Complimentary polymer electrochromic device

• US 9,274,395 B2
• Filed: 11/14/2012
• Issued: 03/01/2016
• Est. Priority Date: 11/15/2011
• Status: Active Grant

• Current Assignee: Ashwin-Ushas Corporation, Inc.
• Original Assignee: Ashwin-Ushas Corporation, Inc.
• Inventors: Chandrasekhar, Prasanna
• Primary Examiner(s): Jarrell, Noble
• Application Number:
  US13/677,197
• Publication Number:
  US 20130120821A1
• Time in Patent Office: 1,203 Days
• Field of Search: 359/368, 359/365
• US Class Current: 1/1
• CPC Class Codes: B05D 5/12 to obtain a coating with specific electrical properties
• CPC Class Codes: C07C 29/147 of carboxylic acids or derivatives thereof
• CPC Class Codes: C07C 33/46 containing only six-membered aromatic rings as cyclic parts
• CPC Class Codes: C07C 57/38 polycyclic
• CPC Class Codes: C07C 69/65 of unsaturated acids
• CPC Class Codes: C07D 495/04 Ortho-condensed systems
• CPC Class Codes: C09D 5/4419 with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C09D 5/4476 comprising polymerisation in situ
• CPC Class Codes: C09K 2211/1433 bridged by heteroatoms, e.g. N, P, Si or B
• CPC Class Codes: C09K 2211/1491 containing other combinations of heteroatoms
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: C25D 3/02 from solutions C25D5/34 - C25D5/46 take precedence
• CPC Class Codes: C25D 9/02 with organic materials
• CPC Class Codes: G02F 1/13439 characterised by their electrical, optical, physical properties; materials therefor; method of making
• CPC Class Codes: G02F 1/1503 caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
• CPC Class Codes: G02F 1/1506 caused by electrodeposition, e.g. electrolytic deposition of an inorganic material on or close to an electrode
• CPC Class Codes: G02F 1/15165 Polymers
• CPC Class Codes: G02F 1/155 Electrodes
• CPC Class Codes: G02F 2001/1502 complementary cell

Abstract

A complimentary polymer or “dual-polymer” electrochromic device and methods of preparing the same are provided.

Claims

1. A complimentary electrochromic device comprising:

(a) a first electrode comprising a cathodically coloring conducting polymeric material, the cathodically coloring conducting polymeric material comprising a substituted or unsubstituted 2,2-dibenzyl-3,4-propylenedioxythiophene monomer;

(b) a second electrode comprising an anodically coloring conducting polymeric material;

(c) an electrolyte disposed between and in electrochemical communication with the first electrode and the second electrode; and

wherein the redox potential of the cathodically coloring conducting polymeric material is substantially matched to the redox potential of the anodically coloring conducting polymeric material such that when one said polymeric material is fully oxidized, the other said polymeric material is fully reduced.

2. The electrochromic device of claim 1, wherein at least one benzyl moiety of the substituted 2,2-dibenzyl-3,4-propylenedioxythiophene is para substituted with a substituent selected from the group consisting of halo, sulfonyl, nitro, and alkyl.

3. The electrochromic device of claim 1, wherein at least one benzyl moiety of the substituted 2,2-dibenzyl-3,4-propylenedioxythiophene has a substituent selected from the group consisting of chloro and bromo.

4. The electrochromic device of claim 1, wherein at least one benzyl moiety of the substituted 2,2-dibenzyl-3,4-propylenedioxythiophene has a substituent selected from the group consisting of n-propyl, iso-propyl, n-butyl, iso-butyl, n-pentyl, and n-hexyl.

5. The electrochromic device of claim 1, wherein at least one benzyl moiety of the substituted 2,2-dibenzyl-3,4-propylenedioxythiophene has an amino substituent.

6. The electrochromic device of claim 1, wherein the cathodically coloring conducting polymeric material comprises a copolymer.

7. The electrochromic device of claim 1, wherein the cathodically coloring conducting polymeric material comprises poly(2,2-dibenzyl-3,4-propylenedioxythiophene), poly(2,2-bis(4-chloro-benzyl)-3,4-propylenedioxythiophene), poly(2,2-bis(4-bromo-benzyl)-3,4-propylenedioxythiophene), poly(2,2-bis(4-nitro-benzyl)-3,4-propylenedioxythiophene), or combinations thereof.

8. The electrochromic device of claim 1, wherein the cathodically coloring conducting polymeric material comprises at least one monomer selected from the group consisting of 2,2-bis(4-chloro-benzyl)-3,4-propylenedioxythiophene, 2,2-bis(4-bromo-benzyl)-3,4-propylenedioxythiophene), and combinations thereof.

9. The electrochromic device of claim 1, wherein the cathodically coloring conducting polymeric material comprises a copolymer of the monomers 2,2-dibenzyl-3,4-propylenedioxythiophene, 2,2-bis(4-chloro-benzyl)-3,4-propylenedioxythiophene), and 2,2-bis(4-bromo-benzyl)-3,4-propylenedioxythiophene).

10. The electrochromic device of claim 1, wherein the cathodically coloring conducting polymeric material comprises a copolymer of the monomers 2,2-dibenzyl-3,4-propylenedioxythiophene, 2,2-bis(4-chloro-benzyl)-3,4-propylenedioxythiophene), and 2,2-bis(4-bromo-benzyl)-3,4-propylenedioxythiophene), in a molar ratio in the range of 1:

1;

1 to 50;

7;

1, respectively.

11. The electrochromic device of claim 1, wherein the cathodically coloring conducting polymeric material comprises a copolymer of the monomers 2,2-dibenzyl-3,4-propylenedioxythiophene, 2,2-bis(4-chloro-benzyl)-3,4-propylenedioxythiophene), and 2,2-bis(4-bromo-benzyl)-3,4-propylenedioxythiophene), in a molar ratio in the range of 1:

1;

1 to 50;

1;

1, respectively.

12. The electrochromic device of claim 1, wherein the cathodically coloring conducting polymeric material comprises a copolymer of the monomers 2,2-dibenzyl-3,4-propylenedioxythiophene, 2,2-bis(4-chloro-benzyl)-3,4-propylenedioxythiophene), and 2,2-bis(4-bromo-benzyl)-3,4-propylenedioxythiophene), in a molar ratio in the range of 50:

1;

1 to 50;

7;

1, respectively.

13. The electrochromic device of claim 1, wherein the cathodically coloring conducting polymeric material comprises a copolymer of the monomers 2,2-dibenzyl-3,4-propylenedioxythiophene, 2,2-bis(4-chloro-benzyl)-3,4-propylenedioxythiophene), and 2,2-bis(4-bromo-benzyl)-3,4-propylenedioxythiophene), in a molar ratio of 10:

1;

1, respectively.

14. The electrochromic device of claim 1, wherein the anodically coloring conducting polymeric material comprises a copolymer.

15. The electrochromic device of claim 1, wherein the anodically coloring conducting polymeric material comprises a poly(aromatic amine).

16. The electrochromic device of claim 1, wherein the anodically coloring conducting polymeric material comprises at least one monomer selected from the group consisting of N,N′

-diphenylbenzidine, diphenyl amine, 4-aminobiphenyl and combinations thereof.

17. The electrochromic device of claim 1, wherein the anodically coloring conducting polymeric material comprises a copolymer of the monomers N,N′

-diphenylbenzidine, diphenyl amine and 4-aminobiphenyl in a molar ratio in the range of 1;

1;

1 to 50;

1;

1, respectively.

18. The electrochromic device of claim 1, wherein the anodically coloring conducting polymeric material comprises a copolymer of the monomers N,N′

-diphenylbenzidine, diphenyl amine and 4-aminobiphenyl in a molar ratio of at least about 1;

1;

1 to 20;

1;

1, respectively.

19. The electrochromic device of claim 1, wherein the anodically coloring conducting polymeric material comprises a copolymer of the monomers N,N′

-diphenylbenzidine, diphenyl amine and 4-aminobiphenyl in a molar ratio in the range of 1;

1;

1 to 9;

1;

1, respectively.

20. The electrochromic device of claim 1, wherein the anodically coloring conducting polymeric material comprises a copolymer of the monomers N,N′

-diphenylbenzidine, diphenyl amine and 4-aminobiphenyl in a molar ratio in the range of 3;

1;

1 to 7;

1;

1, respectively.

21. The electrochromic device of claim 1, wherein the anodically coloring conducting polymeric material comprises a copolymer of the monomers N,N′

-diphenylbenzidine, diphenyl amine and 4-aminobiphenyl in a molar ratio of 5;

1;

1, respectively.

22. The electrochromic device of claim 1, wherein the first electrode comprises a first conductive transparent substrate.

23. The electrochromic device according to claim 22, wherein the first conductive transparent substrate comprises indium-tin-oxide(ITO)/glass, ITO/poly(ethylene terephthalate)(PET), tin-oxide/glass, tin-oxide/PET, gold/glass, carbon-nanotubes/glass, carbon-nanotubes/PET, gold/PET, or a combination thereof.

24. The electrochromic device according to claim 22, wherein the cathodically coloring conducting polymeric material is deposited on a surface of the first conductive transparent substrate.

25. The electrochromic device of claim 1, wherein the second electrode comprises a second conductive transparent substrate.

26. The electrochromic device according to claim 25, wherein the second conductive transparent substrate comprises indium-tin-oxide(ITO)/glass, ITO/poly(ethylene terephthalate)(PET), tin-oxide/glass, tin-oxide/PET, gold/glass, carbon-nanotubes/glass, carbon-nanotubes/PET, gold/PET, or a combination thereof.

27. The electrochromic device according to claim 25, wherein the anodically coloring conducting polymeric material is deposited on a surface of the second conductive transparent substrate.

28. The electrochromic device of claim 1, wherein the electrolyte comprises a liquid electrolyte, solid electrolyte, gel electrolyte, or a combination thereof.

29. The electrochromic device of claim 1, comprising a seal disposed about the edges of the device, said seal being effective to contain the electrolyte within the device.

30. A method for obtaining a complimentary electrochromic device comprising the steps of:

(a) preparing a first electrode by depositing a cathodically coloring conducting polymeric material on a first transparent conductive substrate to obtain the first electrode, wherein the cathodically coloring conducting polymeric material comprises a substituted or unsubstituted 2,2-dibenzyl-3,4-propylenedioxythiophene monomer;

(b) preparing a second electrode by depositing an anodically coloring conductive polymeric material on a second transparent conductive substrate to obtain the second electrode;

(c) superimposing the first electrode and the second electrode and providing a space between the first and second electrodes; and

(d) placing an electrolyte in the space between the first and second electrodes to provide the electrochromic device, wherein the electrolyte is in electrochemical communication with the first and second electrodes; and

wherein the redox potential of the cathodically coloring conducting polymeric material is substantially matched to the redox potential of the anodically coloring conducting polymeric material such that when one said polymeric material is fully oxidized, the other said polymeric material is fully reduced.

31. The method of claim 30, wherein at least one benzyl moiety of the substituted 2,2-dibenzyl-3,4-propylenedioxythiophene is para substituted with a substituent selected from the group consisting of halo, sulfonyl, nitro, and alkyl.

32. The method of claim 30, wherein at least one benzyl moiety of the substituted 2,2-dibenzyl-3,4-propylenedioxythiophene has a substituent selected from the group consisting of chloro and bromo.

33. The method of claim 30, wherein at least one benzyl moiety of the substituted 2,2-dibenzyl-3,4-propylenedioxythiophene has a substituent selected from the group consisting of n-propyl, iso-propyl, n-butyl, iso-butyl, n-pentyl, and n-hexyl.

34. The method of claim 30, wherein at least one benzyl moiety of the substituted 2,2-dibenzyl-3,4-propylenedioxythiophene has an amino substituent.

35. The method of claim 30, wherein the cathodically coloring conducting polymeric material comprises a copolymer.

36. The method of claim 30, wherein the cathodically coloring conducting polymeric material comprises poly(2,2-dibenzyl-3,4-propylenedioxythiophene), poly(2,2-bis(4-chloro-benzyl)-3,4-propylenedioxythiophene), poly(2,2-bis(4-bromo-benzyl)-3,4-propylenedioxythiophene), poly(2,2-bis(4-nitro-benzyl)-3,4-propylenedioxythiophene), or a combination thereof.

37. The method of claim 30, wherein the cathodically coloring conducting polymeric material comprises at least one monomer selected from the group consisting of 2,2-bis(4-chloro-benzyl)-3,4-propylenedioxythiophene, 2,2-bis(4-bromo-benzyl)-3,4-propylenedioxythiophene), and combinations thereof.

38. The method of claim 30, wherein the cathodically coloring conducting polymeric material comprises a copolymer of the monomers 2,2-dibenzyl-3,4-propylenedioxythiophene, 2,2-bis(4-chloro-benzyl)-3,4-propylenedioxythiophene, and 2,2-bis(4-bromo-benzyl)-3,4-propylenedioxythiophene).

39. The method of claim 30, wherein the anodically coloring conducting polymeric material comprises a poly(aromatic amine).

40. The method of claim 30, wherein the anodically coloring conducting polymeric material comprises at least one monomer selected from the group consisting of N,N′

-diphenylbenzidine, diphenyl amine, 4-aminobiphenyl, and combinations thereof.