Solid electrolyte for an electrochemical generator

Patent metadata

Field	Value
Publication number	US-10870730-B2
Application number	US-201615761305-A
Country	US
Kind code	B2
Filing date	Sep 19, 2016
Priority date	Sep 21, 2015
Publication date	Dec 22, 2020
Grant date	Dec 22, 2020

Abstract

A compound containing at least one species of formula (I):

where:
A x− is an anion of valency x equal to 1 or 2 chosen from sulfonate, sulfonylimide of —SO 2 —N − —SO 2 C y F 2y+1 type with y being an integer between 0 and 4; borate, borane, phosphate, phosphinate, phosphonate, silicate, carbonate, sulfide, selenate, nitrate and perchlorate anions;
C x+ is a counter-cation of the anion A x− , chosen from a proton H + and alkali metal and alkaline-earth metal cations;
p is an integer ranging from 1 to 10;
E is an organic spacer comprising a linear sequence of at least two covalent bonds;
n is an integer greater than or equal to 2; and
G represents:
(a) a group

or (b) a group

the anion A x− being covalently bonded to the polycyclic group Ar.

First claim

The invention claimed is:

1. A compound comprising at least one species of formula (I):

wherein:
A x− is an anion of valency x equal to 1 or 2 chosen from sulfonate, sulfonylimide of —SO 2 —N − —SO 2 C y F 2y+1 type with y being an integer between 0 and 4; borate, borane, phosphate, phosphinate, phosphonate, silicate, carbonate, sulfide, selenate, nitrate and perchlorate anions;
C x+ is a counter-cation of the anion A x− , chosen from a proton H + and alkali metal and alkaline-earth metal cations:
p is an integer ranging from 1 to 10;
E is an organic spacer comprising a linear sequence of at least two covalent bonds;
n is an integer greater than or equal to 2; and
G represents:
(a) a group

in which:
X represents N, P or Si—R, with R representing a hydrogen atom or a C 1-4 -alkyl group,
Ar represents a polycyclic group formed from 2 to 6 rings, at least one of which is aromatic, each ring being, independently of each other, 4- to 6-membered, said polycyclic group possibly including up to 18 heteroatoms;
-□ represents a bond with the spacer E; and
-* represents one or more bonds with said anions A x− ;
or (b) a group

in which:
X 1 and X 2 , which may be identical or different, represent NR, O or S, with R representing a hydrogen atom or a C 1-4 -alkyl group; -□ represents a bond with the spacer E; and
-* represents one or more bonds with said anions A x− ;
Ar is as defined previously;
said anion(s) A x− being covalently bonded to the polycyclic group Ar.

2. The compound as claimed in claim 1 , said compound being a polymer comprising, or even being formed from, monomer units of formula (I′) below:

in which G, E, A x− , C x+ and p are as defined in claim 1 .

3. The compound as claimed in claim 1 , said compound being a polymer comprising, or even being formed from, monomer units of formula (II):

in which E, Ar, A x− , C x+ and p are as defined in claim 1 .

4. The compound as claimed in claim 1 , wherein Ar has one of the following polycyclic backbones:

5. The compound as claimed in claim 1 , wherein Ar is an aromatic bicyclic group.

6. The compound as claimed in claim 1 , wherein E is a linear or branched, saturated or unsaturated aliphatic chain, containing at least two double bonds, said chain being optionally interrupted with one or more heteroatoms, with one or more metalloids, and/or with one or more aromatic or nonaromatic, 4- to 6-membered (hetero)cycles; said chain being optionally substituted with one or more fluorine atoms and/or with one or more groups R 1 ,
R 1 representing a group chosen from a hydroxyl group, optionally in protonated form —O − C + ; an —NH 2 group and an oxo group.

7. The compound as claimed in claim 1 , wherein E represents a saturated linear C 4 to C 20 aliphatic chain, said chain being optionally interrupted with one or more heteroatoms, and/or with one or more aromatic or nonaromatic 4- to 6-membered rings, said chain being optionally substituted with one or more hydroxyl groups.

8. The compound as claimed in claim 7 , wherein said optional heteroatom is an oxygen atom.

9. The compound as claimed in claim 7 , wherein said optional aromatic or nonaromatic 4- to 6-membered ring is a benzene ring.

10. The compound as claimed in claim 7 , wherein said optional hydroxyl group is in a protonated form —O − C + .

11. The compound as claimed in claim 1 , wherein n is between 2 and 1500.

12. The compound as claimed in claim 1 , wherein A x− is a sulfonate anion or a trifluoromethylsulfonylimide anion.

13. The compound as claimed in claim 1 , wherein C x+ is a proton H + or the Li + cation.

14. The compound as claimed in claim 1 , said compound being a polymer comprising, or even being formed from, monomer units of formula (III):

in which E, A X− and C x+ are as defined in claim 1 .

15. The compound as claimed in claim 1 , wherein X 1 and X 2 both represent NH or O.

16. The compound as claimed in claim 1 , wherein Ar is an aromatic bicyclic group with a naphthalene aromatic backbone.

17. The compound as claimed in claim 1 , wherein Ar is a naphthalene group.

18. The compound as claimed in claim 1 , wherein E is a linear or branched, saturated or unsaturated aliphatic chain, containing at least two double bonds, said chain being optionally interrupted with one or more heteroatoms, with one or more metalloids, and/or with one or more aromatic or nonaromatic, 4- to 6-membered (hetero)cycles; said chain being optionally substituted with one or more fluorine atoms and/or with one or more groups R 1 ,
R 1 representing a group chosen from a hydroxyl group, optionally in protonated form —O − C + ; an —NH 2 group.

19. A solid electrolyte comprising, one or more compounds as claimed in claim 1 , in the organized state.

20. The electrolyte as claimed in claim 19 , said electrolyte having an ion conductivity at 120° C. of greater than or equal to 10 −9 S/cm.

21. The electrolyte as claimed in claim 19 , said electrolyte an ion conductivity at 200° C. of greater than or equal to 10 −7 S/cm.

22. A process for forming a film comprising a solid electrolyte on the surface of a substrate, comprising:
(a1) adding a solution comprising at least one compound as claimed in claim 1 in a polar solvent;
(b1) depositing said solution from (a1) onto the surface of said substrate; and
(c1) evaporating the solvent under conditions suitable for forming a film comprising the solid electrolyte formed from the compound of formula (I) in its organized state.

23. The process as claimed in claim 22 , wherein said film comprising the solid electrolyte has a thickness of between 5 and 50 μm.

24. The process as claimed in claim 22 , said process further comprising exposing said film formed to an electric or magnetic field or to ionizing radiation.

25. A process for forming a solid electrolyte film, which is self-supported or supported on a substrate, comprising:
(a2) forming a powder from a compound as claimed in claim 1 ;
(b2) melt-extruding said powder in the form of a solid electrolyte film formed from said compound of formula (I) in its organized state; and
(c2) spreading said electrolyte film optionally on the surface of a substrate.

26. The process as claimed in claim 25 , in which said film comprising the solid electrolyte has a thickness of between 5 and 50 μm.

27. The process as claimed in claim 25 , said process further comprising exposing said film formed to an electric or magnetic field or to ionizing radiation.

28. A composite electrode for an electrochemical system, comprising

Assignees

• Commissariat Energie Atomique

Inventors

• Leclere Melody
• Picard Lionel

Classifications

• H01M8/1034

  having phosphorus, e.g. sulfonated polyphosphazenes [S-PPh] · CPC title

• H01M8/1037

  having silicon, e.g. sulfonated crosslinked polydimethylsiloxanes · CPC title

• C08J2379/02

  Polyamines · CPC title

• C08G77/54

  Nitrogen-containing linkages · CPC title

• H01M2300/0082

  Organic polymers · CPC title