Electrolyte for electrochemical generator

Patent metadata

Field	Value
Publication number	US-10833368-B2
Application number	US-201615761257-A
Country	US
Kind code	B2
Filing date	Sep 20, 2016
Priority date	Sep 21, 2015
Publication date	Nov 10, 2020
Grant date	Nov 10, 2020

Abstract

Thermotropic ionic liquid crystal molecules, comprising a so-called rigid part, a so-called flexible part bonded covalently, directly or via a spacer, to said rigid part, and one or more ionic groups bonded covalently to said rigid part. Said molecules can be used as electrolytes in an electrochemical device, in particular a lithium-ion battery.

First claim

The invention claimed is:

1. An electrolyte, comprising a thermotropic ionic liquid crystal molecule, in a mesomorphic state,
wherein the molecule comprises:
a rigid part, comprising a polycyclic group Ar formed from 2 to 6 rings, at least one of which is aromatic, the rings being, independently of each other, 4- to 6-membered, the polycyclic group optionally including up to 18 heteroatoms;
a flexible part, formed from one or more linear or branched, saturated or unsaturated, fluorinated or nonfluorinated aliphatic chains, the chain(s) being optionally interrupted with one or more heteroatoms, metalloids, and/or aromatic or nonaromatic, 4- to 6-membered (hetero)cycles, and optionally substituted with one or more hydroxyl, —NH 2 , and/or oxo groups, the flexible part being covalently bonded, directly or via a spacer, to the rigid part; and
an ionic group -A x− C x+ ,
wherein -A x− is an anionic group covalently bonded to the rigid part, with x being an integer equal to 1 or 2, -A x− being a sulfonate anion, sulfonylimide of formula —SO 2 —N − —SO 2 C y F 2y+1 with y being an integer ranging from 0 to 4, borate, borane, phosphate, phosphinate, phosphonate, silicate, carbonate, sulfide, selenate, nitrate, and/or perchlorate, and
wherein C x+ is a counter-cation of -A x− , and C x+ is H + , an alkali metal cation, and/or an alkaline-earth metal cation.

2. The electrolyte of claim 1 , wherein, in the molecule, the polycyclic group Ar has one of the following backbones:

3. The electrolyte of claim 1 , wherein, in the molecule, the polycyclic group Ar is an aromatic bicyclic group.

4. The electrolyte of claim 1 , wherein, in the molecule, the flexible part is formed from:
a single branched aliphatic chain, comprising a linear sequence of at least 6 covalent bonds; or
at least two linear or branched aliphatic chains, each of the chains comprising a linear sequence of at least 6 covalent bonds.

5. The electrolyte of claim 1 , wherein, in the molecule, each of the aliphatic chains is formed from a single chain segment or from a linear sequence of at least two chain segments.

6. The electrolyte of claim 1 , wherein, in the molecule, the aliphatic chain(s) forming the flexible part are covalently bonded directly to one or more carbon atoms or heteroatoms of the group Ar forming the rigid part.

7. The electrolyte of claim 1 , wherein, in the molecule, the aliphatic chain(s) forming the flexible part are covalently bonded via a spacer to one or more carbon atoms or heteroatoms of the group Ar forming the rigid part.

8. The electrolyte of claim 7 , wherein the aliphatic chain(s) are covalently bonded to a carbon atom of the group Ar via an atom of valency greater than or equal to 2.

9. The electrolyte of claim 8 , wherein the atom of valency greater than or equal to 2 is a nitrogen atom.

10. The electrolyte of claim 7 , wherein, in the molecule, the flexible part is formed from two linear alkyl chains, comprising from 4 to 18 carbon atoms, optionally substituted with one or more hydroxyl groups, optionally interrupted with one or more oxygen atoms,
wherein the chains are bonded to a carbon atom of the group Ar via a nitrogen atom.

11. The electrolyte of claim 1 , wherein, in the molecule, the anionic groups -A x− are sulfonate anions and/or anions of formula —SO 2 —N − —SO 2 —C y F 2y+1 with y ranging from 0 to 4.

12. The electrolyte of claim 1 , wherein, in the molecule, C x+ is H + or a Li + cation.

13. The electrolyte of claim 1 , wherein the molecule has the structure:

wherein E 1 and E 2 represent identical or different linear or branched, saturated or unsaturated, fluorinated or nonfluorinated aliphatic chains, the chain(s) being optionally interrupted with one or more heteroatoms, metalloids, and/or aromatic or nonaromatic, 4- to 6-membered (hetero)cycles, and optionally substituted with one or more groups selected from the group consisting of hydroxyl, —NH 2 and oxo groups.

14. The electrolyte of claim 13 , wherein the chains E 1 and E 2 represent identical or different linear alkyl chains, comprising from 6 to 16 carbon atoms, each being substituted with a hydroxyl group, optionally fluorinated, and optionally interrupted with an oxygen atom.

15. The electrolyte of claim 1 , having a viscosity of greater than or equal to 10 mPa·s at a temperature of between −60° C. and 300° C.

16. The electrolyte of claim 1 , having an ion conductivity at 20° C. of greater than or equal to 10 −9 S/cm, and an ion conductivity at 200° C. of greater than or equal to 10 −5 S/cm.

17. The electrolyte of claim 1 , wherein, in the molecule, the polycyclic group Ar is an aromatic bicyclic group with a naphthalene aromatic backbone.

18. The electrolyte of claim 1 , wherein, in the molecule, the polycyclic group Ar is a naphthalene group.

19. The electrolyte of claim 1 , wherein, in the molecule, each of the aliphatic chains is formed from a linear sequence of two or three chain segments of different chemical nature.

20. The electrolyte of claim 1 , wherein, in the molecule, the anionic groups -A x− are sulfonate anions.

21. The electrolyte of claim 1 , wherein the molecule comprises:

22. An electrochemical system comprising the electrolyte of claim 1 .

23. The electrochemical system of claim 22 , which is a battery.

24. The electrochemical system of claim 23 , wherein the system is a lithium battery.

25. A porous separator, which is impregnated with the electrolyte of claim 1 .

Assignees

• Commissariat Energie Atomique

Inventors

• Picard Lionel
• Gebel Gerard
• Leclere Melody
• Mendil Hakima
• Rannou Patrice

Classifications

• C07C309/47 Primary

  having at least one of the sulfo groups bound to a carbon atom of a six-membered aromatic ring being part of a condensed ring system · CPC title

• C09K19/32

  containing condensed ring systems, i.e. fused, bridged or spiro ring systems · CPC title

• C09K2019/328

  containing a triphenylene ring system · CPC title

• H01M10/0564

  the electrolyte being constituted of organic materials only · CPC title

• H01M2300/0025

  Organic electrolyte · CPC title