, —N(R′) 2 , —CN, —C(O)OH, —C(O)OR′, —C(O)R′, —C(O)N(R′) 2 , —SO 2 N(R′) 2 , —C(O)X, —SO 2 OH, —SO 2 X, —SR′, —S(O)R′, —SO 2 R′, or —NO 2 , and where one or two non-adjacent carbon atoms in R 3 to R 7 which are not in the α-position m

Assignees

• Ignatyev Nikolai Mykola
• Schulte Michael
• Kawata Kentaro
• Goto Tomohisa
• Sprenger Jan
• Finze Maik
• Frank Walter
• Merck Patent Gmbh

Inventors

• Ignatyev Nikolai Mykola
• Schulte Michael
• Kawata Kentaro
• Goto Tomohisa
• Sprenger Jan
• Finze Maik
• Frank Walter

Classifications

• H01M14/005

  Photoelectrochemical storage cells (light sensitive devices H01G9/20, semiconductors sensitive to light H10F) · CPC title

• C07F5/02 Primary

  Boron compounds · CPC title

• H01M10/0568

  characterised by the solutes · CPC title

• H01G9/2013 Primary

  the electrolyte comprising ionic liquids, e.g. alkyl imidazolium iodide · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title