# US 2014/0193707 A1 · Sulfur-containing additives for electrochemical or optoelectronic devices

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- Number: US 2014/0193707 A1
- Document ID: US20140193707A1
- Status: Published application
- Kind: A1
- Application number: 14/239,908
- Filed: 2012-08-22
- Published: 2014-07-10
- Earliest claimed: 2011-08-24
- Assignees: BASF SE
- Inventors: Michael Schmidt; Nikolai Ignatyev; Guenter Semrau; Walter Frank; Peter Barthen; Christoph Breitenstein
- Web page: https://patentgrep.com/patent/US20140193707A1

## CPC

- H01M 10/0567: characterised by the additives
- C07D 207/04: having no double bonds between ring members or between ring members and non-ring members
- C07F 5/022: {without C-boron linkages}
- H01G 11/06: with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
- H01G 11/58: Liquid electrolytes
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- Y02E 60/10: Energy storage using batteries
- Y02E 60/13: Energy storage using capacitors
- Y02P 20/582: Recycling of unreacted starting or intermediate materials
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- H01G: CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE (selection of specified materials as dielectric H01B3/00; capacitors having potential barriers H10D1/62, H10K10/10)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## 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.

## Claims

### Claim 1

A compound of formula I
[K—(CH2)—(CH2)u—SO3—(CH2)v—R″]+[A]− I,
wherein
u is 0, 1, 2, 3, 4, 5, 6 or 7 and where a CH2 group of the —(CH2)u— alkylene chain may be replaced by O or may have a double bond,
v is 0, 1, 2, 3 or 4,
—SO3— 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
R3N+—*, R3P+—*,
wherein
R independently at each occurrence is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, wherein optionally a CH2 group, not directly joined to N or P, in the radicals R is replaced by O,
Y is CH2, 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
[FzB(CmF2m+1)4-z]−,
[FyP(CmF2m+1)6-y]−,
[(CmF2m+1)2P(O)O]−,
[CmF2m+1P(O)O2]2−,
[(O—C(O)—CmF2m+1]−,
[N(C(O)—CmF2m+1)2]−,
[N(S(O)2—CmF2m+1)2]−,
[N(C(O)—CmF2m+1)(S(O)2—CmF2m+1)]−,
[N(C(O)—CmF2m+1)(C(O)F)]−,
[N(S(O)2—CmF2m+1)(S(O)2F)]−,
[N(S(O)2F)2]−,
[C(C(O)—CmF2m+1)3]−,
[C(S(O)2—CmF2m+1)3]−,
[O—S(O)2—CmF2m+1]−,
m is 1, 2, 3, 4, 5, 6, 7 or 8, wherein optionally CF2 groups in the anions are replaced by O, S(O)2, NR or CH2,
z is 1, 2 or 3,
y is 1, 2, 3, 4, 5 or 6,
X is B or Al,
R1 and R2 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.

### Claim 2 (depends on 1)

The compound according to claim 1, wherein v is 0.

### Claim 3 (depends on 1)

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

### Claim 4 (depends on 1)

The compound 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.

### Claim 5 (depends on 1)

The compound according to claim 1, wherein K is cation
and where [A]− is selected from the group consisting of [O—S(O)2—CmF2m+1]− and [FzB(CmF2m+1)4-z], wherein z=4.

### Claim 6 (depends on 1)

The compound according to claim 1, wherein A is an anion selected from the group consisting of
[FzB(CmF2m+1)4-z]−,
[FyP(CmF2m+1)6-y]−,
[O—C(O)—CmF2m+1]−,
[N(S(O)2—CmF2m+1)2]−,
[N(S(O)2F)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,
R1 and R2 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.

### Claim 7 (depends on 1)

A process for preparing a compound of formula I according to claim 1, wherein SO3 is substructure
the process comprising reacting a compound of formula (II)
K−1 (II),
wherein K−1 is selected from the group consisting of R3N, R3P,
R independently at each occurrence is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, and a CH2 group, not joined to N or P, in the radicals R may be replaced by O,
Y is CH2, 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-(CH2)—(CH2)u—OH (III),
wherein u is 1, 2, 3, 4, 5, 6 or 7, and a CH2 group, not attached to the oxygen, in the —(CH2)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—(CH2)—(CH2)u—OH]+[Hal]− (IV),
reacting the resultant intermediate compound of formula (IV) with a compound of formula (V)
R″—(CH2)v—SO2-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—(CH2)—(CH2)u—SO3—(CH2)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.

### Claim 8 (depends on 1)

A process for preparing a compound of formula I according to claim 1, wherein SO3 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 R3N, R3P,
R independently at each occurrence is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, and a CH2 group, not joined to N or P, in the radicals R may be replaced by O,
Y is CH2, O, S or NR′, and
R′ is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, with a compound of formula (VIII)
wherein w is 1, 2, 3 or 4,
to obtain an intermediate compound of formula (IX)
[K—(CH2)—(CH2)—SO3−] (IX),
subsequently reacting the intermediate compound of formula (IX) with an alkylating agent of formula (X)
L*-(CH2)v—R″ (X),
wherein L* is CF3—S(O)2O, C4F9—S(O)2O, (C2F5)2P(O)O, (C4F9)2P(O)O, (alkyl)2O+, alkyl-S(O)2O, alkyl-O—S(O)2O, I or Br, with alkyl independently at each occurrence being a straight-chain or branched alkyl group having 1 to 4 C atoms,
to obtain a resulting compound of formula (XI)
[K—(CH2)—(CH2)u—SO3—(CH2)v—R″]+[L*]− (XI),
and then optionally reacting the resulting compound of formula (XI) with a compound of formula (VII),
[Kt]+[A]− (VII),
wherein [Kt]+ is an alkali metal cation or H+, and [A]− has a definition stated in claim 1.

### Claim 9 (depends on 1)

A process for preparing a compound of formula I according to claim 1, where SO3 is substructure
the process comprising reacting a compound of formula (II)
K−1 (II),
wherein K−1 is selected from the group consisting of R3N, R3P,
R independently at each occurrence is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, and at least one CH2 group, not joined to N or P, in the radicals R may be replaced by O,
Y is CH2, O, S or NR′, and
R′ is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, with a compound of formula (XII),
Hal-(CH2)—(CH2)u-Hal (XII),
wherein u is 0, 1, 2, 3, 4, 5, 6 or 7, and a CH2 group, not attached to Hal, in the —(CH2)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 formula (XIII)
[K—(CH2)—(CH2)u-Hal]+[Hal]− (XIII),
reacting the resultant intermediate compound of formula (XIII) with an alkali metal sulfite or ammonium sulfite and subsequently with a compound of formula (X)
L*-(CH2)v—R″ (X),
wherein L* is CF3—S(O)2O, C4F9—S(O)2O, (C2F5)2P(O)O, (C4F9)2P(O)O, (alkyl)2O+, alkyl-S(O)2O, alkyl-O—S(O)2O, I or Br, with alkyl independently at each occurrence being a straight-chain or branched alkyl group having 1 to 4 C atoms,
to obtain a resulting compound of formula (XI)
[K—(CH2)—(CH2)u—SO3—(CH2)v—R″]+[L*]− (XI),
and then optionally reacting the resulting compound of formula (XI) with a compound of formula (VII),
[Kt]+[A]− (VII),
wherein [Kt]+ is an alkali metal cation or H+, and [A]− has a definition stated in claim 1.

### Claim 10 (depends on 1)

An electrolyte comprising a compound of formula I according to claim 1, wherein [A]− is selected from the group consisting of [O—S)O)2−CmF2m+1]− wherein m=1, 2, 3, 4, 5, 6, 7 or 8 and [FzB(CmF2m+1)4-z]− wherein z=4.

### Claim 11 (depends on 10)

The electrolyte according to claim 10, comprising as conductive salt, a lithium salt, a tetraalkylammonium salt, or both.

### Claim 12 (depends on 10)

The electrolyte according to claim 10, further comprising an additive.

### Claim 13 (depends on 1)

An electrochemical or electrooptical device, comprising the compound of formula I according to claim 1, wherein [A]− is selected from the group consisting of [O—S(O)2—CmF2m+1]− wherein m=1, 2, 3, 4, 5, 6, 7 or 8 and [FzB(CmF2m+1)4-z]− wherein z=4.

### Claim 14 (depends on 1)

The compound of formula I according to claim 1, wherein [A]− is selected from the group consisting of [O—S(O)2—CmF2m+1]− wherein m=1, 2, 3, 4, 5, 6, 7 or 8 and [FzB(CmF2m+1)4-z]− wherein z=4,
wherein the compound is suitable as additives in electrolytes.

### Claim 15 (depends on 1)

The compound of formula I according to claim 1, wherein [A]− is selected from the group consisting of [O—S(O)2—CmF2m+1]− wherein m=1, 2, 3, 4, 5, 6, 7 or 8 and [FzB(CmF2m+1)4-z]− wherein z=4,
wherein the compound is suitable for electrochemical or electrooptical devices.

### Claim 16 (depends on 15)

The compound according to claim 15, wherein the electrochemical or electrooptical device is a lithium battery, a lithium ion battery, a double layer capacitor, a lithium capacitor, a solar cell, an electrochromic display, a sensor or a biosensor.