Electrochromic polymers and polymer electrochromic devices

• US 20030174377A1
• Filed: 11/21/2002
• Published: 09/18/2003
• Est. Priority Date: 11/21/2001
• Status: Active Grant

• Current Assignee: University of Florida (State University System of Florida)
• Original Assignee: University of Florida (State University System of Florida)
• Inventors: Schwendeman, Irina, Sonmez, Gursel, Aubert, Pierre H., Reynolds, John R., Schottland, Philippe, Argun, Avni A., Zong, Kyukwan
• Granted Patent: US 6,791,738 B2
• Time in Patent Office: Days
• US Class Current: 359/265
• CPC Class Codes: C08G 61/123 derived from five-membered heterocyclic compounds
• CPC Class Codes: C08G 61/124 with a five-membered ring containing one nitrogen atom in the ring
• CPC Class Codes: C08G 61/126 with a five-membered ring containing one sulfur atom in the ring
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02F 2001/1502 complementary cell

Abstract

The subject invention pertains to electrochromic polymers and polymer electrochromic devices. In a specific embodiment, two complementary polymers can be matched and incorporated into dual polymer electrochromic devices. The anodically coloring polymers in accordance with the subject invention can allow control over the color, brightness, and environmental stability of an electrochromic window. In addition, high device contrast ratios, high transmittance changes, and high luminance changes can be achieved, along with half-second switching times for full color change. Also provided are electrochromic devices such as advertising signage, video monitors, stadium scoreboards, computers, announcement boards, warning systems for cell phones, warning/information systems for automobiles, greeting cards, electrochromic windows, billboards, electronic books, and electrical wiring. The subject invention also provides for the use of complementary electrochromic polymers in the manufacture of electrochromic devices. In some embodiments, the devices of the invention can be prepared using metal vapor deposition or line patterning.

Claims

1. An electrochromic polymer comprising compounds as set forth in Formula I, Formula II, or combinations thereof,

2. The electrochromic polymer according to claim 1, wherein one of R₁ and R₂ are H, R₃ and R₄ can be the same or different and are H or alkyl, and one of R₅ or R₆ is H.

3. The electrochromic polymer according to claim 1, wherein n is at least 3.

4. The electrochromic polymer according to claim 1, wherein n is at least 4.

5. The electrochromic polymer according to claim 1, wherein n is at least 5.

6. The electrochromic polymer according to claim 1, wherein m is 0, 1, 2, 3, 4, or 5.

7. The electrochromic polymer according to claim 1, wherein Z is Si and R₈ is an alkyl, aryl, or heteroaryl.

8. The electrochromic polymer according to claim 1, wherein double or triple bonds exist between one or more of the following adjacent atom groupings:

X and A₁;

A₁ and A₂ (when m=1);

each of (A₂)_m and (A₂)_m+1 where m=1, 2, 3, 4, 5, 6, 7, 8, or 9;

A₂ and A₃, when m=1;

or A₁ and A₃ when A₂ is absent (m=0).

9. The electrochromic polymer according to claim 1, wherein the polymer comprises only Formula I.

10. The electrochromic polymer according to claim 1, wherein the polymer comprises only Formula II.

11. The electrochromic polymer according to claim 1, wherein the polymer comprises a mixture of Formula I and Formula II.

12. An electrochromic device, comprising:

a first electrode;

a second electrode;

a layer of cathodically coloring polymer in electrical contact with the first electrode;

a layer of anodically coloring polymer in electrical contact with the second electrode;

a layer of electrolyte positioned between the layer of cathodically coloring polymer and the layer of anodically coloring polymer, wherein the layer of electrolyte is in contact with the layer of cathodically coloring polymer and in contact with the layer of anodically coloring polymer,

wherein upon application of a positive voltage to the first electrode with respect to the second electrode, the layer of cathodically coloring polymer is transmissive and the layer of anodically coloring polymer is transmissive,

wherein upon application of a negative voltage to the first electrode with respect to the second electrode, the layer of cathodically coloring polymer is colored and the layer of anodically coloring polymer is colored,

wherein the layer of anodically coloring polymer comprises and electrochromic polymer according to claim 1.

14. The electrochromic device according to claim 12,

wherein the larger of cathodically coloring polymer is a layer of cathodically coloring p-type dopable polymer and the layer of anodically coloring polymer is a layer of anodically coloring p-type dopable polymer.

15. The electrochromic device according to claim 12,

wherein the larger of cathodically coloring polymer is a layer of cathodically coloring n-type dopable polymer and the layer of anodically coloring polymer is a layer of anodically coloring n-type dopable polymer.

16. The electrochromic device according to claim 12,

wherein the larger of cathodically coloring polymer is a layer of cathodically coloring p-type dopable polymer and the layer of anodically coloring polymer is a layer of anodically coloring n-type dopable polymer.

17. The electrochromic device according to claim 12,

wherein the larger of cathodically coloring polymer is a layer of cathodically coloring n-type dopable polymer and the layer of anodically coloring polymer is a layer of anodically coloring p-type dopable polymer.

26. An electrochromic device, comprising:

a first electrode;

a second electrode;

a layer of cathodically coloring polymer in electrical contact with the first electrode;

a layer of anodically coloring polymer in electrical contact with the second electrode;

a layer of electrolyte positioned between the layer of cathodically coloring polymer and the layer of anodically coloring polymer, wherein the layer of electrolyte is in contact with the layer of cathodically coloring polymer and in contact with the layer of anodically coloring polymer,

wherein upon application of a negative voltage to the first electrode with respect to the second electrode, the layer of cathodically coloring polymer is colored and the layer of anodically coloring polymer is colored,

wherein upon application of a positive voltage to the first electrode with respect to the second electrode, the layer of cathodically coloring polymer is transmissive and the layer of anodically coloring polymer is transmissive,

wherein the layer of canodically coloring polymer comprises an electrochromic polymer according to claim 1.

28. The electrochromic device, according to claim 26,

wherein the canodically coloring polymer has a reduction potential of greater than about −

2.0 volts versus saturated calomel electrode (SCE).

29. The electrochromic device, according to claim 26,

wherein the anodically coloring polymer has a reduction potential between about −

2.0 to about −

1.0 volts versus saturated calomel electrode (SCE).

30. The electrochromic device, according to claim 26,

wherein the anodically coloring polymer has a reduction potential between about −

1.8 to about −

1.6 volts versus saturated calomel electrode (SCE).

31. The electrochromic device, according to claim 26,

wherein the canodically coloring polymer has a reduction potential of greater than about −

1.8 volts versus saturated calomel electrode (SCE).

13. An electrochromic device, comprising:

a first electrode;

a second electrode;

a layer of cathodically coloring polymer in electrical contact with the first electrode;

a layer of anodically coloring polymer in electrical contact with the second electrode;

a layer of electrolyte positioned between the layer of cathodically coloring polymer and the layer of anodically coloring polymer, wherein the layer of electrolyte is in contact with the layer of cathodically coloring polymer and in contact with the layer of anodically coloring polymer,

wherein upon application of a positive voltage to the first electrode with respect to the second electrode, the layer of cathodically coloring polymer is transmissive and the layer of anodically coloring polymer is transmissive,

wherein upon application of a negative voltage to the first electrode with respect to the second electrode, the layer of cathodically coloring polymer is colored and the layer of anodically coloring polymer is colored,

wherein the layer of anodically coloring polymer comprises a compound selected from the compounds listed in table 3 and table 4.

18. An electrochromic device, comprising:

a first electrode;

a second electrode;

a layer of cathodically coloring polymer in electrical contact with the first electrode;

a layer of anodically coloring polymer in electrical contact with the second electrode;

a layer of electrolyte positioned between the layer of cathodically coloring polymer and the layer of anodically coloring polymer, wherein the layer of electrolyte is in contact with the layer of cathodically coloring polymer and in contact with the layer of anodically coloring polymer,

wherein upon application of a positive voltage to the first electrode with respect to the second electrode, the layer of cathodically coloring polymer is transmissive and the layer of anodically coloring polymer is transmissive,

wherein upon application of a negative voltage to the first electrode with respect to the second electrode, the layer of cathodically coloring polymer is colored and the layer of anodically coloring polymer is colored,

wherein the anodically coloring polymer has an oxidation potential of less than about 0.5 volts versus saturated calomel electrode (SCE).

19. The electrochromic device according to claim 18,

wherein the anodically coloring polymer has an oxidation potential in the range between about −

0.2 and about +0.5 volts versus saturated calomel electrode (SCE).

20. The electrochromic device according to claim 18,

wherein the anodically coloring polymer has an oxidation potential in the range between about −

0.2 and about −

0.0 volts versus saturated calomel electrode (SCE).

21. The electrochromic device according to claim 18,

wherein the anodically coloring polymer has an oxidation potential of less than about 0.4 volts versus saturated calomel electrode (SCE).

22. The electrochromic device according to claim 18,

wherein the anodically coloring polymer has an oxidation potential of less than about 0.3 volts versus saturated calomel electrode (SCE).

23. The electrochromic device according to claim 18,

wherein the anodically coloring polymer has an oxidation potential of less than about 0.2 volts versus saturated calomel electrode (SCE).

24. The electrochromic device according to claim 18,

wherein the anodically coloring polymer has an oxidation potential of less than about 0.1 volts versus saturated calomel electrode (SCE).

25. The electrochromic device according to claim 18,

wherein the anodically coloring polymer has an oxidation potential of less than about 0.0 volts versus saturated calomel electrode (SCE).

27. An electrochromic device, comprising:

a first electrode;

a second electrode;

a layer of cathodically coloring polymer in electrical contact with the first electrode;

a layer of anodically coloring polymer in electrical contact with the second electrode;

a layer of electrolyte positioned between the layer of cathodically coloring polymer and the layer of anodically coloring polymer, wherein the layer of electrolyte is in contact with the layer of cathodically coloring polymer and in contact with the layer of anodically coloring polymer,

wherein upon application of a negative voltage to the first electrode with respect to the second electrode, the layer of cathodically coloring polymer is colored and the layer of anodically coloring polymer is colored,

wherein upon application of a positive voltage to the first electrode with respect to the second electrode, the layer of cathodically coloring polymer is transmissive and the layer of anodically coloring polymer is transmissive,

wherein the anodically coloring polymer is selected from the compounds listed in table 3 and table 4.

32. An electrochromic device, comprising:

a first electrode;

a second electrode;

a layer of cathodically coloring polymer in electrical contact with the first electrode;

a layer of anodically coloring polymer in electrical contact with the second electrode;

a layer of electrolyte positioned between the layer of cathodically coloring polymer and the layer of anodically coloring polymer, wherein the layer of electrolyte is in contact with the layer of cathodically coloring polymer and in contact with the layer of anodically coloring polymer,

wherein upon application of a negative voltage to the first electrode with respect to the second electrode, the layer of cathodically coloring polymer is colored and the layer of anodically coloring polymer is colored,

wherein upon application of a positive voltage to the first electrode with respect to the second electrode, the layer of cathodically coloring polymer is transmissive and the layer of anodically coloring polymer is transmissive, wherein the anodically coloring polymer has a reduction potential of greater than about −

2.0 volts versus saturated calomel electrode (SCE).

33. The electrochromic device according to claim 32

wherein the anodically coloring polymer has a reduction potential between about −

2.0 and about −

1.0 volts versus saturated calomel electrode (SCE).

34. An electrochromic device, comprising:

a first electrode

a second electrode, wherein the second electrode is porous;

a layer of electroactive polymer, in electrical contact with the first electrode;

a layer of cathodically coloring polymer in electrical contact with the second electrode;

a layer of electrolyte positioned between the layer of electroactive polymer and the second electrode;

wherein the second electrode is positioned between the layer of electrolyte and the layer of cathodically coloring polymer such that the electrolyte soaks through the second electrode and is in electrical contact with the layer of cathodically coloring polymer,

wherein upon application of a positive voltage to the first electrode with respect to the second electrode, the layer of cathodically coloring polymer is colored,

wherein upon application of a negative voltage to the first electrode with respect to the second electrode, the layer of cathodically coloring polymer is transmissive.

35. An electrochromic device, comprising:

a first electrode

a second electrode, wherein the second electrode is porous;

a layer of electroactive polymer, in electrical contact with the first electrode;

a layer of anodically coloring polymer in electrical contact with the second electrode;

a layer of electrolyte positioned between the layer of electroactive polymer and the second electrode;

wherein the second electrode is positioned between the layer of electrolyte and the layer of anodically coloring polymer such that the electrolyte soaks through the second electrode and is in electrical contact with the layer of anodically coloring polymer,

wherein upon application of a positive voltage to the first electrode with respect to the second electrode, the layer of anodically coloring polymer is transmissive,

wherein upon application of a negative voltage to the first electrode with respect to the second electrode, the layer of anodically coloring polymer is colored.

36. An electrochromic device, comprising:

a first electrode

a second electrode, wherein the second electrode is porous;

a layer of electroactive polymer, in electrical contact with the first electrode;

a layer of dual color polymer in electrical contact with the second electrode;

a layer of electrolyte positioned between the layer of electroactive polymer and the second electrode;

wherein the second electrode is positioned between the layer of electrolyte and the layer of dual color polymer such that the electrolyte soaks through the second electrode and is in electrical contact with the layer of dual color polymer,

wherein upon application of a positive voltage to the first electrode with respect to the second electrode, the layer of dual color polymer is a first color,

wherein upon application of a negative voltage to the first electrode with respect to the second electrode, the layer of dual color polymer is a second color.

37. An electrochromic device, comprising:

a first electrode;

at least one additional electrode;

a layer of electro active polymer in electrical contact with the first electrode;

at least one layer of cathodically coloring polymer corresponding to the at least additional electrode, each of the at least one layer of cathodically coloring polymer in electrical contact with the corresponding at least one additional electrode;

a layer of electrolyte;

a porous membrane, wherein each of the at least one additional electrode is in contact with the porous membrane,

wherein the layer of electrolyte is positioned between the layer of electroactive polymer and the porous membrane such that the electrolyte soaks through the porous membrane and is in electrical contact with each of the at least one additional electrode,

wherein upon application of a positive voltage to the first electrode with respect to one or more of the at least one additional electrode, the layer of cathodically coloring polymer of the at least one layer of cathodically coloring polymer corresponding to each of the one or more of the at least one additional electrode is colored,

wherein upon application of a negative voltage to the first electrode with respect to each of the at least one additional electrode, the layer of cathodically coloring polymer of the at least one layer of cathodically coloring polymer corresponding to each of the at least one additional electrode is transmissive.

38. The electrochromic device according to claim 37, further comprising:

a second porous membrane, wherein the second porous membrane is positioned between the first electrode and the layer of electrolyte such that the electrolyte soaks through the second porous membrane and is in electrical contact with the first electrode, wherein the first electrode is positioned between the layer of electroactive polymer and the second porous membrane.

39. The electrochromic device according to claim 38,

wherein the layer of electroactive polymer is a layer of anodically coloring polymer, wherein upon application of a positive voltage to the first electrode with respect to one or more of the at least one additional electrode, the layer of anodically coloring polymer is colored,

wherein upon application of a negative voltage to the first elected with respect to one or more of the at least one additional electrode, the layer of anodically coloring polymer is transmission.

40. An electrochromic device, comprising:

a first electrode;

at least one additional electrode;

a layer of electro active polymer in electrical contact with the first electrode;

at least one layer of anodically coloring polymer corresponding to the at least additional electrode, each of the at least one layer of anodically coloring polymer in electrical contact with the corresponding at least one additional electrode;

a layer of electrolyte;

a porous membrane, wherein each of the at least one additional electrode is in contact with the porous membrane,

wherein the layer of electrolyte is positioned between the layer of electroactive polymer and the porous membrane such that the electrolyte soaks through the porous membrane and is in electrical contact with each of the at least one additional electrode,

wherein upon application of a positive voltage to the first electrode with respect to one or more of the at least one additional electrode, the layer of anodically coloring polymer of the at least one layer of anodically coloring polymer corresponding to each of the one ore more of the at least one additional electrode is transmissive,

wherein upon application of a negative voltage to the first electrode with respect to each of the at least one additional electrode, the layer of anodically coloring polymer of the at least one layer of anodically coloring polymer corresponding to each of the at least one additional electrode is colored.

41. The electrochromic device according to claim 40, further comprising:

a second porous membrane, wherein the second porous membrane is positioned between the first electrode and the layer of electrolyte such that the electrolyte soaks through the second porous membrane and is in electrical contact with the first electrode, wherein the first electrode is positioned between the layer of electroactive polymer and the second porous membrane.

42. The electrochromic device according to claim 41,

wherein the layer of electroactive polymer is a layer of cathodically coloring polymer, wherein upon application of a positive voltage to the first electrode with respect to one or more of the at least one additional electrode, the layer of cathodically coloring polymer is transmissive,

wherein upon application of a negative voltage to the first elected with respect to one or more of the at least one additional electrode, the layer of cathodicallycoloring polymer is colored.

43. An electrochromic device, comprising:

a first electrode;

at least one additional electrode;

a layer of electro active polymer in electrical contact with the first electrode;

at least one layer of dual color polymer corresponding to the at least additional electrode, each of the at least one layer of dual color polymer in electrical contact with the corresponding at least one additional electrode;

a layer of electrolyte;

a porous membrane, wherein each of the at least one additional electrode is in contact with the porous membrane,

wherein the layer of electrolyte is positioned between the layer of electroactive polymer and the porous membrane such that the electrolyte soaks through the porous membrane and is in electrical contact with each of the at least one additional electrode,

wherein upon application of a positive voltage to the first electrode with respect to one or more of the at least one additional electrode, the layer of dual color polymer of the at least one layer of dual color polymer corresponding to each of the one or more of the at least one additional electrode is a first color,

wherein upon application of a negative voltage to the first electrode with respect to each of the at least one additional electrode, the layer of dual color polymer of the at least one layer of dual color polymer corresponding to each of the at least one additional electrode is a second color.

44. An electrochemical device, comprising

a substrate;

a first electrode in contact with the substrate;

a second electrode in contact with the substrate;

a layer of cathodically coloring polymer in electrical contact with the first electrode, wherein the first electrode is positioned between the substrate and the layer of cathodically coloring polymer;

a layer of anodically coloring polymer in electrical contact with the second electrode, wherein the second electrode is positioned between the second electrode, wherein the second electrode is positioned between the substrate and the layer of anodically coloring polymer;

a layer of electrolyte positioned between the layer of cathodically coloring polymer and the layer of anodically coloring polymer, wherein the layer of electrolyte is in contact with the layer of cathodically coloring polymer and is in contact with the layer of anodically coloring polymer,

wherein upon application of a positive voltage to the first electrode with respect to the second electrode, the layer of cathodically coloring polymer is transmissive and the layer of anodically coloring polymer is transmissive,

wherein upon application of a negative voltage to the first electrode with respect to the second electrode, the layer of cathodically coloring polymer is colored and the layer of anodically coloring polymer is colored.