Perfluorinated amide salts and their uses as ionic conducting materials

• US 6,319,428 B1
• Filed: 12/03/1998
• Issued: 11/20/2001
• Est. Priority Date: 12/30/1996
• Status: Expired due to Term

• Current Assignee: Centre National De La Recherche Scientifique, Hydro-Quebec (Province of Québec)
• Original Assignee: Centre National De La Recherche Scientifique, Hydro-Quebec (Province of Québec)
• Inventors: Michot, Christophe, Gauthier, Michel, Armand, Michel, Choquette, Yves
• Primary Examiner(s): KOPEC, MARK T
• Application Number:
  US09/125,797
• Time in Patent Office: 1,083 Days
• Field of Search: 252/500, 252/622, 429/316, 429/245, 429/200, 429/199, 296/231, 564/96, 564/98, 568/27, 526/92, 361/327
• US Class Current: 252/500
• CPC Class Codes: B01J 2231/122 Cationic (co)polymerisation, e.g. single-site or Ziegler-Natta type
• CPC Class Codes: B01J 2231/14 Other (co) polymerisation, e.g. of lactides, epoxides "ROMP", i.e. ring-opening metathesis polymerisation B01J2231/54
• CPC Class Codes: B01J 2231/326 Diels-Alder or other [4+2] cycloadditions, e.g. hetero-analogues
• CPC Class Codes: B01J 2231/341 1,2-additions, e.g. aldol or Knoevenagel condensations
• CPC Class Codes: B01J 2231/348 1,4-additions, e.g. conjugate additions
• CPC Class Codes: B01J 2231/4205 C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
• CPC Class Codes: B01J 2231/543 alkene metathesis
• CPC Class Codes: B01J 2531/35 Scandium
• CPC Class Codes: B01J 2531/824 Palladium
• CPC Class Codes: B01J 31/0215 Sulfur-containing compounds
• CPC Class Codes: B01J 31/0222 comprising sulfonyl groups
• CPC Class Codes: B01J 31/0224 being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
• CPC Class Codes: B01J 31/0225 comprising sulfonic acid groups or the corresponding salts
• CPC Class Codes: B01J 31/0227 being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
• CPC Class Codes: B01J 31/0235 Nitrogen containing compounds
• CPC Class Codes: B01J 31/0239 Quaternary ammonium compounds
• CPC Class Codes: B01J 31/0247 Imides, amides or imidates (R-C=NR(OR))
• CPC Class Codes: B01J 31/0251 Guanidides (R2N-C(=NR)-NR2)
• CPC Class Codes: B01J 31/0252 with a metal-nitrogen link, e.g. metal amides, metal guanidides
• CPC Class Codes: B01J 31/0267 Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
• CPC Class Codes: B01J 31/0271 : also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
• CPC Class Codes: B01J 31/0281 : the nitrogen being a ring member
• CPC Class Codes: B01J 31/0288 : Phosphorus
• CPC Class Codes: B01J 31/0289 : Sulfur
• CPC Class Codes: B01J 31/04 : containing carboxylic acids or their salts B01J31/0277 - B01J31/0298 take precedence; multi-metal carboxylate complexes like Pd (II) acetate, i.e. Pd3 (OAc) 6 or Cr(II)acetate, i.e. Cr2(OAc)4 B01J31/2226
• CPC Class Codes: B01J 31/06 : containing polymers organometallic polymers B01J31/123; polymer-bound organometallic complexes B01J31/165; coordination polymers B01J31/1691
• CPC Class Codes: B01J 31/068 : Polyalkylene glycols
• CPC Class Codes: B01J 31/124 : Silicones or siloxanes or comprising such units
• CPC Class Codes: B01J 31/1815 : with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
• CPC Class Codes: B01J 31/2208 : Oxygen, e.g. acetylacetonates
• CPC Class Codes: C07B 37/02 : Addition
• CPC Class Codes: C07B 37/12 : Diels-Alder reactions
• CPC Class Codes: C07C 255/10 : containing cyano groups and halogen atoms, or nitro or nitroso groups, bound to the same acyclic carbon skeleton
• CPC Class Codes: C07C 255/17 : containing cyano groups and doubly-bound oxygen atoms bound to the same acyclic carbon skeleton
• CPC Class Codes: C07C 255/27 : containing cyano groups, amino groups and doubly-bound oxygen atoms bound to the carbon skeleton
• CPC Class Codes: C07C 255/46 : to carbon atoms of non-condensed rings
• CPC Class Codes: C07C 255/65 : with the nitrogen atoms further bound to nitrogen atoms
• CPC Class Codes: C07C 257/14 : having carbon atoms of amidino groups bound to acyclic carbon atoms
• CPC Class Codes: C07C 2601/10 : the ring being unsaturated
• CPC Class Codes: C07C 2602/42 : the bicyclo ring system containing seven carbon atoms
• CPC Class Codes: C07C 311/03 : having the nitrogen atoms of the sulfonamide groups bound to hydrogen atoms or to acyclic carbon atoms
• CPC Class Codes: C07C 311/04 : to acyclic carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
• CPC Class Codes: C07C 311/09 : the carbon skeleton being further substituted by at least two halogen atoms
• CPC Class Codes: C07C 311/48 : having nitrogen atoms of sulfonamide groups further bound to another hetero atom
• CPC Class Codes: C07C 317/04 : of an acyclic saturated carbon skeleton
• CPC Class Codes: C07C 317/08 : of an acyclic unsaturated carbon skeleton
• CPC Class Codes: C07C 317/14 : having sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings
• CPC Class Codes: C07C 317/22 : with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
• CPC Class Codes: C07C 317/24 : having sulfone or sulfoxide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
• CPC Class Codes: C07C 317/34 : having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
• CPC Class Codes: C07C 317/44 : having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
• CPC Class Codes: C07C 45/46 : Friedel-Crafts reactions
• CPC Class Codes: C07C 45/69 : by addition to carbon-to-carbon double or triple bonds
• CPC Class Codes: C07C 49/553 : polycyclic
• CPC Class Codes: C07C 49/84 : containing ether groups, groups, groups, or groups
• CPC Class Codes: C07C 67/00 : Preparation of carboxylic acid esters
• CPC Class Codes: C07D 207/452 : with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
• CPC Class Codes: C07D 213/76 : to which a second hetero atom is attached nitro radicals C07D213/61
• CPC Class Codes: C07D 219/10 : attached in position 9
• CPC Class Codes: C07D 231/18 : One oxygen or sulfur atom
• CPC Class Codes: C07D 233/90 : Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
• CPC Class Codes: C07D 239/60 : Three or more oxygen or sulfur atoms
• CPC Class Codes: C07D 241/42 : with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
• CPC Class Codes: C07D 249/04 : 1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
• CPC Class Codes: C07D 249/10 : with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
• CPC Class Codes: C07D 249/12 : Oxygen or sulfur atoms
• CPC Class Codes: C07D 251/70 : Other substituted melamines
• CPC Class Codes: C07D 277/64 : with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
• CPC Class Codes: C07D 277/82 : Nitrogen atoms
• CPC Class Codes: C07D 285/125 : with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
• CPC Class Codes: C07D 285/135 : Nitrogen atoms
• CPC Class Codes: C07D 285/15 : Six-membered rings
• CPC Class Codes: C07D 285/16 : Thiadiazines; Hydrogenated thiadiazines
• CPC Class Codes: C07D 303/34 : with hydrocarbon radicals, substituted by sulphur, selenium or tellurium atoms
• CPC Class Codes: C07D 307/54 : Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
• CPC Class Codes: C07D 307/64 : Sulfur atoms
• CPC Class Codes: C07D 311/52 : Enol-esters or -ethers, or sulfur analogues thereof
• CPC Class Codes: C07D 311/58 : other than with oxygen or sulphur atoms in position 2 or 4
• CPC Class Codes: C07D 311/82 : Xanthenes
• CPC Class Codes: C07D 319/06 : not condensed with other rings
• CPC Class Codes: C07D 333/16 : by oxygen atoms
• CPC Class Codes: C07D 333/24 : Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
• CPC Class Codes: C07D 405/06 : linked by a carbon chain containing only aliphatic carbon atoms
• CPC Class Codes: C07D 409/12 : linked by a chain containing hetero atoms as chain links
• CPC Class Codes: C07D 417/10 : linked by a carbon chain containing aromatic rings
• CPC Class Codes: C07D 417/14 : containing three or more hetero rings
• CPC Class Codes: C07F 17/02 : of metals of Groups 8, 9 or 10 of the Periodic System
• CPC Class Codes: C08F 4/04 : Azo-compounds
• CPC Class Codes: C08G 65/3344 : containing oxygen in addition to sulfur
• CPC Class Codes: C09B 69/00 : Dyes not provided for by a single group of this subclass
• CPC Class Codes: C09B 69/02 : Dyestuff salts, e.g. salts of acid dyes with basic dyes for Na, K or NH4+ salts or for chlorides, sulfates or chlorozincates, see the relevant dye groups
• CPC Class Codes: C09B 69/10 : Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds addition products of alkylene oxide to dyes, C09B69/00; dyeing with polymeric dyes D06P1/0056
• CPC Class Codes: G02F 1/1525 : characterised by a particular ion transporting layer, e.g. electrolyte
• CPC Class Codes: G02F 2001/1518 : Ferrocene compounds
• CPC Class Codes: H01B 1/122 : Ionic conductors
• CPC Class Codes: H01B 1/128 : comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
• CPC Class Codes: H01G 11/02 : using combined reduction-oxidation reactions, e.g. redox arrangement or solion
• CPC Class Codes: H01G 11/62 : characterised by the solute, e.g. salts, anions or cations therein
• CPC Class Codes: H01G 9/022 : Electrolytes; Absorbents
• CPC Class Codes: H01M 10/052 : Li-accumulators
• CPC Class Codes: H01M 10/0525 : Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 10/0565 : Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: H01M 10/0567 : characterised by the additives
• CPC Class Codes: H01M 10/0568 : characterised by the solutes
• CPC Class Codes: H01M 4/00 : Electrodes
• CPC Class Codes: H01M 4/02 : Electrodes composed of, or comprising, active material
• CPC Class Codes: H01M 4/131 : Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/133 : Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/134 : Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/382 : Lithium H01M4/405 takes precedence
• CPC Class Codes: H01M 4/405 : Alloys based on lithium
• CPC Class Codes: H01M 4/48 : of inorganic oxides or hydroxides
• CPC Class Codes: H01M 4/485 : of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/505 : of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• CPC Class Codes: H01M 4/525 : of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 4/5815 : Sulfides
• CPC Class Codes: H01M 4/5825 : Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: H01M 4/60 : of organic compounds
• CPC Class Codes: H01M 4/625 : Carbon or graphite
• CPC Class Codes: H01M 4/661 : Metal or alloys, e.g. alloy coatings H01M4/669 take precedence
• CPC Class Codes: H01M 6/00 : Primary cells; Manufacture thereof
• CPC Class Codes: H01M 6/04 : Cells with aqueous electrolyte
• CPC Class Codes: H01M 6/164 : by the solvent
• CPC Class Codes: H01M 6/166 : by the solute
• CPC Class Codes: H01M 6/168 : by additives
• CPC Class Codes: H01M 6/181 : with polymeric electrolytes
• CPC Class Codes: H01M 6/183 : with fluoride as solid electrolyte
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02E 60/13 : Energy storage using capacitors
• CPC Class Codes: Y10S 430/127 : Spectral sensitizer containing
• CPC Class Codes: Y10T 29/49108 : Electric battery cell making
• CPC Class Codes: Y10T 428/2918 : including free carbon or carbide or therewith [not as steel]

Abstract

The invention concerns ionic compounds in which the anionic load has been delocalized. A compound disclosed by the invention is comprised of an amide or one of its salts, including an anionic portion combined with at least one cationic portion M ^m in sufficient numbers to ensure overall electronic neutrality; the compound is further comprised of M as a hydroxonium, a nitrosonium NO , an ammonium —NH₄ , a metallic cation with the valence m, an organic cation with the valence m, or an organometallic cation with the valence m. The anionic portion matches the formula R_F—SO_x—N⁻Z, wherein R_F is a perfluorinated group, x is 1 or 2, and Z is an electroattractive substituent. The compounds can be used notably for ionic conducting materials, electronic conducting materials, colorants, and the catalysis of various chemical reactions.

Claims

1. Electrochemical generator comprising a negative electrode and a positive electrode both separated by an electrolyte, characterized in that the electrolyte is a material comprising an ionic compound in a solvent, wherein said ionic compound consists of an amide or salts thereof, comprising an anionic part associated with at least one cationic part M ^m in sufficient number to ensure an electronic neutrality thereto, characterized in that M is a hydroxonium, a nitrosonium NO , an amionium —

NH₄ , a metallic cation having a valency m, an organic onium cation having a valency m or an organo-metallic cation having a valency m and in that the anionic part corresponds to the formula R_F—

SO_X—

N⁻

—

Z in which;

the group —

S(O)_X—

represents a sulfonic group —

SO₂—

or a sulfinyl group —

SO—

;

R_F is a halogen or a perhalogenated alkyl, alkylaryl, oxa-alkyl, aza-alkyl or thia-alkyl radical, or a radical corresponding to one of the formulae R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

or CF₃C(R_A)F—

in which R_A—

represents a non-perhalogenated organic radical;

Z represents an electro-attractor radical having a Hammett parameter at least equal to that of a phenyl radical, selected from;

j) —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, R′

_FCH₂—

(R′

_F being a perfluorinated radical) or a fluoroalkylthioxy radical,

jj) radicals comprising one or more aromatic nuclei optionally containing at least one hydrogen, oxygen, sulfur or phosphorus atom, said nuclei optionally being condensed nuclei and/or said nuclei optionally carrying at least one substituent selected from halogens, —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, CF₃CH₂—

, CF₂═

CF—

O—

, CF₂═

CF—

S—

, perfluoroalkyl groups, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl radicals, polymer radicals, radicals having at least one cationic ionophoric group and/or at least one anionic ionophoric group;

 

with the proviso that a substituent Z may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_F—

S(O)_X—

N—

, or a polymer segment;

or

Z is a radical R_D—

Y—

in which Y is a sulfonyl, sulfinyl or phosphonyl group and R_D is a radical selected from the group consisting of;

a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, alicyclic, heterocyclic radicals, or polycyclic radicals;

b) alkyl or alkenyl radicals comprising at least one functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate group;

c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which the aromatic nuclei and/or at least one substituent of the nucleus comprises heteroatoms selected from nitrogen, oxygen, sulfur;

d) radicals comprising condensed aromatic cycles which optionally comprise at least one heteroatom selected from nitrogen, oxygen, sulfur;

e) halogenated alkyl, alkenyl, aryl, arylalkyl, alkylaryl or alkenylaryl radicals in which the number of carbon atoms carrying at least one halogen is at most equal to the number of non-halogenated carbon atoms, the carbon in α

position of group Y not being halogenated when Y is —

SO₂—

, said radicals optionally comprising functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate groups;

f) radicals R_CC(R′

)(R″

)—

O—

in which R_C is an alkyl perfluorinated radical and R′ and

R″

are independently from one another, an hydrogen atom or a radical as defined in a), b), c) or d) above;

g) radicals (R_B)₂N—

, in which the R_B, identical or different, as defined in a), b), c), d) and e) above, one of the R_B may be a hydrogen atom, or the two radicals R_B together form a bivalent radical which forms a cycle with N;

h) radicals consisting of a polymer chain;

i) radicals having one or more cationic ionophoric groups and/or one or more anionic ionophoric groups;

 

with the proviso that a substituent R_D may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_FS(O)_X—

N—

Y—

, or a segment of a polymer;

 

with the proviso that, when Y is a sulfonyl and R_D is a radical such as defined in a), R_F is R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

, CF₃C(R_A)F—

or a perhaloalkyl radical having 1 to 2 carbon atoms.

2. Generator according to claim 1, characterized in that the negative electrode consists of metallic lithium, or an alloy thereof, optionally in the form of nanometric dispersion in lithium oxide, or a double nitride of lithium and a transition metal, or an oxide with low potential having the general formula Li_{1 y x/3}Ti₂₋

x/3O₄ (0≦

x≦

1, 0≦

y≦

1), or carbon and carbon products originating from pyrolysis of organic materials.

3. Generator according to claim 1, characterized in that the positive electrode is selected from vanadium oxides VO_x (2≦

x≦

2.5), LiV₃O₈, Li_yNi<sub>1−

x</sub>Co_xO₂, (0≦

x≦

1;

0≦

y≦

1), spinels of manganese Li_yMn<sub>1−

x</sub>M_xO₂ (M=Cr, Al, V, Ni, 0≦

x≦

0,5;

0≦

y≦

2), organic polydisulfides FeS, FeS₂, iron sulfate Fe₂(SO₄)₃, phosphates and phophosilicates of iron and lithium of olivine structure, or substituted products where iron is substituted by manganese, used alone or in admixtures.

4. Generator according to claim 1, characterized in that the collector of the cathode is made of aluminum.

5. An ionically conducting material according to claim 1, characterized in that the cation M is a metallic cation selected from the group consisting of cations of alkali metals, cations of alkali-earth metals, cations of transiton metals, cations of trivalent metals, cations of rare earth metals and organometallic cations.

6. An tonically conducting material according to claim 1, characterized in that R_F is a fluorine atom or a perhalogenated alkyl radical having 1 to 12 carhon atoms, or a perhalogenated alkylaryl radical having 6 to 9 carbon atoms.

7. An tonically conducting material according to claim 1, characterized in that R_D is sclocted from alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl or thia-alkenyl radicals having 1 to 24 carbon atoms, or from aryl arylalkyl, alkylaryl or alkenylaryl radicals having 5 to 24 carbon atoms in which the lateral chains and/or the aromatic nuclei comprise heteroatoms.

8. An ionically conducting material according to claim 1, characterized in that R_D is selected from alkyl or alkenyl radicals having 1 to 12 carbon atoms and optionally comprising at least one heterostom O, N or S in the main chain or in a lateral chain, and/or optionally carrying a hydroxy group, a carbonyl group, an aminc group, a carboxyl group, an isocyanate group or a thloisocyanate group.

9. An ionically conducting material according to claim 1, characterized in that R_D is part of a poly(oxyalkylene) radical or a polystyrene radical.

10. An ionically conducting maerial according to claim 1, characterized in that the solvent is either an aprotic liquid solvent, selected from linear others and cyclic ethers, esters, nitriles, nitro derivatives, amides, sulfones, sulfolanes, alkylsulfamides and partially halogenated hydrocarbons, or a polar polymer, or a mixture thereof.

11. A supercapacitor using at least one carbon electrode with high specific surface, or at least an electrode containing a redox polymer, with an electrolyte material, in which the electrolyte is a material comprising an ionic compound in a solvent, wherein said ionic compound consists of an amide or salts thereof, comprising an anionic part associated with at least one cationic part M ^m in sufficient number to ensure an electronic neutrality thereto, characterized in that M is a hydroxonium, a nitrosonium NO , an ammonium —

NH₄ , a metallic cation having a valency m, an organic onium cation having a valency m or an organo-metallic cation having a valency m and in that the anionic part corresponds to the formula R_F—

SO_X—

N⁻

—

Z in which;

the group —

S(O)_X—

represents a sulfonic group —

SO₂—

or a sulfinyl group —

SO—

;

R_F is a halogen or a perhalogenated alkyl, alkylaryl, oxa-alkyl, aza-alkyl or thia-alkyl radical, or a radical corresponding to one of the formulae R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

or CF₃C(R_A)F—

in which R_A—

represents a non-perhalogenated organic radical;

Z represents an electro-attractor radical having a Hammett parameter at least equal to that of a phenyl radical, selected from;

j) —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, R′

_FCH₂—

(R′

_F being a perfluorinated radical) or a fluoroalkylthioxy radical,

jj) radicals comprising one or more aromatic nuclei optionally containing at least one hydrogen, oxygen, sulfur or phosphorus atom, said nuclei optionally being condensed nuclei and/or said nuclei optionally carrying at least one substituent selected from halogens, —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, CF₃CH₂—

, CF₂═

CF—

O—

, CF₂═

CF—

S—

, perfluoroalkyl groups, fluoroalkyloxy groups, fluoroalfylthioxy groups, alkyl alkenyl oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl radicals, polymer radicals, radicals having at least one cationic ionophoric group and/or at least one anionic ionophoric group;

 

with the proviso that a substituent Z may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_F—

S(O)_X—

N—

, or a polymer segment;

or

Z is a radical R_D—

Y—

in which Y is a sulfonyl, sulfinyl or phosphonyl group and R_D is a radical selected from the group consisting of;

a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, alicyclic, heterocyclic radicals, or polycyclic radicals;

b) alkyl or alkenyl radicals comprising at least one functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate group;

c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which the aromatic nuclei and/or at least one substituent of the nucleus comprises heteroatoms selected from nitrogen, oxygen, sulfur;

d) radicals comprising condensed aromatic cycles which optionally comprise at least one heteroatom selected from nitrogen, oxygen, sulfur,

e) halogenated alkyl, alkenyl, aryl, arylalkyl, alkylaryl or alkenylaryl radicals in which the number of carbon atoms carrying at least one halogen is at most equal to the number of non-halogenated carbon atoms, the carbon in α

position of group Y not being halogenatod when Y is —

SO₂—

, said radicals optionally comprising functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate groups;

f) radicals R_CC(R′

)(R″

)—

O—

in which R_C is an alkyl perfluorinated radical and R′ and

R″

are independently from one another, an hydrogen atom or a radical as defined in a), b), c) or d) above;

g) radicals (R_B)₂N—

, in which the R_B, identical or different, as defined in a), b), c), d) and a) above, one of the R_B may be a hydrogen atom, or the two radicals R_B together form a bivalent radical which forms a cycle with N;

h) radicals consisting of a polymer chain;

i) radicals having one or more catonic ionophoric groups and/or one or more anionic ionophoric groups;

 

with the proviso that a substituent R_D may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_FS(O)x—

N—

Y—

, or a segment of a polymer;

 

with the proviso that, when Y is a sulfonyl and R_D is a radical such as defined in a), R_F is R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

, CF₃C(R_A)F—

or a perhaloalkyl radical having 1 to 2 carbon atoms.

12. An ionically conducting material according to claim 11, characterizcd in that M is an organic onium cation selected from the group consisting of R₃O (oxonium), NR₄ (ammonium), RC(NHR₂)₂ (amidinium), C(NHR₂)₃ (guanidinium), C₅R₆N (pyridinium), C₃R₅N₂ (imidazolium), C₂R₄N₃ (triazolium), C₃R₇N₂ (imidazolinium), SR₃ (sulfonium), PR₄ (phosphonium), IR₂ (iodonium), (C₆R₅)₃C (carbonium), the radicals R independently representing II or a radical selecled from the group consisting of

alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl, sila-alkyl, sila-alkenyl, aryl, arylalkyl, alkylaryl, alkenylaryl radicals, dialkylamino radicals and dialkylazo radicals;

cyclic or heterocyclic radicals optionally comprising at least one lateral chain comprising heteroatoms such as nitrogen, oxygen, sulfur;

cyclic or heterocyclic radicals optionally comprising heteroatoms in the aromatic nuclei;

groups comprising a plurality of aromatic or heterocyclic, condensed or non-condensed nuclei, optionally containing at least one nitrogen, oxygen, sulfur or phosphorus atom;

 

with the proviso that a plurality of radicals R may together form aliphatic or aromatic cycles optionally enclosing the center carrying tile cationic charge.

13. An ionically conductingmaterial accotding to claim 11, characterized in that the cation M is a metallic cation selected from the group consisting of cations of alkali metals, cations of alkali-earth metals, cations of transition metals, cations of trivalent metals, cations of rare earth metals and organometallic cations.

14. An ionically conducting material according to claim 11, characterized in that the solvent is either an aprotic liquid solvent, selected from linear ethers and cyclic ethers, esters, nitriles, nitro derivatives, amides, sulfones, sulfolanes, alkylsulfamides and partially halogenated hydrocatons, or a polar polymer, or a mixture thereof.

15. Use of a material comprising an ionic compound in a solvent, wherein said ionic compound consists of an amide or salts thereof, comprising an anionic part associated with at least one cationic part M ^m in sufficient number to ensure an electronic neutrality thereto, characterized in that M is a hydroxonium, a nitrosonium NO , an ammonium —

NH₄ , a metallic cation having a valency m, an organic onium cation having a valency m or an organo-metallic cation having a valency m and in that the anionic part corresponds to the formula R_F—

SO_X—

N⁻

—

Z in which;

the group —

S(O)_X—

represents a sulfonic group —

SO₂—

or a sulfinyl group —

SO—

;

R_F is a halogen or a perhalogenated alkyl, alkylaryl, oxa-alkyl, aza-alkyl or thia-alkyl radical, or a radical corresponding to one of the formulae R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

or CF₃C(R_A)F—

in which R_A—

represents a non-perhalogenated organic radical;

Z represents an electro-attractor radical having a Hammett parameter at least equal to that of a phenyl radical, selected from;

j) —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, R′

_FCH₂—

(R′

_F being a perfluorinated radical) or a fluoroalkylthioxy radical,

jj) radicals comprising one or more aromatic nuclei optionally containing at least one hydrogen, oxygen, sulfur or phosphorus atom, said nuclei optionally being condensed nuclei and/or said nuclei optionally carrying at least one substituent selected from halogens, —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, CF₃CH₂—

, CF₂═

CF—

O—

, CF₂═

CF—

S—

, perfluoroalkyl groups, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl radicals, polymer radicals, radicals having at least one cationic ionophoric group and/or at least one anionic ionophoric group;

 

with the proviso that a substituent Z may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_F—

S(O)_X—

N—

, or a polymer segment;

or

Z is a radical R_D—

Y—

in which Y is a sulfonyl, sulfinyl or phosphonyl group and R_D is a radical selected from the group consisting of;

a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, alicyclic, heterocyclic radicals, or polycyclic radicals;

b) alkyl or alkenyl radicals comprising at least one functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate group;

c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which the aromatic nuclei and/or at least one substituent of the nucleus comprises heteroatoms selected from nitrogen, oxygen, sulfur;

d) radicals comprising condensed aromatic cycles which optionally comprise at least one heteroatom selected from nitrogen, oxygen, sulfur;

e) halogenated alkyl, alkenyl, aryl, arylalkyl, alkylaryl or alkenylaryl radicals in which the number of carbon atoms carrying at least one halogen is at most equal to the number of non-halogenated carbon atoms, the carbon in α

position of group Y not being halogenated when Y is —

SO₂—

, said radicals optionally comprising functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate groups;

f) radicals R_CC(R′

)(R″

)—

O—

in which R_C is an alkyl perfluorinated radical and R′ and

R″

are independently from one another, an hydrogen atom or a radical as defined in a), b), c) or d) above;

g) radicals (R_B)₂N—

, in which the R_B, identical or different, as defined in a), b), c), d) and e) above, one of the R_B may be a hydrogen atom, or the two radicals R_B together form a bivalent radical which forms a cycle with N;

h) radicals consisting of a polymer chain;

i) radicals having one or more cationic ionophoric groups and/or one or more anionic ionophoric groups;

 

with the proviso that a substituent R_D may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_FS(O)_X—

N—

Y—

, or a segment of a polymer;

 

with the proviso that, when Y is a sulfonyl and R_D is a radical such as defined in a), R_F is R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

, CF₃C(R_A)F—

or a perhaloalkyl radical having 1 to 2 carbon atoms;

 

wherein the material is used for p or n doping of an electronically conductive polymer, by addition to at least a halogenated hydrocarbon and sulfonic anhydride solution.

16. An ionically conducting material acording to claim 15, characterized in that M is an organic onium cation seleted from the group consisting of R₃O (oxonium), NR₄ (ammonium), RC(NHR₂)₂ (amidinium), C(NHR₂)₃ (guanidinium), C₅R₆N (pyridinium), C₃R₅N₂ (imidazolium), C₂R₄N₃ (triazolium), C₃R₇N₂ (imidazolinium), SR₃ (sulfonium), PR₄ (phosphonium) IR₂ (iodonium), (C₆R₅)₃C (carbonium), the radicals R independently representing H or a radical selected from the group consisting of:

alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl, sila-alkyl, sila-alkenyl, aryl, arylalkyl, alkylaryl, alkenylaryl radicals, dialkylamino radicals and dialkylazo radicals;

cyclic or heterocyclic radicals optionally comprising at least one lateral chain comprising heteroatoms such as nitrogen, oxygen, sulfur;

cyclic or heterocyclic radicals optionally comprising heteroatoms in the aromatic nuclei;

groups comprising a plurality of aromatic or heterocyclic, condensed or non-condensed nuclei, optionally containing at least one nitrogen, oxygen, sulfur or phosphorus atom;

 

with the proviso that a plurality of radicals R may together form aliphatic or aromatic cycles optionally enclosing the center carrying the cationic charge.

17. An ionically conducting material according to claim 15, characterized in that the cation M is a metallic cation selected from the group consisting of cations of alkali metals, cations of alkali-earth metals, cations of transition metals, cations of trivalent metals, cations of rare earth metals and organometallic cations.

18. An ionically conducting material according to claim 15, characterized in that R_F is a fluorine atom or a perhalogenad alkyl radical having 1 to 12 carbon atoms, or a perhalogenated alkylaryl radical having 6 to 9 carbon atoms.

19. An ionically conducting material according to claim 15, characterized in that R_D is selected from alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl or thia-alkenyl radicals having 1 to 24 carbon atoms, or from aryl, arylalkyl, alkylaryl or alkenylaryl radicals having 5 to 24 carbon atoms in which the lateral chains and/or the aromatic nuclei comprise heteroatoms.

20. An ionically conducting material according to claim 15, characterized in that R_D is selected from alkyl or alkenyl radicals having 1 to 12 carbon atoms and optionally comprising at least one heteroatom O, N or S in the main chain or in a lateral chain, and/or optionally carrying a hydroxy group, a carbonyl group, an amino group, a carboxyl group, an isocyanate group or a thioisocyanate group.

21. An ionically conducting material according to claim 15, characterized in that R_D is part of a poly(oxyalkylyene) radical or a polystyrene radical.

22. Electrochrome device in which the electrolyte is a material comprising an ionic compound in a solvent, wherein said ionic compound consists of an amide or salts thereof, comprising an anionic part associated with at least one cationic part M ^m in sufficient number to ensure an electronic neutrality thereto, characterized in that M is a hydroxonium, a nitrosonium NO , an ammonium —

NH₄ , a metallic cation having a valency m, an organic onium cation having a valency m or an organo-metallic cation having a valency m and in that the anionic part corresponds to the formula R_F—

SO_X—

N⁻

—

Z in which;

the group —

S(O)_X—

represents a sulfonic group —

SO₂—

or a sulfinyl group —

SO—

;

R_F is a halogen or a perhalogenated alkyl, alkylaryl, oxa-alkyl, aza-alkyl or thia-alkyl radical, or a radical corresponding to one of the formulae R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

or CF₃C(R_A)F—

in which R_A—

represents a non-perhalogenated organic radical;

Z represents an electro-attractor radical having a Hammett parameter at least equal to that of a phenyl radical, selected from;

j) —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, R′

_FCH₂—

(R′

_F being a perfluorinated radical) or a fluoroalkylthioxy radical,

jj) radicals comprising one or more aromatic nuclei optionally containing at least one hydrogen, oxygen, sulfur or phosphorus atom, said nuclei optionally being condensed nuclei and/or said nuclei optionally carrying at least one substituent selected from halogens, —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, CF₃CH₂—

, CF₂═

CF—

O—

, CF₂═

CF—

S—

, perfluoroalkyl groups, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl radicals, polymer radicals, radicals having at least one cationic ionophoric group and/or at least one anionic ionophoric group;

 

with the proviso that a substituent Z may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_F—

S(O)_X—

N—

, or a polymer segment;

or

Z is a radical R_D—

Y—

in which Y is a sulfonyl, sulfinyl or phosphonyl group and R_D is a radical selected from the group consisting of;

a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, alicyclic, heterocyclic radicals, or polycyclic radicals;

b) alkyl or alkenyl radicals comprising at least one functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate group;

c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which the aromatic nuclei and/or at least one substituent of the nucleus comprises heteroatoms selected from nitrogen, oxygen, sulfur;

d) radicals comprising condensed aromatic cycles which optionally comprise at least one heteroatom selected from nitrogen, oxygen, sulfur;

e) halogenated alkyl, alkenyl, aryl, arylalkyl, alkylaryl or alkenylaryl radicals in which the number of carbon atoms carrying at least one halogen is at most equal to the number of non-halogenated carbon atoms, the carbon in α

position of group Y not being halogenated when Y is —

SO₂—

, said radicals optionally comprising functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate groups;

f) radicals R_CC(R′

)(R″

)—

O—

in which R_C is an alkyl perfluorinated radical and R′ and

R″

are independently from one another, an hydrogen atom or a radical as defined in a), b), c) or d) above;

g) radicals (R_B)₂N—

, in which the R_B, identical or different, as defined in a), b), c), d) and e) above, one of the R_B may be a hydrogen atom, or the two radicals R_B together form a bivalent radical which forms a cycle with N;

h) radicals consisting of a polymer chain;

i) radicals having one or more cationic ionophoric groups and/or one or more anionic ionophoric groups;

 

with the proviso that a substituent R_D may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_FS(O)_X—

N—

Y—

, or a segment of a polymer;

 

with the proviso that, when Y is a sulfonyl and R_D is a radical such as defined in a), R_F is R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

, CF₃C(R_A)F—

or a perhaloalkyl radical having 1 to 2 carbon atoms.

23. An ionically conducting material according to claim 22, characterized in that M is an organic onium cation selected from the group consisting of R₃O (oxonium), NR₄ (ammonium), RC(NHR₂)₂ (amidinium), C(NHR₂)₃ (guanidinium), C₅R₆N (pyridinium), C₃R₅N₂ (imidazolium), C₂R₄N₃ (triazolium), C₃R₇N₂ (imidazolinium), SR₃ (sulfonium), PR₄ (phosphonium), IR₂ (iodonium), (C₆R₅)₃C (carbonium), the radicals R independently representing H or a radical selected from the group consisting of:

alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl aza-alkenyl, thia-alkyl, thia-alkenyl, sila-alkyl, sila-alkenyl, aryl, arylalkyl, alkylaryl, alkenylaryl radicals, dialkylamino radicals and dialkylazo radicals;

cyclic or heterocyclic radicals optionally comprising at least one lateral chain comprising heteroatoms such as nitrogen, oxygen, sulfur;

cyclic or heterocyclic radicals optionally comprising heteroatoms in the aromatic nuclei;

groups comprising a plurality of aromatic or heterocyclic, condensed or non-condensed nuclei, optionally containing at least one nitrogen, oxygen, sulfur or phosphorus atom;

 

with the proviso that a plurality of radicals R may together form aliphatic or aromatic cycles optionally enclosing the center carrying the cationic charge.

24. An ionically conducting material according to claim 22, characterized in that the cation M is a metallic cation selected from the group consisting of cations of alkali metals, cations of alkali-earth metals, cations of transition metals, cations of trivalent metals, cations of rare earth metals and organometallie cations.

25. An ionically conducting material according to claim 22, characterized in that R_F is a fluorine atom or a perhalogenated alkyl radical having 1 to 12 carbon atoms, or a perhalogenated alkylaryl radical having 6 to 9 carbon atoms.

26. An ionically conducting material according to claim 22, characterized in that R_D selected from alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl or thia-alkenyl radicals having 1 to 24 carbon atoms, or from aryl, arylalkyl, alkylaryl or alkenylaryl radicals having 5 to 24 carbon atoms in which the lateral chains and/or the aromatic nuclei comprise heteroatoms.

27. An ionically conducting material according to claim 22, characterized in that R_D is selected from alkyl or alkenyl radicals having 1 to 12 carbon atoms and optionally comprising at least one heteroatom O, N or S in the main chain or in a lateral chain, and/or optionally carryig a hydroxy group, a carbonyl group, an amine group, a carboxyl group, an isocyanate group or a thioisocyanate group.

28. An ionically conducting material according to claim 22, characterized in that R_D is part of a poly(oxyalkylene) radical or a polystyrene radical.

29. An ionically conducting material according to claim 22, characterized in that the solvent is either an aprotic liquid solvent, selected from linear ethers and cyclic ethers, esters, nitriles, nitro derivatives, amides, sulfones, sulfolanes, alkylsulfamides and partially halogenated hydrocarbons, or a polar polymer, or a mixture thereof.

30. Electronically conductive material comprising an ionic compound in a solvent, wherein said ionic compound consists of an amide or salts thereof, comprising an anionic part associated with at least one cationic part M ^m in sufficient number to ensure an electronic neutrlty thereto, characterized in that M is a hydroxonium, a nitrosonium NO , an ammonium —

NH₄ , a metallic cation having a valency m, an organic onium cation having a valency m or an organo-metallie cation having a valency m and in that the anionic part corresponds to the formula R_F—

SO_X—

N⁻

—

Z in which;

the group —

S(O)_X—

represents a sulfonic group —

SO₂—

or a sulfinyl group —

SO—

;

R_F is a halogen or a perhalogenated alkyl alkylaryl, oxa-alkyl, aza-alkyl or thia-alkyl radical, or a radical corresponding to one of the formulae R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

or CF₃C(R_A)F—

in which R_A—

represents a non-perhalogenated organic radical;

Z represents an electro-attractor radical having a Hammett parameter at least equal to that of a phenyl radical, selected from;

j) —

CN, —

NO₂, —

SCN, —

N₃, CF₃, R′

_FCH₂—

(R′

_F being a perfluorinated radical) or a fluoroalkylthioxy radical,

jj) radicals comprising one or more aromatic nuclei optionally containing at least one hydrogen, oxygen, sulfur or phosphorus atom, said nuclei optionally being condensed nuclei and/or said nuclei optionally carrying at least one substituent selected from halogens, —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, CF₃CH₂═

, CF₂—

CF—

O—

, CF₂═

CF—

S—

, perfuoroalkyl groups, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl radicals, polymer radicals, radicals having at least one cationic ionophoric group and/or at least one anionic ionophoric group;

 

with the proviso that a substituent Z may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_F—

S(O)_X—

N—

, or a polymer segment;

or

Z is a radical R_D—

Y—

in which Y is a sulfonyl, sulfinyl or phosphonyl group and R_D is a radical selected from the group consisting of;

a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, alicyclic, heterocyclic radicals, or polycyclic radicals;

b) alkyl or alkenyl radicals comprising at least one functional ether, thioether, amine, imine, carboxyl, carbonyl hydroxy, silyl, isocyanate or thioisocyanate group;

c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which the aromatic nuclei and/or at least one substituent of the nucleus comprises heteroatoms selected from nitrogen, oxygen, sulfur;

d) radicals comprising condensed aromatic cycles which optionally comprise at least one heteroatom selected from nitrogen, oxygen, sulfur;

c) halogenated alkyl, alkenyl, aryl, arylalkyl, alkylaryl or alkenylaryl radicals in which the number of carbon atoms carrying at least one halogen is at most equal to the number of non-halogenated carbon atoms, the carbon in α

position of group Y not being halogenated when Y is —

SO₂—

, said radicals optionally comprising functional others thioether, amine, imine, carboxyl, cabonyl, hydroxy, silyl, isocyanate or thioisocyanate groups;

f) radicals R_CC(R′

)(R″

)—

O—

in which R_C is an alkyl perfluorinated radical and R′ and

R″

are independently from one another, an hydrogen atom or a radical as defined in a), b), c) or d) above;

g) radicals (R_B)₂N—

, in which the R_B, identical or different, as defined in a), b), c), d) and c) above, one of the R_B may be a hydrogen atom, or the two radicals R_B together form a bivalent radical which forms a cycle with N;

h) radicals consisting of a polymer chain;

i) radicals having one or more cationic ionophoric groups and/or one or more anionic ionophoric groups;

 

with the proviso that a substituent R_D may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_FS(O)X—

N—

Y—

, or a segment of a polymer;

 

with the proviso that, when Y is a sulfonyl and R_D is a radical such as defined in a), R_F is R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

, CF₃C(R_A)F—

or a perhaloalkyl radical having 1 to 2 carbon atoms, characterized in that the cationic part of the ionic compound is a polycation consisting of a doped conjugated polymer “

p”

.

31. An ionically conducting material according to claim 30, charactcdzed in that the solvent is either an aprotic liquid solvent, selected from linear ethers and cyclic ethers, esters, nitriles, nitro derivatives, amides, sulfones, sulfolanes, alkylsulfamides and parlially halogenated hydrocarbons, or a polar polymer, or a mixture thereof.

32. Electronically conductive material comprising an ionic compound in a solvent, wherein said ionic compound consists of an amide or salts thereof, comprising an anionic part associated with at least one cationic part M ^m sufficicent number to ensure an electronic neutrality thereto, characterized in that M is a hydroxonium, a nitrosonium NO³⁰ , an ammonium —

NH , a metallic cation having a valency m, an organic onium cation having a valency m or an organo-metallic cation having a valency m and in that the anionic part corresponds to the formula R_F—

SO_X—

N⁻

—

Z in which;

the group —

S(O)_X—

represents a sulfonic group —

SO₂—

or a sulfinyl group —

SO—

;

R_F is a halogen or a perhalogenated alkyl alkylaryl, oxa-alkyl, aza-alkyl or thia-alkyl radical, or a radical corresponding to one of the formulae R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

or CF₃C(R_A)F—

in which R_A—

represents a non-perhalogenated organic radical;

Z represents an elcctro-attractor radical having a Hammett parameter at least equal to that of a phenyl radical, selected from;

j) —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, R′

_FCH₂—

(R′

_F being a perfluorinated radical) or a fluoroalkylthioxy radical,

jj) radicals comprising one or more aromatic nuclei optionally containing at least one hydrogen, oxygen, sulfur or phosphorus atom, said nuclei optionally being condensed nuclei and/or said nuclei optionally carrying at least one substituent selected from halogens, —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, CF₃CH₂—

, CF₂═

CF—

O—

, CF₂═

CF—

S—

, perfluoroalkyl groups, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl thia-alkenyl radicals, polymer radicals, radicals having at least one cationic ionophoric group and/or at least one anionic ionophoric group;

 

with the proviso that a substituent Z may be a monovalent radical part of a multivalent radical carrying a plurality of groups R_F—

S(O)_X—

N—

, or a polymer segment;

or

Z is a radical R_D—

Y—

in which Y is a sulfonyl, sulfinyl or phosphonyl group and R_D is a radical selected from the group consisting of;

a) alkyl or alkenyl radicals, aryl, arylalkyl alkylaryl or alkenylaryl radicals, alicyclic, heterocyclic radicals, or polycyclic radicals;

b) alkyl or alkenyl radicals comprising at least one functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate group;

c) aryl arylkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which the aromatic nuclei and/or at least one substituent of the nucleus comprises heteroatoms selected from nitrogen, oxygen, sulfur;

d) radicals comprising condensed aromatic cycles which optionally comprise at least one heteroatom selected from nitrogen, oxygen, sulfur;

e) halogenated alkyl, alkenyl, aryl, arylalkyl, alkylaryl or alkenylaryl radicals in which the nunmber of carbon atoms carrying at least one halogen is at most equal to the number of non-halogenated carbon atoms, the carbon in α

position of group Y not being halogenated when Y is —

SO₂—

, said radicals optionally comprising functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate groups;

f) radicals R_CC(R′

)(R″

)—

O—

in which R_C is an alkyl perfluorinated radical and R′ and

R″

are indepedently from one another, an hydrogen atom or a radical as defined in a), b), c) or d) above;

g) radicals (R_B)₂N—

, in which the R_B, identical or different, as defined in a), b), c), d) and e) above, one of the R_B may be a hydrogen atom, or the two radicals R_B together form a bivalent radical which forms a cycle with N;

h) radicals consisting of a polymer chain;

i) radicals having one or more cationic ionophoric groups and/or one or more anionic ionophoric groups;

 

with the proviso that a substituent R_D may be a monovalent radical, part of a multivalent radical carrying a plurity of groups R_FS(O)X—

N—

Y—

, or a segment of a polymer;

 

with the proviso that, when Y is a sulfonyl and R_D is a radical such as defined in a), R_F is R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

, CF₃C(R_A)F—

or a perhaloalkyl radical having 1 to 2 carbon atoms, characterized in that the substituent Z of the ionic compound comprises an alkyl chain having 6 to 20 carbon atoms.

33. An ionically conducdng material comprising an ionic compound in a solvent, wherein said ionic compound consists of an amide or salts thereof, comprising an anionic part associated with at least one cationic part M ^m in sufficient number to ensure an electronic neutrality thereto, characterized in that M is a hydroxonium, a nitrosonium NO , an ammonium —

NH₄ , a metallic cation having a valency m, an organic onium cation having a valency m or an organo-metallic cation having a valency m and in that the anionic part corresponds to tho formula R_F—

SO_XN⁻

—

Z in which;

the group —

S(O)_X—

represents a sulfonic group —

SO₂—

or a salfinyl group —

SO—

;

R_F is a halogen or a perhalogenated alkyl, alkylaryl, oxa-alkyl, aza-alkyl or thia-alkyl radical, or a radical corresponding to one of the formulae R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

or CF₃C(R_A)F—

in which R_A—

represents a non-perhalogenated organic radical;

Z represents an electro-attractor radical having a Hammett parameter at least equal to that of a phenyl radical, selected from;

j) —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, R′

_FCH₂—

(R′

_F being a perfluorinated radical) or a fluoroalkylthioxy radical,

jj) radicals comprising one or more aromatic nucli optionally containing at least one hydrogen, oxygen, sulfur or phosphorus atom, said nuclei optionally being condensed nuclei and/or said nuclei optionally carrying at least one substituent selected from halogens, —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, CF₃CH₂—

, CF₂═

CF—

O—

, CF₂═

CF—

S—

, perfluoroalkyl groups, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkeniyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl radicals, polymer radicals, radicals having at least one cationic ionophoric group and/or at least one anionic ionophoric group;

 

with the proviso that a substituent Z may be a monovalont radical, part of a multivalent radical carying a plurality of groups R_F—

S(O)_X—

N—

, or a polymer segment;

or

Z is a radical R_D—

Y—

in which Y is a sulfonyl, sulfinyl or phosphonyl group and R_D is a radical selected from the group consisting of;

a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, alicyclic, heterocyclic radicals, or polycyclic radicals;

b) alkyl or alkenyl radicals comprising at least one functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate group;

c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which the aromatic nuclei and/or at least one substituent of the nucleus comprises heteroatoms selected from nitrogen, oxygen, sulfur;

d) radicals comprising condensed aromatic cycles which optionally comprise at least one hetoroatom selected from nitrogen, oxygen, sulfur;

e) halogenated alkyl, alkenyl, aryl, arylalkyl, alkylaryt or alkenylaryl radicals in which the number of carbon atoms carrying at least one halogen is at most equal to the number of non-halogenated carbon atoms, the carbon in α

position of group Y not being halogenated when Y is —

SO₂—

, said radicals optionally comprising functional ether, thioether, amine, imino, carboxyl, caibonyl, hydroxy, silyl, isocyanate or thioisocyanate groups;

f) radicals R_CC(R′

)(R″

)—

O—

in which R_C is an alkyl perfluorinatcd radical and R′ and

R″

are independently from one mother, an hydrogen atom or a radical as defined in a), b), c) or d) above;

g) radicals (R_B)₂N—

, in which the R_B, identical or different, as defined in a), b), c), d) and c) above, one of the R_B may be a hydrogen atom, or the two radicals R_B together fonn a bivalent radical which forms a cycle with N;

h) radicals consisting of a polymer chain;

i) radicals having one or more cationic ionophoric groups and/or one or more anionic ionophoric groups;

 

with the proviso that a substituent R_D may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_FS(O)_X—

N—

Y—

, or a segment of a polymer;

 

with the proviso that, when Y is a sulfonyl and R_D is a radical such as defined in a), R_F is R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

, CF₃C(R_A)F—

or a perhaloalkyl radical having 1 to 2 carbon atoms,

characterized in that M is an organic onium cation selected from the group consisting of R₃O (oxonium), NR₄ (ammonium), RC(NHR₂)₂ (amidinium), C(NHR₂)₃ (guanidinium), C₅R₆N (pyridinium), C₃R₅N₂ (imidazolium), C₂R₄N₃ (triazolium), C₃R₇N₂ (imidazolinium), SR₃ (sulfonium), PR₄ (phosphonium), IR₂ (iodonium), (C₆R₅)₃C (carbonium), the radicals R independently representing H or a radical selected from the group consisting of;

alkyl, alkenyl, oxa-alkyl oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl, sila-alkyl, sila-alkenyl, aryl, arylalkyl, alkylaryl, alkenylaryl radicals, dialkylamino radicals and dialkylazo radicals;

cyclic or heterocyclic radicals optionally comprising at least one lateral chain comprising heteroatoms such as nitrogen, oxygen, sulfur;

cyclic or heterocyclic radicals optionally comprising heteroatoms in the aromatic nuclei;

groups comprising a plurality of aromatic or heterocyclic, condensed or non-condensed nuclei, optionally containing at least one nitrogen, oxygen, sulfur or phosphorus atom;

 

with the proviso that a plurality of radicals R may together form aliphatic or aromatic cycles optionally enclosing the center carrying the cationic charge and characterized in that M is an organic onium cation that is part of a recurring unit of a polymer.

34. An ionically conducting material comprising an ionic compound in a solvent, wherein said ionic compound consists of an amide or salts therof, comprising an anionic pat associated with at least one calionic part M ^m in sufficient number to ensure an electronic neutrality thereto, characterized in that M is a hydroxonium, a nitrosonium NO , an ammonium —

NH₄ , a metallic cation having a valency m, an organic onium cation having a valency m or an organo-metallic cation having a valency m and in that the anionic part corresponds to the formula R_F—

SO_X—

N⁻

—

Z in which;

the group —

S(O)_X—

represents a sulfonic group —

SO₂—

or a sulfinyl group —

SO—

;

R_F is a halogen or a perhalogenated alkyl, alkylaryl, oxa-alkyl, aza-alkyl or thia-alkyl radical, or a radical corresponding to one of the formulae R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

or CF₃C(R_A)F—

in which R_A—

represents a non-perhalogenated organic radical;

Z represents an electro-attractor radical having a Hammett parameter at least equal to that of a phenyl radical, selected from;

j) —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, R′

_FCH₂—

(R′

_F being a perfluorinatcd radical) or a fluoroalkylthioxy radical,

jj) radicals comprising one or more aromatic nuclei optionally containing at least one hydrogen, oxygen, sulfur or phosphorus atom, said nuclei optionally being condensed nuclei and/or said nuclei optionally carrying at least one substituent selected from halogens, —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, CF₃CH₂—

, CF₂═

CF—

O—

, CF₂═

CF—

S—

, perufloroaklyl groups, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl radicals, polymer radicals, radicals having at least one cationic ionophoric group and/or at least one anionic ionophoric group;

 

with the proviso that a substituent Z may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_F—

S(O)_X—

N—

, or a polymer segment;

or

Z is a radical R_D—

Y—

in which Y is a sulfonyl, sulfinyl or phosphonyl group and R_D is a radical selected from the group consisting of;

a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, alicyclic, heterocyclic radicals, or polycyclic radicals;

b) alkyl or alkenyl radicals comprising at least one functional ether, thioether, amine, iminee, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate group;

c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which the aromatic nuclei and/or at least one substituent of the nucleus comprises heteroatoms selected from nitrogen, oxygen, sulfur;

d) radicals comprising condensed aromatic cycles which optionally comprise at least one heteroatom selected from nitrogen, oxygen, sulfur;

e) halogenated alkyl, alkenyl, aryl, arylalkyl alkylaryl or alkenylaryl radicals in which the number of carbon atoms carrying at least one halogon is at most equal to the number of non-halogenated carbon atoms, the carbon in α

position of group Y not being halogenated when Y is —

SO₂—

, said radicals optionally comprising functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanato groups;

f) radicals R_CC(R′

)(R″

)—

O—

in which R_C is an alkyl perfluorinated radical and R′ and

R″

are indpdently from one another, an hydrogen atom or a radical as dcfined in a), b), c) or d) above;

g) radicals (R_B)₂N—

, in which the R_B, identical or different, as defined in a), b), c), d) and c) above, one of the R_B may be a hydrogen atom, or the two radicals R_B togother form a bivalent radical which forms a cycle with N;

h) radicals consisting of a polymer chain;

i) radicals having one or more cationic ionophoric groups and/or one or more anionic ionophoric groups;

 

with the proviso that a substituent R_D may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_FS(O)X—

N—

Y—

, or a segment of a polymer;

 

with the proviso that, when Y is a sulfonyl and R_D is a radical such as defined in a), R_F is R_AC₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

, CF₃C(R_A)F—

or a perhaloalkyl radical having 1 to 2 carbon atoms,

 

characterized that M is an organic onium cation selected from the group consisting of R₃O (oxonium), NR₄ (ammonium), RC(NHR₂)₂ (amidinium), C(NHR₂)₃ (guanidinium), C₅R₆N (pyridinium), C₃R₅N₂ (imidazolium), C₂R₄N₃ (triazolium), C₃R₇N₂ (imidazolinium), SR₃ (sulfonium), PR₄ (phosphonium), IR₂ (iodonium), (C₆R₅)₃C (carbonium), the rdicals R independently representing H or a radical selected from the group consisting of;

alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl, sila-alkyl, sila-alkenyl, aryl, arylalkyl, alkylaryl, alkenylaryl radicals, dialkylamino radicals and dialkylazo radicals;

cyclic or heterocyclic radicals optionally comprising at least one lateral chain comprising heteroatoms such as nitrogen, oxygen, sulfur,

cyclic or heterocyclic radicals optionally comprising heteroatoms in the aromatic nuclei;

groups comprising a plurality of aromatic or heterocyclic, condensed or non-condensed nuclei, optionally containing at least one nitrogen, oxygen, sulfur or phosphorus atom;

with the proviso that a plurality of radicals R may together form aliphatic or aromatic cycles optionally enclosing the center carrying the cationic charge and characterized in that the cation M is a group having a bond —

N═

N—

, —

N═

N , a sulfonium group, an iodonium group, or a substituted or non-substituted arene-ferocenium cation, optionally incorporated in a polymer network.

35. An ionically conducting material comprising an ionic compound in a solvent, wherein said ionic compound consists of an amide or salts thereof, comprising an anionic part associated with at least one cationic part M ^m in sufficient number to ensure an electronic neutrality thereto, characterzed in that M is a hydroxonium, a nitrosonium NO , an ammionium —

NH₄ , a metallic cation having a valency m, an organic onium cation having a valency m or an organo-metallic cation having a valency m and in that the anionic part corresponds to the formula R_F—

SO_X—

N⁻

—

Z in which;

the group —

S(O)_X—

represents a sulfonic group —

SO₂—

or a sulfinyl group —

SO—

;

R_F is a halogen or a perhalogenated alkyl, alkylaryl, oxa-alkyl, aza-alkyl or thia-alkyl radical, or a radical corresponding to one of the formulae R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

or CF₃C(R_A)F—

in which R_A—

represents a non-perhalogenated organic radical;

Z represents an electro-attractor radical having a Hammett parameter at least equal to that of a phenyl radical, selected from;

j) —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, R′

_FCH₂—

(R′

_F being a perfluorinated radical) or a fluoroalkylthioxy radical,

jj) radicals comprising one or more aromatic nuclei optionally containing at least one hydrogen, oxygen, sulfur or phosphoms atom, said nuclei optionally being condensed nuclei and/or said nuclei optionally carrying at least one substituent selected from halogen, —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, CF₃CH₂—

, CF₂═

CF—

O—

, CF₂═

CF—

S—

, perfluoroalkyl groups, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl radicals, polymer radicals, radicals having at least one cationic ionophonic group and/or at least one anionic ionophoric group;

 

with the proviso that a substituent Z may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_F—

S(O)_X—

N—

, or a polymer segment;

or

Z is a radical R_D—

Y—

in which Y is a sulfonyl, sulfinyl or phosphonyl group and R_D is a radical selected from the group consisting of;

a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, alicyclic, heterocyclic radicals, or polycyclic radicals;

b) alkyl or alkenyl radicals comprising at least one functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate group;

c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which the aromatic nuclei and/or at least one substituent of the nucleus comprises heteroatoms selected from nitrogen, oxygen, sulfur;

d) radicals corprising condensed aromatic cycles which optionally comprise at least one heteroatom selected fronn nitrogen, oxygen, sulfur;

e) halogenated alkyl, alkenyl, aryl, alylalkyl alkylaryl or alkenylaryl radicals in which the number of carbon atoms carryng at least one halogen is at most equal to the number of non-halogenated carbon atoms, the carbon in α

position of group Y not being halogenated when Y is —

SO₂—

, said radicals optionally comprising functional other, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate groups;

f) radicals R_CC(R′

)(R″

)—

O—

in which R_C is an alkyl perfluorinated radical and R′ and

R″

are independently from one another, an hydrogen atom or a radical as defined in a), b), c) or d) above;

g) radicals (R_B)₂N—

, in which the R_B, identical or different, as defined in a), b), c), d) and e) above;

one of the R_B may be a hydrogen atom, or the two radicals R_B together form a bivalent radical which forms a cycle with N;

h) radicals consisting of a polymer chain;

i) radicals having one or more cationic ionophoric groups and/or one or more anionic ionophoric groups;

 

with the proviso that a substituent R_D may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_FS(O)x—

N—

Y—

, or a segment of a polymer;

 

with the proviso that when Y is a sulfonyl and R_D is a radical such as defined in a), R_F is R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

, CF₃C(R_A)F—

or a perhaloalkyl radical having 1 to 2 carbon atoms,

 

characterized in that M is an organic onium cation selected from the group consisting of R₃O (oxonium), NR₄ (ammonium), RC(NHR₂)₂ (amidinium), C(NHR₂)₃ (guanidinium), C₅R₆N (pyridinium), C₃R₅N₂ (imidazolium), C₂R₄N₃ (triazolium), C₃R₇N₂ (imidazolinium), SR₃ (sulfonium), PR₄ (phosphonium), IR₂ (iodonium), (C₆R₅)₃C (carbonium), the radicals R independently representing H or a radical selected from the group consisting of;

alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl, sila-alkyl, sila-alklenyl, aryl, arylalkyl, alkylaryl, alkenylaryl radicals, dialkylamino radicals and dialkylazo radicals;

cyclic or heterocyclic radicals optionally comprising at least one lateral chain comprising heteroatoms such as nitrogen, oxygen, sulfur;

cyclic or heterocyclic radicals optionally comprising heteroatoms in the aromatic nuclei;

groups comprising a plurality of aromatic or heterocyclic, condensed or non-condensed nuclei, optionally containing at least one nitrogen, oxygen, sulfur or phosphorus atom;

 

with the proviso that a plurality of radicals R may together forn aliphatic or aromatic cycles optionally enclosing the center carrying the cationic charge and characterized in that M is a cation that is a diaryliodonium cation, a dialkylaryliodonium cation, a triarylsulifonium cation, a trialkylaryl sulfonium cation, or a substituted or non-substituted phenacyl-alkyl sulfonium cation.

36. An ionically conducting material according to claim 35, chacterized in that M is a cation that is part of a polymer chain.

37. An ionically conducting material comprising an ionic compound in a solvent, wherein said ionic compound consists of an amide or salts thereof, comprising an anionic part associated with at least one cationic part M ^m in sufficient number to ensure an electronic neutrality thereto, characterized in that M is a hydroxonium, a nitrosonium NO , an ammonium —

NH₄ , a metallic cation having a valency m, an organic onium cation having a valency m or an organo-metallic cation having a valency m and in that the anionic part corresponds to the fomula R_F—

SO_X—

N⁻

—

Z in which;

the group —

S(O)_X—

represents a sulfonic group —

SO₂—

or a sulfinyl group —

SO—

;

R_F is a halogen or a perhalogenated alkyl, alkylaryl, oxa-alkyl, aza-alkyl or thia-alkyl radical, or a radical corresponding to one of the formulae R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

or CF₃C(R_A)F—

in which R_A—

represents a non-perhalogenated organic radical;

Z represents an electro-attractor radical having a Hammett parameter at least equal to that of a phenyl radical, selected from;

j) —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, R′

_FCH₂—

(R′

_F being a perfluorinated radical) or a fluoroalkylthioxy radical,

jj) radicals comprising one or more aromatic nuclei optionally containing at least one hydrogen, oxygen, sulfur or phosphorus atom, said nuclei optionally being condensed nuclei and/or said nuclei optionally carrying at least one substituent selected from halogens, —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, CF₃CH₂—

, CF₂═

CF—

O—

, CF₂═

CF—

S—

, perfluoroalkyl groups, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl radicals, polymer radical, radicals having at least one cationic ionophoric group and/or at least one anionic ionophoric group;

 

with the proviso that a substituent Z may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_FS(O)_X—

N—

, or a polymer segment;

or

Z is a radical R_D—

Y—

in which Y is a sulfonyl, sulfinyl or phosphonyl group and R_D is a radical selectcd from the group consisting of;

a) alkyl or alkenyl radicals aryl, arylalkyl, alkylaryl or alkenylaryl radicals, alicyclic, heterocyclic radicals, or polycyclic radicals;

b) alkyl or alkenyl radicals comprising at least one functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate group;

c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which the aromatic nuclei and/or at least one substituent of the nucleus comprises heteroatoms selected from nitrogen, oxygen, sulfur;

d) radicals comprising condensed aromatic cycles which optionally comprise at least one heteroatom selected from nitrogen, oxygen, sulfur;

e) halogenated alkyl, alkenyl, ayl arylalkyl, alkylaryl or alkenylaryl radicals in which the number of carbon atoms carrying at least one halogen is at most equal to the number of non-halogenated carbon atoms, the carbon in α

position of group Y not being halogenated when Y is —

SO₂—

, said radicals optionally comprising functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate groups;

f) radicals R_CC(R′

)(R″

) in which R_C is an alkly perfluorinated radical and R′ and

R″

are independently from one another, an hydrogen atom or a radical as defined in a), b), c) or d) above;

g) radicals (R_B)₂N—

, in which the R_B, identical or different, as defined in a), b), c), d) and e) above, one of the R_B may be a hydrogen atom, or the two radicals R_B together fonn a bivalent radical which forms a cycle with N;

h) radicals consisting of a polymer chain;

i) radicals having one or more cationic ionophonic groups and/or one or more anionic ionophoric groups;

 

with the proviso that a substituent R_D may be a monovalent radical, part of a multivalent radical carring a plurality of groups R_FS(O)x—

N—

Y—

, or a segment of a polymer;

 

with the proviso that when Y is a sulfonyl and R_D is a radical such as defined in a), R_F is R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

, CF₃C(R_A)F—

or a perhaloalkyl radical having 1 to 2 carbon atoms,

 

characterized in that M is an orgmiic onium cation selected from the group consisting of R₃O (oxonium), NR₄ (ammonium), RC(NHR₂)₂ (amidinium), C(NHR₂)₃ (guanidinium), C₅R₆N (pyridinium), C₃R₅N₂ (imidazolium), C₂R₄N₃ (triazolium), C₃R₇N₂ (imidazolinium), SR₃ (sulfonium), PR₄ (phosphonium), IR₂ (iodonium), (C₆R₅)₃C (carbonium), the radicals R independently representing H or a radical selected from the group consisting of;

alkyl, alkenyl, oxa-alkyl oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl, sila-alkyl, sila-alkenyl, aryl, arylalkyl, alkylaryl, alkenylaryl radicals, dialkylamino radicals and dialkylazo radicals;

cyclic or heterocyclic radicals optionally comprising at least one lateral chain comprising heteroatoms such as nitrogen, oxygen, sulfur;

cyclic or heterocyclic radicals optionally comprising heteroatoms in the aromatic nuclei;

groups comprising a plurlity of aromatic or heterocyclic, condensed or non-condensed nuclei, optionally containing at least one nitrogen, oxygen, sulfur or phosphorus atom;

 

with the proviso that a plurality of radicals R may together fonn aliphatic or aromatic cycles optionally enclosing the center carrying the cationic charge and characterized in that M is an organic cation, incorporating a group 2,2′

(azobis(2-2′

-imidazolinio-2-yl)propane)² or 2,2′

-2 azobis(2-amidiniopropane)² .

38. An ionically conducting material, comprising an ionic compound in a solvent, wherein said ionic compound consists of an amide or salts thereof, comprising an anionic part associated with at least one cationic part M ^m in sufficient number to ensure an electronic neutrality thereto, characterized in that M is a hydroxonium, a nitrosonium NO , an ammonium —

NH₄ , a metallic cation having a valency m, an organic onium cation having a valency m or an organo-metallic cation having a valency m and in that the anionic part corresponds to the formula R_F—

SO_x—

N⁻

—

Z in which;

the group —

S(O)_X—

represents a sulfonic group —

SO₂—

or a sulfinyl group —

SO—

;

R_F is a halogen or a perhalogenated alkyl, alkylaryl, oxa-alkyl, aza-alkyl or thia-alkyl radical, or a radical corresponding to one of the formulae R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

or CF₃C(R_A)F—

in which R_A—

represents a non-perhalogenated organic radical;

Z represents an electro-attractor radical having a Hammett parameter at least equal to that of a phenyl radical, selected from;

j) —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, R′

_FCH₂—

(R′

_F being a perfluorinated radical) or a fluoroalkylthioxy radical,

jj) radicals comprising one or more aromatic nuclei optionally containing at least one hydrogen, oxygen, sulfur or phosphorus atom, said nuclei optionally being condensed nuclei and/or said nuclei optionally carrying at least one substituent selected from halogens, —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, CF₃CH₂—

, CF₂═

CF—

O—

, CF₂═

CF—

S—

, perfluoroalkyl groups, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl radicals, polymer radicals, radicals having at least one cationic ionophoric group and/or at least one anionic lonophoric group;

 

with the proviso that a substituent Z may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_F—

S(O)_X—

N—

, or a polymer segment;

or

Z is a radical R_D—

Y—

in which Y is a sulfonyl, sulfinyl or phosphonyl group and R_D is a radical selected from the group consisting of;

a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, alicyclic, heterocyclic radicals, or polycyclic radicals;

b) alkyl or alkenyl radicals comprising at least one functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate group;

c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which the aromatic nuclei and/or at least one substituent of the nucleus comprises heteroatoms selected from nitrogen, oxygen, sulfur;

d) radicals comprising condensed aromatic cycles which optionally comprise at least one heteroatom selected from nitrogen, oxygen, sulfur;

e) halogenated alkyl, alkenyl, aryl, arylalkyl, alkylaryl or alkenylaryl radicals in which the number of carbon atoms carrying at least one halogen is at most equal to the number of non-halogenated carbon atoms, the carbon in α

position of group Y not being halogenated when Y is —

SO₂—

, said radicals optionally comprising functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate groups;

f) radicals R_CC(R′

)(R″

)—

O—

in which R_C is an alkyl perfluorinated radical and R′ and

R″

are independently from one another, an hydrogen atom or a radical as defined in a), b), c) or d) above;

g) radicals (R_B)₂N—

, in which the R_B, identical or different, as defined in a), b), c), d) and e) above, one of the R_B may be a hydrogen atom, or the two radicals R_B together form a bivalent radical which forms a cycle with N;

h) radicals consisting of a polymer chain;

i) radicals having one or more cationic ionophoric groups and/or one or more anionic ionophoric groups;

 

with the proviso that a substituent R_D may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_FS(O)x—

N—

Y—

, or a segment of a polymer;

 

with the proviso that, when Y is a sulfonyl and R_D is a radical such as defined in a), R_F is R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

, CF₃C(R_A)F—

or a perhaloalkyl radical having 1 to 2 carbon atoms;

further characterized in that the cation is a metallocenium, selected from the group consisting of cations derived from ferrocene, titanocene, zirconocene, indenocenium cations, arene metallocenium cations, cations of transition metals complexed with phosphine ligands optionally having a chirality and organometallic cations having one or more alkyl or aryl groups covalently fixed to an atom or a group of atoms, said cations optionally being part of a polymer chain.

39. An ionically conducting material, comprising an ionic compound in a solvent, wherein said ionic compound consists of an amide or salts thereof, comprising an anionic part associated with at least one cationic part M ^m in sufficient number to ensure an electronic neutrality thereto, characterized in that M is a hydroxonium, a nitrosoniurn NO , an annmonium —

NH₄ , a metallic cation having a valency m, an organic onium cation having a valency m or an organo-metallic cation having a valency m and in that the anionic part corresponds to the formula R_F—

SO_X—

N⁻

—

Z in which;

the group —

S(O)_X—

represents a sulfonic group —

SO₂—

or a sulfinyl group —

SO—

;

R_F is a halogen or a perhalogenated alkyl, alkylaryl, oxa-alkyl, aza-alkyl or thia-alkyl radical, or a radical corresponding to one of the formulae R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

or CF₃C(R_A)F—

in which R_A—

represents a non-perhalogenated organic radical;

Z represents an electro-attractor radical having a Hammett parameter at least equal to that of a phenyl radical, selected from;

j) —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, R′

_FCH₂—

(R′

_F being a perfluorinated radical) or a fluoroalkylthioxy radical,

jj) radicals comprising one or more aromatic nuclei optionally containing at least one hydrogen, oxygen, sulfur or phosphorus atom, said nuclei optionally being condensed nuclei and/or said nuclei optionally carrying at least one substituent selected from halogens, —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, CF₃CH₂—

, CF₂═

CF—

O—

, CF₂═

CF—

S—

, perfluoroalkyl groups, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl radicals, polymer radicals, radicals having at least one cationic ionophoric group and/or at least one anionic ionophoric group;

 

with the proviso that a substituent Z may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_F—

S(O)_X—

N—

, or a polymer segment;

or

Z is a radical R_D—

Y—

in which Y is a sulfonyl, sulfinyl or phosphonyl group and R_D is a radical selected from the group consisting of;

a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, alicyclic, heterocyclic radicals, or polycyclic radicals;

b) alkyl or alkenyl radicals comprising at least one functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate group;

c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which the aromatic nuclei and/or at least one substituent of the nucleus comprises heteroatoms selected from nitrogen, oxygen, sulfur;

d) radicals comprising condensed aromatic cycles which optionally comprise at least one heteroatom selected from nitrogen, oxygen, sulfur;

e) halogenated alkyl, alkenyl, aryl, arylalkyl, alkylaryl or alkenylaryl radicals in which the number of carbon atoms carrying at least one halogen is at most equal to the number of non-halogenated carbon atoms, the carbon in α

position of group Y not being halogenated when Y is —

SO₂—

, said radicals optionally comprising functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate groups;

f) radicals R_CC(R′

)(R″

)—

O—

in which R_C is an alkyl perfluorinated radical and R′ and

R″

are independently from one another, an hydrogen atom or a radical as defined in a), b), c) or d) above;

g) radicals (R_B)₂N—

, in which the R_B, identical or different, as defined in a), b), c), d) and e) above, one of the R_B may be a hydrogen atom, or the two radicals R_B together form a bivalent radical which forms a cycle with N;

h) radicals consisting of a polymer chain;

i) radicals having one or more cationic ionophoric groups and/or one or more anionic ionophoric groups;

 

with the proviso that a substituent R_D may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_FS(O)x—

N—

Y—

, or a segment of a polymer;

 

with the proviso that, when Y is a sulfonyl and R_D is a radical such as defined in a), R_F is R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

, CF₃C(R_A)F—

or a perhaloalkyl radical having 1 to 2 carbon atoms;

further characterized in that Z represents a recurring unit of a polymer chain.

40. An ionically conducting material, comprising an ionic compound in a solvent, wherein said ionic compound consists of an amide or salts thereof, comprising an anionic part associated with at least one cationic part M ^m in sufficient number to ensure an electronic neutrality thereto, characterized in that M is a hydroxonium, a nitrosonium NO , an ammonium —

NH₄ , a metallic cation having a valency m, an organic onium cation having a valency m or an organo-metallic cation having a valency m and in that the anionic part corresponds to the formula R_F—

SO_X—

N⁻

—

Z in which;

the group —

S(O)_X—

represents a sulfonic group —

SO₂—

or a sulfinyl group —

SO—

;

R_F is a halogen or a perhalogenated alkyl, alkylaryl, oxa-alkyl, aza-alkyl or thia-alkyl radical, or a radical corresponding to one of the formulae R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

or CF₃C(R_A)F—

in which R_A—

represents a non-perhalogenated organic radical;

Z represents an electro-attractor radical having a Hammett parameter at least equal to that of a phenyl radical, selected from;

j) —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, R′

_FCH₂—

(R′

_F being a perfluorinated radical) or a fluoroalkylthioxy radical,

jj) radicals comprising one or more aromatic nuclei optionally containing at least one hydrogen, oxygen, sulfur or phosphorus atom, said nuclei optionally being condensed nuclei and/or said nuclei optionally carrying at least one substituent selected from halogens, —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, CF₃CH₂—

, CF₂═

CF—

O—

, CF₂═

CF—

S—

, perfluoroalkyl groups, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl radicals, polymer radicals, radicals having at least one cationic ionophoric group and/or at least one anionic ionophonrc group;

 

with the proviso that a substituent Z may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_F—

S(O)_X—

N—

, or a polymer segment;

or

Z is a radical R_D—

Y—

in which Y is a sulfonyl, sulfinyl or phosphonyl group and R_D is a radical selected from the group consisting of;

a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, alicyclic, heterocyclic radicals, or polycyclic radicals;

b) alkyl or alkenyl radicals comprising at least one functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate group;

c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which the aromatic nuclei and/or at least one substituent of the nucleus comprises heteroatoms selected from nitrogen, oxygen, sulfur;

d) radicals comprising condensed aromatic cycles which optionally comprise at least one heteroatom selected from nitrogen, oxygen, sulfur;

e) halogenated alkyl, alkenyl, aryl, arylalkyl, alkylaryl or alkenylaryl radicals in which the number of carbon atoms carrying at least one halogen is at most equal to the number of non-halogenated carbon atoms, the carbon in α

position of group Y not being halogenated when Y is —

SO₂—

, said radicals optionally comprising functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate groups;

f) radicals R_CC(R′

)(R″

)—

O—

in which R_C is an alkyl perfluorinated radical and R′ and

R″

are independently from one another, an hydrogen atom or a radical as defined in a), b), c) or d) above;

g) radicals (R_B)₂N—

, in which the R_B, identical or different, as defined in a), b), c), d) and e) above, one of the R_B may be a hydrogen atom, or the two radicals R_B together form a bivalent radical which forms a cycle with N;

h) radicals consisting of a polymer chain;

i) radicals having one or more cationic ionophoric groups and/or one or more anionic ionophoric groups;

 

with the proviso that a substituent R_D may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_FS(O)x—

N—

Y—

, or a segment of a polymer;

 

with the proviso that, when Y is a sulfonyl and R_D is a radical such as defined in a), R_F is R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

, CF₃C(R_A)F—

or a perhaloalkyl radical having 1 to 2 carbon atoms;

further characterized in that the substituent Z is selected from the group consisting of —

OC_nF_{2n 1}, —

OC₂F₄H, —

SC_nF_{2n 1} and —

SC₂F₄H, —

OCF═

CF₂, —

SCF═

CF₂ and C_nF_2n 1CH<sub>2−

n</sub> being a whole number from 1 to 8.

41. Ionically conductive material comprising an ionic compound in a solvent, wherein said ionic compound consists of an amide or salts thereof, comprising an anionic part associated with at least one cationic part M ^m in sufficient number to ensure an electrotnic neutrality thereto, characterized in that M is a hydroxonium, a nitrosonium NO , an ammonium —

NH₄ , a metallic cation having a valency m, an organic onium cation having a valency m or an organo-motallic cation having a valency m and in that the anionic part corresponds to the formula R_F—

SO_X—

N —

Z in which;

the group —

S(O)_X—

represents a sulfonic group —

SO₂—

or a sulfinyl group —

SO—

;

R_F is a halogen or a perhalogenated alkyl, alkylaryl oxa-alkyl, aza-akyl or thia-alkyl radical, or a radical corresponding to one of the formulae R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

or CF₃C(R_A)F—

in which R_A—

represents a non-perhalogenated organic radical;

Z represents an electro-attractor radical having a Hammett parameter at least equal to that of a phenyl radical, selected from;

j) —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, R′

_FCH₂—

(R_F being a perfluorinated radical) or a fluroalkylthioxy radical,

jj) radicals comprising one or more aromatic nuclei optionally containing at least one hydrogen, oxygen, sulfur or phosphorus atom, said nuclei optionally being condensed nuclei and/or said nuclei optionally carrying at least one substituent selected from halogens, —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, CF₃CH₂—

, CF₂═

CF—

O—

, CF₂═

CF—

S—

, perfluoroalkyl groups, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl radicals, polymer radicals, radicals having at least one cationic ionophoric group and/or at least one anionic ionophoric group;

 

with the proviso that a substituent Z may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_FS(O)_X—

N—

, or a polymer segment;

or

Z is a radical R_D—

Y—

in which Y is a sulfonyl, sulfinyl or phosphonyl group and R_D is a radical selected from the group consisting of;

a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, alicyclic, heterocyclic radicals, or polycyclic radicals;

b) alkyl or alkenyl radicals comprising at least one functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate group;

c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which the aromatic nuclei and/or at least one substituent of the nucleus comprises heteroatoms selected from nitrogen, oxygen, sulfur,

d) radicals comprising condensed aromatic cycles which optionally comprise at least one heteroatom selected from nitrmgon, oxygen, sulfur;

e) halogenated alkyl, alkenyl, aryl, arylalkyl, alkylaryl or alkenylaryl radicals in which the number of carbon atoms carrying at least one halogen is at most equal to the number of non-halogenated carbon atoms, the carbon in α

position of group Y not being halogenated when Y is —

SO₂—

, said radicals optionally comprising functional other, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate groups;

f) radicals R_CC(R′

)(R″

)—

in which R_C is an alkyl perfluorinated radical and R′ and

R″

are independently from one another, an hydrogen atom or a radical as defined in a), b), c) or d) above;

g) radicals (R_B)₂N—

, in which the R_B, identical or different, as defined in a), b), c), d) and e) above, one of the R_B may be a hydrogen atom, or the two radicals R_B together form a bivalent radical which forms a cycle with N;

h) radicals consisting of a polymer chain;

i) radicals having one or more cationic ionophoric groups and/or one or more anionic ionophoric groups;

 

with the proviso that a substituent R_D may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_FS(O)x—

N—

Y—

, or a segment of a polymer;

 

with the proviso that when Y is a sulfonyl and R_D is a radical such as defined in a), R_F is R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

, CF₃C(R_A)F—

or a perhaloalkyl radical having 1 to 2 carbon atoms;

 

characterized in that the solvent is a crosslinked or non-cross-linked solvating polymer, which may carry grafted ionic groups.

42. Ionically conductive material according to claim 41, characterized in that the solvating polymer is selected from polyethers of linear structure, comb or blocks, which may form a network, based on poly (ethylene oxide), copolymers containing ethylene oxide, propylene oxide or allylglycidylether units, polyphosphazenes, cross-linked networks based on polyethylene glycol cross-linked with isocyanates, polymer networks obtained by polycondensation and carrying groups which enable the incorporation of cross-linkable groups and block copolymers in which some blocks carry functions which have redox properties.

43. Ionically conductive material, comprising an ionic compound in a solvent, wherein said ionic compound consists of an amide or salts thereof, comprising an anionic part associated with at least one cationic part M ^m in sufficient number to ensure an electronic neutrality thereto, characterized in that M is a hydroxonium, a nitrosonium NO , an ammonium —

NH₄ , a metallic cation having a valency m, an organic onium cation having a valency m or an organo-metallic cation having a valency m and in that the anionic part corresponds to the formula R_F—

SO_X—

N⁻

—

Z in which;

the group —

S(O)_X—

represents a sulfonic group —

SO₂—

or a sulfinyl group —

SO—

;

R_F is a halogen or a perhalogenated alkyl, alkylaryl, oxa-alkyl, aza-alkyl or thia-alkyl radical, or a radical corresponding to one of the formulae R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

or CF₃C(R_A)F—

in which R_A—

represents a non-perhalogenated organic radical;

Z represents an electro-attractor radical having a Hammett parameter at least equal to that of a phenyl radical, selected from;

j) —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, R′

_FCH₂—

(R′

_F being a perfluorinated radical) or a fluoroalkylthioxy radical,

jj) radicals comprising one or more aromatic nuclei optionally containing at least one hydrogen, oxygen, sulfur or phosphorus atom, said nuclei optionally being condensed nuclei and/or said nuclei optionally carrying at least one substituent selected from halogens, —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, CF₃CH₂—

, CF₂═

CF—

O—

, CF₂═

CF—

S—

, perfluoroalkyl groups, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl radicals, polymer radicals, radicals having at least one cationic ionophoric group and/or at least one anionic ionophoric group;

 

with the proviso that a substituent Z may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_F—

S(O)_X—

N—

, or a polymer segment;

or

Z is a radical R_D—

Y—

in which Y is a sulfonyl, sulfinyl or phosphonyl group and R_D is a radical selected from the group consisting of;

a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, alicyclic, heterocyclic radicals, or polycyclic radicals;

b) alkyl or alkenyl radicals comprising at least one functional ether, thioether amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate group;

c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which the aromatic nuclei and/or at least one substituent of the nucleus comprises heteroatoms selected from nitrogen, oxygen, sulfur;

d) radicals comprising condensed aromatic cycles which optionally comprise at least one heteroatom selected from nitrogen, oxygen, sulfur;

e) halogenated alkyl, alkenyl, aryl, arylalkyl, alkylaryl or alkenylaryl radicals in which the number of carbon atoms carrying at least one halogen is at most equal to the number of non-halogenated carbon atoms, the carbon in α

position of group Y not being halogenated when Y is —

SO₂—

, said radicals optionally comprising functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate groups;

f) radicals R_CC(R′

)(R″

)—

O—

in which R_C is an alkyl perfluorinated radical and R′ and

R″

are independently from one another, an hydrogen atom or a radical as defined in a), b), c) or d) above;

g) radicals (R_B)₂N—

, in which the R_B, identical or different, as defined in a), b), c), d) and e) above, one of the R_B may be a hydrogen atom, or the two radicals R_B together form a bivalent radical which forms a cycle with N;

h) radicals consisting of a polymer chain;

i) radicals having one or more cationic ionophoric groups and/or one or more anionic ionophoric groups;

 

with the proviso that a substituent R_D may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_FS(O)x—

N—

Y—

, or a segment of a polymer;

 

with the proviso that, when Y is a sulfonyl and R_D is a radical such as defined in a), R_F is R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

, CF₃C(R_A)F—

or a perhaloalkyl radical having 1 to 2 carbon atoms;

further characterized in that the solvent essentially consists of a liquid aprotic solvent and a polar polymer solvent comprising units containing at least one heteroatom selected from sulfur, oxygen, nitrogen and fluorine.

44. Ionically conductive material according to claim 43, characterized in that the polar polymer mainly contains units derived from acrylonitrile, vinylidene fluoride, N-vinylpyrrolidone or methyl methacrylate.

45. Ionically conductive material, comprising an ionic compound in a solvent, wherein said ionic compound consists of an amide or salts thereof, comprising an anionic part associated with at least one cationic part M ^m in sufficient number to ensure an electronic neutrality thereto, characterized in that M is a hydroxonium, a nitrosonium NO , an ammonium —

NH₄ , a metallic cation having a valency m, an organic onium cation having a valency m or an organo-metallic cation having a valency m and in that the anionic part corresponds to the formula R_F—

SO_X—

N⁻

—

Z in which;

the group —

S(O)_X—

represents a sulfonic group —

SO₂—

or a sulfinyl group —

SO—

;

R_F is a halogen or a perhalogenated alkyl, alkylaryl, oxa-alkyl, aza-alkyl or thia-alkyl radical, or a radical corresponding to one of the formulae R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

or CF₃C(R_A)F—

in which R_A—

represents a non-perhalogenated organic radical;

Z represents an electro-attractor radical having a Hammett parameter at least equal to that of a phenyl radical, selected from;

j) —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, R′

_FCH₂—

(R′

_F being a perfluorinated radical) or a fluoroalkylthioxy radical,

jj) radicals comprising one or more aromatic nuclei optionally containing at least one hydrogen, oxygen, sulfur or phosphorus atom, said nuclei optionally being condensed nuclei and/or said nuclei optionally carrying at least one substituent selected from halogens, —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, CF₃CH₂—

, CF₂═

CF—

O—

, CF₂═

CF—

S—

, perfluoroalkyl groups, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl radicals, polymer radicals, radicals having at least one cationic ionophoric group and/or at least one anionic ionophoric group;

 

with the proviso that a substituent Z may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_F—

S(O)_X—

N—

, or a polymer segment;

or

Z is a radical R_D—

Y—

in which Y is a sulfonyl, sulfinyl or phosphonyl group and R_D is a radical selected from the group consisting of;

a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, alicyclic, heterocyclic radicals, or polycyclic radicals;

b) alkyl or alkenyl radicals comprising at least one functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate group;

c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which the aromatic nuclei and/or at least one substituent of the nucleus comprises heteroatoms selected from nitrogen, oxygen, sulfur;

d) radicals comprising condensed aromatic cycles which optionally comprise at least one heteroatom selected from nitrogen, oxygen, sulfur;

e) halogenated alkyl, alkenyl, aryl, arylalkyl, alkylaryl or alkenylaryl radicals in which the number of carbon atoms carrying at least one halogen is at most equal to the number of non-halogenated carbon atoms, the carbon in α

position of group Y not being halogenated when Y is —

SO₂—

, said radicals optionally comprising functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate groups;

f) radicals R_CC(R′

)(R″

)—

O—

in which R_C is an alkyl perfluorinated radical and R′ and

R″

are independently from one another, an hydrogen atom or a radical as defined in a), b), c) or d) above;

g) radicals (R_B)₂N—

, in which the R_B, identical or different, as defined in a), b), c), d) and e) above, one of the R_B may be a hydrogen atom, or the two radicals R_B together form a bivalent radical which forms a cycle with N;

h) radicals consisting of a polymer chain;

i) radicals having one or more cationic ionophoric groups and/or one or more anionic ionophoric groups;

 

with the proviso that a substituent R_D may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_FS(O)x—

N—

Y—

, or a segment of a polymer;

 

with the proviso that, when Y is a sulfonyl and R_D is a radical such as defined in a), R_F is R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

, CF₃C(R_A)F—

or a perhaloalkyl radical having 1 to 2 carbon atoms;

further characterized in that it additionally contains at least one second salt.

46. Ionically conductive material, comprising an ionic compound in a solvent, wherein said ionic compound consists of an amide or salts thereof, comprising an anionic part associated with at least one cationic part M ^m in sufficient number to ensure an electronic neutrality thereto, characterized in that M is a hydroxonium, a nitrosonium NO , an ammonium —

NH₄ , a metallic cation having a valency m, an organic onium cation having a valency m or an organo-metallic cation having a valency m and in that the anionic part corresponds to the formula R_F—

SO_X—

N⁻

—

Z in which;

the group —

S(O)_X—

represents a sulfonic group —

SO₂—

or a sulfinyl group —

SO—

;

R_F is a halogen or a perhalogenated alkyl, alkylaryl, oxa-alkyl, aza-alkyl or thia-alkyl radical, or a radical corresponding to one of the formulae R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

or CF₃C(R_A)F—

in which R_A—

represents a non-perhalogenated organic radical;

Z represents an electro-attractor radical having a Hammett parameter at least equal to that of a phenyl radical, selected from;

j) —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, R′

_FCH₂—

(R′

_F being a perfluorinated radical) or a fluoroalkylthioxy radical,

jj) radicals comprising one or more aromatic nuclei optionally containing at least one hydrogen, oxygen, sulfur or phosphorus atom, said nuclei optionally being condensed nuclei and/or said nuclei optionally carrying at least one substituent selected from halogens, —

CN, —

NO₂, —

SCN, —

N₃, —

CF₃, CF₃CH₂—

, CF₂═

CF—

O—

, CF₂═

CF—

S—

, perfluoroalkyl groups, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl radicals, polymer radicals, radicals having at least one cationic ionophoric group and/or at least one anionic ionophoric group;

 

with the proviso that a substituent Z may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_F—

S(O)_X—

N—

, or a polymer segment;

or

Z is a radical R_D—

Y—

in which Y is a sulfonyl, sulfinyl or phosphonyl group and R_D is a radical selected from the group consisting of;

a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, alicyclic, heterocyclic radicals, or polycyclic radicals;

b) alkyl or alkenyl radicals comprising at least one functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate group;

c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which the aromatic nuclei and/or at least one substituent of the nucleus comprises heteroatoms selected from nitrogen, oxygen, sulfur;

d) radicals comprising condensed aromatic cycles which optionally comprise at least one heteroatom selected from nitrogen, oxygen, sulfur;

e) halogenated alkyl, alkenyl, aryl, arylalkyl, alkylaryl or alkenylaryl radicals in which the number of carbon atoms carrying at least one halogen is at most equal to the number of non-halogenated carbon atoms, the carbon in α

position of group Y not being halogenated when Y is —

SO₂—

, said radicals optionally comprising functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate groups;

f) radicals R_CC(R′

)(R″

)—

O—

in which R_C is an alkyl perfluorinated radical and R′ and

R″

are independently from one another, an hydrogen atom or a radical as defined in a), b), c) or d) above;

g) radicals (R_B)₂N—

, in which the R_B, identical or different, as defined in a), b), c), d) and e) above, one of the R_B may be a hydrogen atom, or the two radicals R_B together form a bivalent radical which forms a cycle with N;

h) radicals consisting of a polymer chain;

i) radicals having one or more cationic ionophoric groups and/or one or more anionic ionophoric groups;

 

with the proviso that a substituent R_D may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_FS(O)_X—

N—

Y—

, or a segment of a polymer;

 

with the proviso that, when Y is a sulfonyl and R_D is a radical such as defined in a), R_F is R_ACF₂—

, R_ACF₂CF₂—

, R_ACF₂CF(CF₃)—

, CF₃C(R_A)F—

or a perhaloalkyl radical having 1 to 2 carbon atoms;

further characterized in that it additionally contains a mineral or organic charge in the form of powder or fibres.