Polymers containing grafted bis(sulfonyl)imide sodium or lithium salts, methods for production thereof and uses of same as electrolytes for batteries

Patent metadata

Field	Value
Publication number	US-10141603-B2
Application number	US-201515327609-A
Country	US
Kind code	B2
Filing date	Jul 20, 2015
Priority date	Jul 23, 2014
Publication date	Nov 27, 2018
Grant date	Nov 27, 2018

Abstract

The invention relates to novel polymers containing grafted sodium or lithium bis(sulfonyl)imides, to the methods for the production thereof, and to the uses of same as electrolytes in batteries.

First claim

The invention claimed is:

1. A polymer of the polyaryl ether ketone family or a polyether sulfone polymer containing a grafted bis(sulfonyl)imide lithium or sodium salt selected from the group consisting of bis(sulfonyl)imide lithium or sodium salts satisfying formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV

wherein:
M represents a lithium or sodium atom
R represents a group or different groups chosen from:
an alkyl or cycloalkyl group having 1 to 30 linear or branched carbon atoms optionally substituted by a cycloalkyl, aryl, perfluoroalkyl polyfluoroalkyl, mono or polyethoxylated motif;
a perfluoro- or polyfluoroalkyl group optionally substituted by aromatic groups;
an aryl or polyaryl group optionally substituted by alkyl, cycloalkyl, polyfluoro- or perfluoroalkyl chains, nitrile functions, alkyl or alkylsulfonyl functions, fluorine atoms;

m represents the percentage of polymer units having an oxoaryl or dioxoaryl motif having a grafted bis(sulfonyl)imide salt, this percentage varying between 50 and 100%,
n represents the percentage of polymer units having no oxoaryl or dioxoaryl motif functionalized by a bis(sulfonyl)imide motif, this percentage varying between 0 and 50%,
p represents the number of polymer units of the polymer; p varying from 40 to 300.

2. The polymer according to claim 1 , wherein:
M represents a lithium or sodium atom;
R represents one or more different groups chosen from:
an alkyl group with 1 to 10 carbon atoms;
a trifluoromethyl, pentafluoroethyl, nonafluorobutyl, 1,1,2,2-tetrafluoroethyl group;
an aryl group of the phenyl, tolyl, naphthyl, trifluoromethylphenyl, bis(trifluoromethyl)phenyl, cyanophenyl, alkylsulfonylphenyl, arylsulfonylphenyl, methoxyphenyl, butoxyphenyl, pentafluorophenyl, alkylsulfonylphenyl, fluorophenyl type,
m represents the percentage of polymer units having an oxoaryl or dioxoaryl motif functionalized by a bis(sulfonyl)imide motif, this percentage varying between 90 and 100%;

n represents the percentage of polymer units having an oxoaryl or a dioxoaryl motif non-functionalized by a bis(sulfonyl)imide motif, this percentage varying between 0 and 10%;
p represents the number of polymer units of the polymer; p varying from 60 to 200.

3. The polymer according to claim 2 , wherein R is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, and ethylhexyl groups.

4. The polymer according to claim 1 , wherein:
M represents a lithium or sodium atom,
R is a methyl, ethyl, propyl, cyclopropyl, butyl, 1-decyl, 1-dodecyl, 1-hexanedecyl, 1-octyldecyl, (7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methyl, ((1R)-7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methyl, (1S)-(7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methyl, cyclohexylmethyl, trifluoromethyl, phenyl, tolyl, naphthyl, 4-trifluoromethylphenyl, 3,5-bis(trifluoromethyl)phenyl, 4-cyanophenyl, 1,1,2,2,2-pentafluoroethanyl, nonafluorobutyl, pentafluorophenyl, 2,3,5,6-tetrafluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 3,5-difluorophenyl, 2,3,4,5,6-pentafluorophenyl, 4-cyanophenyl, 4-(trifluoromethyl)phenyl, 3-(trifluoromethyl)phenyl, 2-(trifluoromethyl)phenyl, 4-methylphenyl, 1-naphthyl, 2-naphthyl, 3,5-difluorobenzyl, 4-fluorobenzyl, 3-trifluoromethylbenzyl, 4-trifluoromethylbenzyl, 2,5-dimethylbenzyl, 2-phenylethyl, 4-methoxyphenyl, 4-n-butylphenyl, 4-t-butylphenyl, 4-butoxyphenyl, 2-fluoro-5-(trifluoromethyl)phenyl, or 4-ethylphenyl group;

m represents the percentage of polymer units having a dioxoaryl motif functionalized by a bis(sulfonyl)imide, this percentage varying between 90 and 100%;
n represents the percentage of polymer units having a dioxoaryl motif non-functionalized by a bis(sulfonyl)imide, this percentage varying between 0 and 10%;
p represents the number of polymer units of the polymer, p varying from 60 to 200.

5. A method for synthesis of a polymer according to claim 1 , comprising:
in a first step, performing the chlorosulfonation of a polymer selected from the group consisting of polymers of formulas XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII by a mixture of chlorosulfonic acid, thionyl chloride and a formamide

wherein:
p represents the number of polymer units of the polymer, p varying from 40 to 300, in order to obtain the polymer selected from the group consisting of polymers of formulas XXIV, XXV, XXVI, XVII, XXVIII, XIX, XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV, XXXVI, XXXVII and XXXVIII

wherein:
m represents the percentage of polymer units having an oxoaryl or dioxoaryl motif functionalized by a chlorosulfonated group, this percentage varying between 50 and 100%,
n represents the percentage of polymer units having a dioxoaryl motif non-functionalized by a chlorosulfonated group, this percentage varying between 0 and 50%,
p represents the number of polymer units of the polymer, p varying from 40 to 300,

in a second step, producing a reaction on the polymer selected from the group consisting of polymers of formulas XXIV, XXV, XXVI, XVII, XXVIII, XIX, XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV, XXXVI, XXXVII and XXXVIII with a sulfonamide of formula XXXIX in a solvent medium

wherein
R represents a group or different groups chosen from:
an alkyl or cycloalkyl group having 1 to 30 linear or branched carbon atoms, optionally substituted by a cycloalkyl, aryl, perfluoroalkyl, polyfluoroalkyl, mono or polyethoxyl motif;
a perfluoro- or polyfluoroalkyl group optionally substituted by aromatic groups;
an aryl or polyaryl group optionally substituted by alkyl, cycloalkyl, polyfluoro- or perfluoroalkyl, motifs, by nitrile functions, by alkyl- or alkylsulfonyl functions, by fluorine atoms;

m represents the percentage of polymer units having an oxoaryl or dioxoaryl motif having a grafted bis(sulfonyl)imide, this percentage varying between 50 and 100%, in the presence of a lithium or sodium base.

6. The method according to claim 5 , wherein the R group of the XXXIX sulfonamide is chosen from the methyl, ethyl, propyl, cyclopropyl, butyl, 1-decyl, 1-dodecyl, 1-hexanedecyl, 1-octyldecyl, (7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methyl, (1R)-7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methyl, (1S)-(7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methyl, cyclohexylmethyl, phenyl, tolyl, naphthyl, 4-trifluoromethylphenyl, 3,5-bis (trifluoromethyl)phenyl, 2,5-bis (trifluoromethyl)phenyl, 4-cyanophenyl, 1,1,2,2,2-pentafluoroethanyl, nonafluorobutyl, pentafluorophenyl, 2,3,5,6-tetrafluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 3,5-difluorophenyl, 2,3,4,5,6-pentafluorophenyl, 4-cyanophenyl, 3 (trifluoromethyl)phenyl, 2-(trifluoromethyl)phenyl, 4-methylphenyl, 1-naphthyl, 2-naphthyl, 3,5-difluorobenzyl, 4-fluorobenzyl, 3-trifluoromethylbenzyl, 4-trifluoromethylbenzyl, 2,5-dimethylbenzyl, 2-phenylethyl, 4-methoxyphenyl, 4-n-butylphenyl, 4-t-butylphenyl, 4-butoxyphenyl, 2-fluoro-5-(trifluoromethyl)phenyl, or 4-ethylphenyl groups.

7. The method according to claim 5 , wherein the chloros

Assignees

• Cdp Innovation
• Centre Nat Rech Scient
• Univ Aix Marseille
• Cpd Innovation

Inventors

• Desmurs Jean-Roger
• DUNACH CLINET Elisabet
• Knauth Philippe
• MORIZUR Vincent
• Olivero Sandra

Classifications

• H01M2300/0082

  Organic polymers · CPC title

• C08G65/4012 Primary

  Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01B1/128

  comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes · CPC title

• H01M10/0565 Primary

  Polymeric materials, e.g. gel-type or solid-type · CPC title