Materials for use as electrolytic solutes

Details Materials for use as electrolytic solutes Materials for use as electrolytic solutes

1999-09-24

2003-09-16

Ryan, Patrick (Department: 1745)

Chemistry: electrical current producing apparatus, product, and

Current producing cell, elements, subcombinations and...

Include electrolyte chemically specified and method

C429S199000, C252S062200, C564S096000

Reexamination Certificate

active

06620546

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The subject-matter of the present invention is ionic compositions having a high ionic conductivity, comprising a salt in which the anionic charge is delocalized, and their uses, in particular as electrolyte.
2. Description of the Related Art
It is known and particularly advantageous to introduce ionic groups into organic molecules or polymers having various functions. This is because the coulombic forces correspond to the strongest available interactions at the molecular level and the ionic groups modify in the most pronounced way the molecules to which they are attached. Mention may be made of dyes, which are rendered soluble in water using sulfonate or carboxylate functional groups.
However, the groups of this type, —CO
2
−
1/mM
m+
or —SO
3
−
1/mM
m+
, are not dissociated and they do not induce solubility in solvents other than water or some very polar protic solvents, such as light alcohols, which greatly restrict the scope of their use.
Furthermore, salts of the compounds 1/mM
m+
C
−
(SO
2
R
F
)
3
, in which R
F
is a perfluorinated group and M
m+
a cation with the valency m, are known which are soluble and dissociated in organic aprotic media or in solvating polymers. However, it is considered that the existence of at least two perfluoroalkylsulfonyl groups (in particular the existence of fluorine atoms on the carbon atom &agr; to each of the sulfonyl groups), which exert a large attractant power on the electrons of the anionic charge, is a necessary condition for the solubility and dissociation properties to be obtained.
SUMMARY OF THE INVENTION
Surprisingly, the inventors have found that the excellent solubility and dissociation properties of the
−
C(SO
2
R
F
)
3
ionic groups are retained when a single sulfone group has fluorine atoms on atoms adjacent to the sulfur atom, allowing an extremely wide choice of functional molecules. In just as unexpected a way, it was found that it is possible, with the same properties being obtained, to omit the —SO
2
— group attached to the nonperfluorinated group, provided that the group attached directly to the carbon has a Hammett parameter &sgr;* of greater than 0.55. By way of comparison, the Hammett parameter &sgr;* of an —SO
2
— group connected to a nonperfluorinated group is 3.5 and 4.55 for a CF
3
SO
2
— group.
The subject-matter of the present invention is an ionic composition comprising at least one ionic compound in solution in a solvent, the said ionic compound comprising an anionic part associated with at least one cationic part M
m+
in a number sufficient to ensure the electronic neutrality of the combination. The said composition is characterized in that it has a conductivity of greater than 10
−5
S.cm
−1
at a temperature of between −30° C. and 150° C, in that M
m+
is a proton, a hydronium, a hydroxonium, a nitrosonium NO
+
, an ammonium —NH
4
+
or a cation having the valency m chosen from metal cations, organic cations and organometallic cations, and in that the anionic part corresponds to one of the formulae X
F
—SO
x
—C
−
(Z)(Z′), X
F
—SO
x
—C
−
(YR)(Y′R′) or X
F
—SO
x
—C
−
—(Z)(YR) in which:
x is 2 (sulfonyl group) or 1 (sulfinyl group)
X
F
represents a monovalent or multivalent radical chosen from the group consisting of linear, branched or cyclic perhalogenated radicals of the alkyl, alkylaryl, oxa-alkyl, aza-alkyl, thia-alkyl, alkenyl, oxa-alkenyl, aza-alkenyl, thia-alkenyl or dialkylazo type or from the group consisting of organic radicals in which the carbon &agr; to the SO
x
group carries at least one F atom, it being understood that a multivalent X
F
radical is connected to more than one —SO
x
C— group;
Z and Z′ represent, independently of one another, a monovalent or multivalent electron-withdrawing radical, it being understood that a multivalent Z or Z′ radical can form part of a ring or be connected to several —C
−
SO
x
—X
F
groups;
Y or Y′ represent a sulfonyl, sulfinyl, carbonyl or phosphonyl group;
R is a monovalent or multivalent organic radical and R′ is H or a monovalent or multivalent organic radical, R and R′ being other than a perfluoroalkyl when x=2; it being understood that each of the substituents R, R′, Z or Z′ can form part of an aromatic or nonaromatic ring or of a polymer, and that each of the substituents X
F
, R, R′, Z or Z′ can be connected to a substituent X
F
, R, R′, Z or Z′ carried by the same anionic center C
−
or by another anionic center.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the ionic compound of a composition of the present invention, the cation can be a metal cation chosen from alkali metal cations, alkaline earth metal cations, transition metal cations, in the divalent or trivalent state, and rare earth cations. Mention may be made, by way of example, of Na
+
, Li
+
, K
+
, Sm
3+
, La
3+
, Ho
3+
, Sc
3+
, Al
3+
, Y
3+
, Yb
3+
, Lu
3+
or Eu
3+
.
The cation can also be an organometallic cation, in particular a metallocenium. Mention may be made, by way of example, of the cations derived from ferrocene, from titanocene, from zirconocene, from an indenocenium or from a metallocenium arene, the cations of transition metals complexed by ligands of phosphine type optionally possessing a chirality, or the organometallic cations possessing one or more alkyl or aryl groups covalently attached to an atom or a group of atoms, such as the methylzinc, phenylmercury, trialkyltin or trialkyllead cations. The organometallic cation can form part of a polymer chain.
The cation of the salt of a composition of the invention can be an organic cation chosen from the group consisting of the R″
3
O
+
(onium), NR″
4
+
(ammonium), R″C(NHR″
2
)
2
+
(amidinium), C (NHR″
2
)
3
+
(guanidinium), C
5
R″
6
N
+
(pyridinium), C
3
R″
5
N
2
+
(imidazolium), C
2
R″
4
N
3
+
(triazolium), C
3
R″
7
N
2
+
(imidazolinium), SR″
3
+
(sulfonium), PR″
4
+
(phosphonium), IR″
2
+
(iodonium) or (C
6
R″
5
)
3
C
+
(carbonium) cations, the R″ radicals independently representing H or a nonperfluorinated organic radical. The organic radicals R″, which are identical or different, are preferably chosen from the group consisting of
the proton, alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl, optionally hydrolyzable sila-alkyl or optionally hydrolyzable sila-alkenyl radicals and dialkylazo radicals, it being possible for the said radicals to be linear, branched or cyclic;
cyclic or heterocyclic radicals optionally comprising at least one side chain comprising heteroatoms, such as nitrogen, oxygen or sulfur;
aryl groups, arylalkyl groups, alkylaryl groups and alkenylaryl groups optionally comprising heteroatoms in the aromatic nucleus or in a substituent;
groups comprising several condensed or noncondensed, aromatic or heterocyclic nuclei, optionally comprising at least one nitrogen, oxygen, sulfur or phosphorus atom. When an onium cation carries at least two R″ radicals other than H, these radicals can together form an aromatic or nonaromatic ring, optionally encompassing the center carrying the cationic charge.
A cationic onium group can be polycationic, for example when an R″ substituent is a divalent substituent connected to two cationic centers. Mention may be made, by way of example, of the cation of the following compound
When the cationic part of the ionic compound is an onium cation, it can be provided either in the form of an independent cationic group which is only bonded to the anionic part via the ionic bond between the positive charge of the cation and the negative charge of the anionic part. In this case, the cationic part can form part of a repeat unit of a polymer.

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