Polymers comprising imidazole derivatives and their use in electrochemical cells

Patent metadata

Field	Value
Publication number	US-11643497-B2
Application number	US-201816627594-A
Country	US
Kind code	B2
Filing date	Jul 6, 2018
Priority date	Jul 6, 2017
Publication date	May 9, 2023
Grant date	May 9, 2023

Abstract

Here are described polymers comprising monomeric units from vinylimidazole derivatives and their use in electrode materials and/or electrolyte compositions, as well as their methods of preparation. Also described are electrode materials, electrodes, and electrochemical cells comprising the polymers and their use.

First claim

The invention claimed is:

1. An element of an electrochemical cell comprising a polymer, wherein said polymer:
(i) comprises monomeric units derived from Formulae I and II:

(ii) is a random or a block copolymer of Formula IV:

(iii) is a random or a block copolymer of Formula V:

(iv) comprises monomeric units derived from Formula I:

or
(v) is a homopolymer of Formula III:

wherein,
R 1 and R 2 are each independently selected from H, CN, F, and optionally fluorinated C 1-6 alkyl groups, wherein at least one R 1 and R 2 is CN;
R 3 is a hydrogen atom or an optionally substituted C 1-6 alkyl group;
R 4 , R 6 , and R 7 are each independently selected from a hydrogen atom and optionally substituted C 1-6 alkyl groups; and
R 5 is selected from —CO 2 H, optionally substituted —CO 2 C 1-6 alkyl groups, —C(O)NH 2 , optionally substituted —OC 1-6 alkyl groups, optionally substituted C 6 aryl groups, optionally substituted C 5-6 heteroaryl groups, —CN, —SO 3 H, —SO 2 NH 2 , and optionally substituted —SO 3 C 1-6 alkyl groups;
or
R 5 taken together with R 7 and their adjacent carbon atoms form a 5 or 6-membered heterocycle;
L 1 and L 2 are independently selected from H, an alkyl group, a residue of a polymerisation initiator, and a linker between two or more of the polymer chains;
L 3 is selected from linear or branched alkyl groups and linkers between polymer chains;
n 1 is an integer selected such that the average molecular weight is from about 2,000 to about 50,000 g/mol;
n 2 and n 3 are integers representing the number of each monomeric unit within the polymer and wherein, in Formula IV, n 2 and n 3 are selected such that the average molecular weight is from about 2,000 to about 50,000 g/mol; and the ratio n 2 :n 3 range from 9:1 to 1:1; and
n 4 and n 5 are each selected from 1 to 4, wherein, in Formula V, n 2 , n 3 , n 4 and n 5 are selected such that the number average molecular weight is from about 2 000 to about 50 000 g/mol, or from about 3 000 to about 10 000 g/mol, and the ratio (n 2 ×n 4 ):(n 3 ×n 5 ) range from 9:1 to 1:1;
or a salt thereof.

2. The element of claim 1 , wherein R 1 is CN and R 2 is an optionally fluorinated C 1-6 alkyl group, or R 2 is CN and R 1 is an optionally fluorinated C 1-6 alkyl group, or both R 1 and R 2 are CN.

3. The element of claim 1 , wherein R 3 is H.

4. The element of claim 1 , wherein R 3 is an optionally substituted C 1-6 alkyl group.

5. The element of claim 1 , wherein at least one of R 4 , R 6 , and R 7 is H.

6. The element of claim 1 , wherein R 4 is an optionally substituted C 1-6 alkyl group.

7. The element of claim 1 , wherein R 5 is CO 2 H, or an optionally substituted —CO 2 C 1-6 alkyl group.

8. The element of claim 1 , wherein R 5 is an optionally substituted —OC 1-6 alkyl group.

9. The element of claim 1 , wherein R 5 taken together with R 7 and their adjacent carbon atoms form a 5-membered heterocycle.

10. The element of claim 1 , wherein the polymer in (i) to (iii) comprises between 10 mol % and 90 mol % or between 10 mol % and 60 mol % or between 15 mol % and 40 mol % of monomeric units derived from a vinylimidazole derivative of Formula I, each upper and lower values being included.

11. The element of claim 1 , wherein the polymer is of Formula IV and the ratio n 2 :n 3 ranges from 4:1 to 3:2, or is of about 7:3.

12. The element of claim 1 , wherein the polymer is of Formula V and the ratio (n 2 ×n 4 ):(n 3 ×n 5 ) ranges from 4:1 to 3:2, or is of about 7:3, and/or wherein n 4 +n 5 =3 or 4.

13. The element of claim 1 , wherein the polymer is of Formula V and L 3 is selected from branched alkyl groups and functionalized branched alkyl groups.

14. The element of claim 1 , wherein said polymer is as defined in (i) to (iii) and is a random copolymer.

15. The element of claim 1 , wherein said polymer is as defined in (i) to (iii) and is a block copolymer.

16. The element of claim 1 , wherein said polymer is as defined in (i) to (iii) and is a branched or hyperbranched copolymer including comb and dendritic, or is a star copolymer wherein linear chains of said star copolymer are homogeneous or heterogenous in length and structure.

17. The element of claim 1 , wherein said linkers L 1 and L 2 are selected from a group consisting of linear or branched alkyl, alkoxyl, and aryl groups, each of which may be further substituted.

18. The element of claim 1 , wherein said linkers L 1 and L 2 groups optionally comprise two or more functional groups comprising heteroatoms selected from oxygen, nitrogen and sulfur.

19. The element of claim 1 , wherein the said salts of the polymers are selected from alkali, and alkaline earth metal salts.

20. The element of claim 1 , wherein said element is an electrode material, an electrolyte composition and/or a separator.

21. An electrode material, the electrode material being an element as defined in claim 1 comprising the polymer and an electrochemically active material.

22. The electrode material of claim 21 , wherein said polymer is a binder.

23. The electrode material of claim 22 , wherein said binder further comprises a second polymer selected from polymers based on glycidyl, acrylic or methacrylic acid, vinyl alkyl ether, thiol-containing monomers, fluorine containing polymers, water soluble binders, styrene butadiene rubber, butadiene acrylonitrile rubber, hydrogenated butadiene acrylonitrile rubber, epichlorohydrin rubber, acrylate rubber, cellulose-based binders, ion-conductive polymer binders and any combination of two or more of these.

24. The electrode material of claim 21 , wherein said electrode material comprises particles having a core-shell structure, wherein the shell comprises a shell composition comprising the polymer and the core comprises the electrochemically active material.

25. An electrolyte, the electrolyte being an element as defined in claim 1 comprising the polymer and optionally a lithium salt, wherein said electrolyte is a solid polymer electrolyte (SPE) or a gel electrolyte composition.

26. The electrolyte of claim 25 , wherein the electrolyte composition further comprises a second polymer.

27. An electrolyte comprising a separator and an electrolyte composition, wherein said separator is an element as defined in claim 1 , and the electrolyte optionally further comprises a lithium salt.

28. An electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein at least one of the negative electrode, positive electrode and electrolyte comprises an element as defined in claim 1 .

29. An electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein at le

Assignees

• Hydro Quebec
• Murata Manufacturing Co

Inventors

• Daigle Jean-Christophe
• Mallet Charlotte
• Asakawa Yuichiro
• Beaupre Melanie
• Uesaka Shinichi
• Zaghib Karim

Classifications

• C08F299/024 Primary

  the unsaturation being in acrylic or methacrylic groups · CPC title

• H01M50/417

  Polyolefins · CPC title

• H01M2300/0085

  Immobilising or gelification of electrolyte · CPC title

• C08F230/04

  containing a metal · CPC title

• H01M4/623

  fluorinated polymers · CPC title