Electroactive ionic liquids and surface-modified substrates containing them

Patent metadata

Field	Value
Publication number	US-10910634-B2
Application number	US-201716099068-A
Country	US
Kind code	B2
Filing date	May 5, 2017
Priority date	May 6, 2016
Publication date	Feb 2, 2021
Grant date	Feb 2, 2021

Abstract

The present invention relates an electro-active polymeric ionic liquid including imidazolium-based molecules, said imidazolium-based molecule comprising each at least: —one imidazolium moiety associated with a negatively-charged counter-ion, and —one reducible group selected from: Formula (IV), —an anthraquinone derivative of formula (IV): with R1 representing a hydrogen atom or a C1-C6-alkyl group, —a viologen group, and —a metallocene reducible group such as a cobaltocene group.

First claim

The invention claimed is:

1. An electro-active polymeric ionic liquid comprising imidazolium-based repeated units, each of said imidazolium-based repeated units comprising at least:
an imidazolium moiety associated with a negatively charged counter-ion,
a metallocene oxidizable group and/or a reducible group,
the reducible group being selected from:
an anthraquinone derivative of formula (IV):

 with R 1 representing a hydrogen atom or a C 1 -C 6 -alkyl group,
a viologen group of formula (V):

 with R′ 2 representing a hydrogen atom, a C 1 -C 8 alkyl group or a C 2 -C 6 alkenyl group,

X and X′ identical or different, and each independently representing a halogen group, or
a metallocene reducible group.

2. The electro-active polymeric ionic liquid according to claim 1 , wherein the polymeric ionic liquid presents:
imidazolium-based repeated units, each of said imidazolium-based repeated units comprising at least:
an imidazolium moiety associated with a negatively charged counter-ion, and
a metallocene oxidizable group and
imidazolium-based repeated units, each of said imidazolium-based repeated units comprising at least:
an imidazolium moiety associated with a negatively charged counter-ion, and
a reducible group, the reducible group being selected from an anthraquinone derivative, a viologen group, or a metallocene reducible group.

3. The electro-active polymeric ionic liquid according to claim 1 , wherein the imidazolium-based repeated units comprise:
an imidazolium moiety associated with a negatively charged counter ion, and
a metallocene oxidizable group, and
a reducible group selected from anthraquinone derivative, a viologen group, or a metallocene reducible group.

4. Electro-active polymeric ionic liquid of claim 1 , wherein the polymeric ionic liquid is polymerized from an imidazolium-based molecule of formula (I):

wherein
m is 0 or 1;
n is equal to 0 or 1;
L 1 is selected from: a bond, a C 1 -C 6 alkyl group where one or two carbon atoms are optionally replaced by an oxygen atom, a CO—(C1-C6)alkyl group, a (C1-C6)alkyl-CO— group, a CONH—(C 1 -C 6 )alkyl group, a (C 1 -C 6 )alkyl-CONH— group, a COO—(C 1 -C 6 )alkyl group, and a (C 1 -C 6 )alkyl-COO— group;
A and B are different and are selected from:

an imidazolium group of formula (IIa):

 Z − being a negatively charged counter ion,
a metallocene oxidizable group of formula (III)

 M being a transition metal ion, or
a reducible group selected from:
an anthraquinone derivative of formula (IV):

 with R 1 representing a hydrogen atom or a C 1 -C 6 -alkyl group, or
a metallocene reducible group, or
a viologen group of formula (V):

 with R′2 representing a hydrogen atom, a C 1 -C 8 alkyl group or a C 2 -C 6 alkenyl group, and X and X′ identical or different, and each independently representing a halogen group,
provided that at least A or B is an imidazolium group of formula (IIa),
when n is 1, then
C is selected from:

 a metallocene oxidizable group of formula (III) as defined above, or
 a reducible group as defined above,
provided that A, B and C are different;
L 2 is selected from a bond, a C 1 -C 6 alkyl group, a CONH—(C 1 -C 6 )alkyl group, a (C 1 -C 6 )alkyl-CONH— group, a COO—(C 1 -C 6 )alkyl group, and a (C 1 -C 6 )alkyl-COO— group,

 wherein one or two carbon atoms in the (C 1 -C 6 )-alkyl group are optionally replaced by an oxygen atom, a CO—(C 1 -C 6 )alkyl group, a (C 1 -C 6 )alkyl-CO— group,
when n is 0, then

A and B are different and are selected from an imidazolium group of formula (IIa) as defined above, and a reducible group as defined above
L 2 is a C 1 -C 6 alkyl group if B is an imidazolium group of formula (IIa)
when m is 1 then
A or B is an imidazolium group of formula (IIa),
A is not a viologen group of formula (V) as defined above,
L 3 is selected from a bond, a C 1 -C 6 alkyl group, a CONH—(C 1 -C 6 )alkyl group, a (C 1 -C 6 )alkyl-CONH— group, a COO—(C 1 -C 6 )alkyl group, and a (C 1 -C 6 )alkyl-COO— group,

wherein one or two carbon atoms in the (C 1 -C 6 )-alkyl group are optionally replaced by an oxygen atom, and
 R is a hydrogen atom, a C 1 -C 6 alkyl group or a C 5 -C 10 -aryl group;
when m is 0 then

 L 3 is a hydrogen atom if A is metallocene oxidizable group of formula (III) or a reducible group,
 L 3 is a C 1 -C 6 alkyl group if A is an imidazolium group of formula (IIa), and
 one of A and C is a viologen group of formula (V) as defined above with R′ 2 representing a C 2 -C 6 alkenyl group.

5. The electro-active polymeric ionic liquid of claim 1 , wherein the reducible group is an anthraquinone derivative of formula (IV) with R 1 representing a hydrogen atom.

6. The electro-active polymeric ionic liquid of claim 1 , wherein the metallocene oxidizable group is a ferrocene group.

7. The electro-active polymeric ionic liquid of claim 1 , wherein the negatively charged counter-ion is PF 6 − , BF 4 − , Cl − , Br − or bis(trifluoromethanesulfonyl)imidate CF 3 SO 2 NSO 2 CF 3 − .

8. The electro-active polymeric ionic liquid of claim 1 , wherein said imidazolium-based molecule is selected from:

with Z − , Z 1 − , X − and X′ − as defined in claim 4 .

9. The electro-active polymeric ionic liquid of claim 1 , wherein said imidazolium-based molecule is:

with Z − being a negatively charged counter ion, X − and X′ − being identical or different, and each independently representing a halogen group.

10. Surface-modified substrate with an immobilized electro-active polymeric ionic liquid as defined in claim 1 .

11. The surface-modified substrate of claim 10 , wherein the substrate is a current collector of an electrode.

12. The surface-modified substrate of claim 10 , wherein on the substrate is immobilized:
a combination of:
1) an electro-active polymeric ionic liquid comprising imidazolium-based repeated units comprising at least one imidazolium moiety, one negatively charged counter-ion and one metallocene oxidizable group, and
2) an electro-active polymeric ionic liquid comprising imidazolium-based repeated units comprising at least one imidazolium moiety, one negatively charged and one reducible group,

or
an electro-active polymeric ionic liquid comprising imidazolium-based repeated units comprising at least: 1) one imidazolium moiety associated with one negatively charged counter-ion, 2) one metallocene oxidizable group and 3) one reducible group.

13. An energy storage device c

Assignees

• Centre Nat Rech Scient
• Univ Paris Diderot Paris 7

Inventors

• Jalal Ghilane
• Trippe Allard Gaëlle
• Bui Thi Tuyet Van
• Randriamahazaka Hyacinthe
• Pham Truong Thuan Nguyen

Classifications

• H01M4/1399

  of electrodes based on electro-active polymers · CPC title

• H01G11/58

  Liquid electrolytes · CPC title

• H01G11/02

  using combined reduction-oxidation reactions, e.g. redox arrangement or solion · CPC title

• H01M4/60

  of organic compounds · CPC title

• H01B1/122

  Ionic conductors · CPC title