Polymer serving as an electrode material for lithium secondary batteries

Patent metadata

Field	Value
Publication number	US-9640797-B2
Application number	US-201314394963-A
Country	US
Kind code	B2
Filing date	Apr 10, 2013
Priority date	Apr 16, 2012
Publication date	May 2, 2017
Grant date	May 2, 2017

Abstract

The present invention relates to a polymer possessing a linear backbone selected from the homopolymers belonging to the family of polyfluorenes, polycarbazoles, polyanilines, polyphenylenes, polyisothionaphthenes, polyacetylenes, polyphenylene vinylenes, and copolymers thereof, said backbone bearing at least one side group possessing at least one nitroxide function.
It also relates to an electrode material, an electrode and a lithium secondary battery obtained from such a polymer.

First claim

The invention claimed is:

1. A polymer possessing a linear backbone selected from the polymers belonging to the family of polyfluorenes, polycarbazoles, polyanilines, polyphenylenes, polyisothionaphthenes, polyacetylenes, and combinations thereof, said backbone bearing at least one side group possessing at least one nitroxide function in NO. radical form, wherein the polymer has the structure (I) below:

wherein:
A and B represent, independently of one another, a hydrogen atom, a halogen atom, an acetylenic function, a boronic acid or borane function, a stannic function, a zincic group or a magnesian group;
—(Z 1 ) m — and —(Z 2 ) p — represent the sequence of one or more monomers selected from carbazole, aniline, phenylene, isothionaphthene, acetylene and phenylene vinylene monomers; —(Z 1 ) m — being at position 5, 6, 7 or 8 of the fluorene, —(Z 2 ) p — being at position 1, 2, 3 or 4 of the fluorene;
at least one of R 1 and R 2 represents *—Y(G) t , with:
* representing a covalent bond with the fluorene;
t being equal to 1 or 2;
if t is equal to 1, Y represents a covalent bond; a linear or branched, saturated or unsaturated (C 1 -C 5 )alkyl group, optionally interrupted by one or more heteroatom(s) or by one or more ether, ester or amide functions; —O—; —COO—or —CONH;
if t is equal to 2, Y represents a linear or branched, saturated or unsaturated (C 1 -C 5 )alkyl group, optionally interrupted by one or more heteroatom(s) or by one or more ether, ester or amide functions; —O—; —COO—or —CONH;
G representing a group possessing at least one nitroxide function in NO. radical form;

the other one of R 1 and R 2 represents *—Y(G) t , which may be identical or different, or a hydrogen atom;
m and p represent integers ranging from 0 to 50000; and
n represents an integer ranging from 1 to 50000, on condition that when n=1, at least one of m and p is other than 0.

2. The polymer as claimed in claim 1 , said polymer being crosslinked.

3. The polymer as claimed in claim 1 , wherein said side group(s) bearing at least one nitroxide function has (have) one of the following structures:

with * depicting the location of the site of bonding to said linear backbone.

4. The polymer as claimed in claim 1 , wherein at least one portion of said side groups possess at least two nitroxide functions in NO. radical form.

5. The polymer as claimed in claim 1 , wherein at least one portion of said side groups has the structure 2,2,6,6-tetramethylpiperidinyl-N-oxy.

6. The polymer as claimed in claim 1 , possessing a linear backbone formed completely or partly from a polyfluorene.

7. The polymer as claimed in claim 1 , having the structure (I) wherein A and B represent, independently of one another, a hydrogen atom or a halogen atom; R 1 represents a *—Y(G) t group with t equal to 1, Y representing a covalent bond, and G being selected from the structures (G1) to (G8):

with * depicting the location of the site of bonding to said linear backbone; R 2 represents H; m and p are equal to 0 and n is an integer ranging from 2 to 50000.

8. The polymer as claimed in claim 7 , wherein G represents structure (G1).

9. The polymer as claimed in claim 7 , wherein A and B represent, independently of one another, a hydrogen atom or a bromine atom.

10. The polymer as claimed in claim 7 , said polymer having a number-average degree of polymerization ranging from 5 to 5000.

11. The polymer as claimed in claim 1 , said polymer having a molar degree of grafting of nitroxide functions in NO. radical form ranging from 1% to 800%.

12. The polymer as claimed in claim 1 , said polymer having a molar degree of grafting of nitroxide functions in NO. radical form ranging from 50% to 200%.

13. The polymer as claimed in claim 4 , wherein all of said side groups possess at least two nitroxide functions in NO. radical form.

14. The polymer as claimed in claim 5 , wherein all of said side groups has the structure 2,2,6,6-tetramethylpiperidinyl-N-oxy.

15. The polymer as claimed in claim 10 , said polymer having a number-average degree of polymerization ranging from 10 to 100.

Assignees

• Commissariat Energie Atomique

Inventors

• Gutel Thibaut
• Kervella Yann
• Picard Lionel
• Denis Jean-Benoit

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• C08G2261/3142

  fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene · CPC title

• C08G61/02 Primary

  Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• C08G2261/143

  Side-chains containing nitrogen · CPC title