Electrochromic polymers and polymer electrochromic devices

• US 6,791,738 B2
• Filed: 11/21/2002
• Issued: 09/14/2004
• Est. Priority Date: 11/21/2001
• Status: Expired due to Term

• Current Assignee: University of Florida (State University System of Florida)
• Original Assignee: University of Florida (State University System of Florida)
• Inventors: Aubert, Pierre-Henri, Argun, Avni A., Schwendeman, Irina, Sonmez, Gursel, Reynolds, John R., Schottland, Philippe, Zong, Kyukwan
• Primary Examiner(s): Dang, Hung Xuan
• Assistant Examiner(s): Tra, Tuyen
• Application Number:
  US10/302,164
• Publication Number:
  US 20030174377A1
• Time in Patent Office: 663 Days
• Field of Search: 359/265, 359/273, 359/275, 204/290.07, 428/426, 252/583, 252/600, 546/257, 544/347
• 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. A composition of matter, comprising:

an anodically coloring polymer providing a band gap (E_g)>

3.0 eV in its neutral state, being fully conjugated in its neutral state and having an oxidation potential less than 0.5 V versus a saturated calomel electrode (SCE).

2. The composition of claim 1, wherein said polymer comprises a poly (3,4-alkylenedioxyheterocycle).

3. The composition of claim 2, wherein said alkylenedioxyheterocycle comprises at least one selected from the group consisting of an alkylenedioxypyrrole, an alkylenedioxythiophene and an alkylenedioxyfuran.

4. The composition of claim 2, wherein said poly(3,4-alkylenedioxyheterocycle) comprises N-alkyl substituted poly(3,4-alkylenedioxypyrrole).

5. The composition of claim 4, wherein said N-alkyl substituted poly(3,4-alkylenedioxypyrrole) is N-Pr PProDOP, N-Gly PProDOP or N-propane sulfonated PProDOP (PProDOP-NPrS).

6. The composition of claim 2, wherein said poly(3,4-alkylenedioxyheterocycle) comprises poly(3,4-propylenedioxypyrrole).

7. The composition of claim 6, said poly(3,4-propylenedioxypyrrole) comprises N-alkyl substituted poly(3,4-propylenedioxypyrrole).

8. The composition of claim 7, wherein said N-alkyl substituted poly(3,4-propylenedioxypyrrole) is N-Pr PProDOP, N-Gly PProDOP or N-propane sulfonated PProDOP (PProDOP-NPrS).

9. The composition of claim 2, wherein said poly(3,4-alkylenedioxyheterocycle) comprises poly(3,4-ethylenedioxypyrrole).

10. The composition of claim 9, wherein said poly(3,4-ethylenedioxypyrrole) comprises N-alkyl substituted poly(3,4-ethylenedioxypyrrole).

11. The composition of claim 1, wherein said polymer has an oxidation potential in the range between −

0.2 and −

0.0 volts versus a saturated calomel electrode (SCE).

12. The composition of claim 1, wherein said polymer has an oxidation potential less than 0.0 volts versus a saturated calomel electrode (SCE).

13. The device of claim 12, wherein said oxidation potential is in the range between −

0.2 and −

0.0 volts.

14. The composition of claim 1, wherein said polymer has an oxidation potential less than 0.2 volts versus a saturated calomel electrode (SCE).

15. The composition of claim 1, wherein said oxidation potential is less than 0.4 volts.

16. An electrochromic device, comprising:

a first electrode;

a second electrode;

an anodically coloring polymer providing a band gap (E_g)>

3.0 eV in its neutral state, being fully conjugated in its neutral state and having an oxidation potential less than 0.5 V versus a saturated calomel electrode (SCE) in electrical contact with said second electrode and a reducible species in contact with said first electrode, and

an electrolyte interposed between said anodically coloring polymer and said first electrode, wherein said device is optically clear when a positive voltage is applied to said first electrode with respect to the second electrode, and colored upon application of a negative voltage to said first electrode with respect to said second electrode.

17. The device of claim 16, wherein said reducible species comprises a cathodically coloring material.

18. The device of claim 16, wherein said anodically coloring polymer comprises a poly(3,4-alkylenedioxyheterocycle).

19. The device of claim 18, wherein said alkylenedioxyheterocycle comprises at least one selected from the group consisting of an alkylenedioxypyrrole, an alkylenedioxythiophene and an alkylenedioxyfuran.

20. The device of claim 18, wherein said poly(3,4-alkylenedioxyheterocycle) comprises N-alkyl substituted poly(3,4-alkylenedioxypyrrole).

21. The device of claim 20, wherein said N-alkyl substituted poly(3 4-alkylenedioxypyrrole) is N-Pr PrroDOP, N-Gly PProDOP or N-propane sulfonated PProDOP (PProDOP-NPrS).

22. The device of claim 18, wherein said poly(3,4-alkylenedioxyheterocycle) comprises poly(3,4-propylenedioxypyrrole).

23. The device of claim 18, wherein said poly(3,4-alkylenedioxyheterocycle) comprises poly(3,4-ethylenedioxypyrrole).

24. The device of claim 16, wherein said oxidation potential is less than 0.4 volts.

25. The device of claim 16, wherein said device switches between an optically clear and a colored state in less than one second.