Sulfur-containing additives for electrochemical or optoelectronic devices

Patent metadata

Field	Value
Publication number	US-9748605-B2
Application number	US-201214239908-A
Country	US
Kind code	B2
Filing date	Aug 22, 2012
Priority date	Aug 24, 2011
Publication date	Aug 29, 2017
Grant date	Aug 29, 2017

Abstract

The invention relates to sulfur-containing compounds of the formula I, to their preparation, and to their use as additives in electrochemical or electrooptical devices, more particularly in electrolytes for lithium batteries, lithium ion batteries, double layer capacitors, lithium ion capacitors, solar cells, electrochromic displays, sensors and/or biosensors.

First claim

The invention claimed is:

1. An electrolyte additive comprising a compound of formula I
[K—(CH 2 )—(CH 2 ) u —SO 3 —(CH 2 ) v —R″] + [A] −   I,

wherein
u is 0, 1, 2, 3, 4, 5, 6 or 7 and where a CH 2 group of the —(CH 2 ) u -alkylene chain may be replaced by O or may have a double bond,
v is 0, 1, 2, 3 or 4,
—SO 3 — is

R″ independently at each occurrence is a straight-chain or branched alkyl group having 1 to 20 C atoms, and may be unfluorinated, partly fluorinated or fully fluorinated, or is a straight-chain or branched alkenyl group having 2 to 20 C atoms and a double bond, a straight-chain or branched alkynyl group having 2 to 20 C atoms and a triple bond, or an aryl group having 6 to 12 C atoms, which group may be singly or multiply substituted by at least one selected from the group consisting of F, Cl, and a straight-chain or branched, partly fluorinated or fully fluorinated alkyl group having 1 to 8 C atoms,
K is a cation selected from the group consisting of
R 3 N + —*, R 3 P + —*,

wherein
R independently at each occurrence is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, wherein optionally a CH 2 group, not directly joined to N or P, in the radicals R is replaced by O,
Y is CH 2 , O, S or NR′,
R′ is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl,
A is an anion selected from the group consisting of
[F z B(C m F 2m+1 ) 4-z ] − ,
[F y P(C m F 2m+1 ) 6-y ] − ,
[(C m F 2m+1 ) 2 P(O)O] − ,
[C m F 2m+1 P(O)O 2 ] 2− ,
[O—C(O)—C m F 2m+1 ] − ,
[N(C(O)—C m F 2m+1 ) 2 ] − ,
[N(S(O) 2 —C m F 2m+1 ) 2 ] − ,
[N(C(O)—C m F 2m+1 )(S(O) 2 —C m F 2m+1 )] − ,
[N(C(O)—C m F 2m+1 )(C(O)F)] − ,
[N(S(O) 2 —C m F 2m+1 )(S(O) 2 F)] − ,
[N(S(O) 2 F) 2 ] − ,
[C(C(O)—C m F 2m+1 ) 3 ] − ,
[C(S(O) 2 —C m F 2m+1 ) 3 ] − ,
[O—S(O) 2 —C m F 2m+1 ] − ,

m is 1, 2, 3, 4, 5, 6, 7 or 8, wherein optionally CF 2 groups in the anions are replaced by O, S(O) 2 , NR or CH 2 ,
z is 1,2 or 3,
y is 1, 2, 3, 4, 5 or 6,
X is B or Al,
R 1 and R 2 are each independently of one another F, Cl, Br, I, a straight-chain or branched perfluoroalkyl group having 1 to 20 C atoms, a straight-chain or branched alkoxy group having 1 to 20 C atoms, which may be unfluorinated, partly fluorinated or fully fluorinated, or —O—C(O)— alkyl, where alkyl is a straight-chain or branched alkyl group having 1 to 20 C atoms, and may be unfluorinated, partly fluorinated or perfluorinated,
and
where

independently at each occurrence is a bidentate radical which derives from a 1,2- or 1,3-diol, from a 1,2- or 1,3-dicarboxylic acid or from a 1,2- or 1,3-hydroxycarboxylic acid, by entering of pairs of adjacent OH groups in the compound into one bond each to the central atom X, accompanied by formal elimination of two H atoms,
wherein an electroneutrality of a corresponding salt thereof is observed.

2. The electrolyte additive according to claim 1 , wherein v is 0.

3. The electrolyte additive according to claim 1 , wherein u is 1, 2 or 3.

4. The electrolyte additive according to claim 1 , wherein R″ is a straight-chain or branched alkyl group having 1 to 8 C atoms, and may be unfluorinated, partly fluorinated or fully fluorinated.

5. The electrolyte additive according to claim 1 , wherein K is cation

and where [A] − is selected from the group consisting of [O—S(O) 2 —C m F 2m+1 ] − and [F z B(C m F 2m+1 ) 4-z ], wherein z=4.

6. The electrolyte additive according to claim 1 , wherein A is an anion selected from the group consisting of
[F z B(C m F 2m+1 ) 4-z ] − ,
[F y P(C m F 2m+1 ) 6-y ] − ,
[O—C(O)—C m F 2m+1 ] − ,
[N(S(O) 2 —C m F 2m+1 ) 2 ] − ,
[N(S(O) 2 F) 2 ] − ,

wherein
m is 1, 2, 3, 4, 5, 6, 7 or 8,
z is 1, 2 or 3,
y is 3, 4, 5 or 6,
X is B,
R 1 and R 2 are each independently of one another F, a straight-chain or branched perfluoroalkyl group having 1 to 4 C atoms, a straight-chain or branched alkoxy group having 1 to 4 C atoms or —O—C(O)-alkyl, where alkyl is a straight-chain or branched alkyl group having 1 to 20 C atoms, and may be unfluorinated, partly fluorinated or perfluorinated,
and
where

independently at each occurrence is a bidentate radical which derives from a 1,2- or 1,3-diol, from a 1,2- or 1,3-dicarboxylic acid or from a 1,2- or 1,3-hydroxycarboxylic acid, by entering of pairs of adjacent OH groups in the compound into one bond each to the central atom X, accompanied by formal elimination of two H atoms.

7. A process for preparing a compound of formula I according to claim 1 , wherein SO 3 is substructure

the process comprising reacting a compound of formula (II)
K-1  (II),

wherein K-1 is selected from the group consisting of R 3 N, R 3 P,

R independently at each occurrence is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, and a CH 2 group, not joined to N or P, in the radicals R may be replaced by O,
Y is CH 2 , O, S or NR′, and
R′ is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl,

with a compound of formula (III),
Hal-(CH 2 )—(CH 2 ) u —OH  (III),

wherein u is 1, 2, 3, 4, 5, 6 or 7, and a CH 2 group, not attached to the oxygen, in the —(CH 2 ) u -alkylene chain may be replaced by O or may contain a double bond, and Hal is Cl, Br or I,
to obtain a resultant intermediate compound of the formula (IV)
[K—(CH 2 )—(CH 2 ) u —OH] + [Hal] −   (IV),

reacting the resultant intermediate compound of formula (IV) with a compound of formula (V)
R″—(CH 2 ) v —SO 2 -L  (V),

wherein L is a leaving group selected from a straight-chain or branched alkoxy group having 1 to 3 C atoms, Cl or F,

with acid catalysis in the case of the alkoxy group as leaving group, or in the presence of a base in the case of Cl or F as leaving group, to obtain a resulting compound of formula (VI)
[K—(CH 2 )—(CH 2 ) u —SO 3 —(CH 2 ) v —R″] + [Hal] −   (VI),

and then reacting the resulting compound of formula (VI) in a metathesis reaction with a compound of formula (VII),
[Kt] + [A] −   (VII),

wherein [Kt] + is an alkali metal cation or H + , and [A] − has a definition indicated in claim 1 .

8. A process for preparing a compound of formula I according to claim 1 , wherein SO 3 is substructure

and u is 2, 3, 4 or 5, the process comprising reacting a compound of formula (II)
K-1  (II),

wherein K-1 is selected from the group R 3 N, R 3 P,

R

Assignees

• Schmidt Michael
• Ignatyev Nikolai
• Semrau Guenter
• Frank Walter
• Barthen Peter
• Breitenstein Christoph
• Basf Se

Inventors

• Schmidt Michael
• Ignatyev Nikolai
• Semrau Guenter
• Frank Walter
• Barthen Peter
• Breitenstein Christoph

Classifications

• H01G11/58

  Liquid electrolytes · CPC title

• C07D295/088 Primary

  to an acyclic saturated chain · CPC title

• C07D207/04 Primary

  having no double bonds between ring members or between ring members and non-ring members · CPC title

• H01M10/0567 Primary

  characterised by the additives · CPC title

• H01G11/06

  with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC] · CPC title