Color-stabilized electrochromic devices

• US 6,735,011 B2
• Filed: 11/25/2002
• Issued: 05/11/2004
• Est. Priority Date: 08/19/1999
• Status: Expired due to Term

• Current Assignee: Gentex Corporation
• Original Assignee: Gentex Corporation
• Inventors: Guarr, Thomas F., Lomprey, Jeffrey R.
• Primary Examiner(s): Schwartz, Jordan M.
• Assistant Examiner(s): THOMPSON, TIMOTHY J
• Application Number:
  US10/303,930
• Publication Number:
  US 20030174378A1
• Time in Patent Office: 533 Days
• Field of Search: 359/265, 359/272, 359/273, 359/275, 359/321, 359/322, 252/583
• US Class Current: 359/265
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02F 1/1503 caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
• CPC Class Codes: G02F 1/1525 characterised by a particular ion transporting layer, e.g. electrolyte
• CPC Class Codes: G02F 2001/1502 complementary cell
• CPC Class Codes: G02F 2001/15145 the electrochromic layer comprises a mixture of anodic and cathodic compounds

Abstract

An electrochromic medium for use in a normally operating electrochromic device comprising an anodic material and a cathodic material wherein both of the anodic and cathodic materials are electroactive and at least one of the anodic and cathodic materials is electrochromic, an additive, and means associated with the additive for maintaining a colorless or nearly colorless electrochromic medium while the electrochromic medium is in a high transmission state relative to an electrochromic medium without the additive.

Claims

1. An electrochromic device, comprising:

(a) a first substantially transparent substrate having an electrically conductive material associated therewith;

(b) a second substrate having an electrically conductive material associated therewith;

and

(c) an electrochromic medium contained within a chamber positioned between the first and second substrates which comprises;

(1) a solvent;

(2) an anodic electroactive material;

(3) a cathodic electroactive material, wherein at least one of the anodic and cathodic electroactive materials is electrochromic; and

(4) a color-stabilizing additive, wherein the color-stabilizing additive is more easily reduced than the cathodic material, and further wherein the color-stabilizing additive substantially precludes the formation of a residual reduced cathodic material while the electrochromic medium is in a high transmission state.

2. The electrochromic device according to claim 1, wherein either the front surface or the rear surface of the second substrate has a reflective material disposed thereon.

3. The electrochromic device according to claim 1, wherein the color-stabilizing additive comprises an oxidized form of the anodic material.

4. The electrochromic device according to claim 1, wherein the color-stabilizing additive comprises an additional material present in an oxidized form.

5. The electrochromic device according to claim 1, wherein the color-stabilizing additive is selected from the group consisting of ferrocinium salts, substituted ferrocinium salts, phenazinium salts, substituted phenazinium salts, and combinations thereof.

6. The electrochromic device according to claim 1, wherein the cathodic material comprises tungsten oxide.

7. An electrochromic device, comprising:

(a) a first substantially transparent substrate having an electrically conductive material associated therewith;

(b) a second substrate having an electrically conductive material associated therewith; and

(c) an electrochromic medium contained within a chamber positioned between the first and second substrates which comprises;

(1) a solvent;

(2) an anodic electroactive material;

(3) a cathodic electroactive material, wherein at least one of the anodic and cathodic electroactive materials is electrochromic; and

(4) a color-stabilizing additive, wherein the color-stabilizing additive comprises a reduced form of the cathodic material.

8. The electrochromic device according to claim 7, wherein either the front surface or the rear surface of the second substrate has a reflective material disposed thereon.

9. The electrochromic device according to claim 7, wherein the color-stabilizing additive substantially precludes the formation of a residual oxidized anodic material while the electrochromic medium is in a high transmission state.

10. An electrochromic device, comprising:

(a) a first substantially transparent substrate having an electrically conductive material associated therewith;

(b) a second substrate having an electrically conductive material associated therewith; and

(c) an electrochromic medium contained within a chamber positioned between the first and second substrates which comprises;

(1) a solvent;

(2) an anodic electroactive material;

(3) a cathodic electroactive material, wherein at least one of the anodic and cathodic electroactive materials is electrochromic; and

(4) a color-stabilizing additive, wherein the color-stabilizing additive is more easily oxidized than the anodic material, and wherein the color-stabilizing additive substantially precludes the formation of a residual oxidized anodic material while the electrochromic medium is in a high transmission state.

11. The electrochromic device according to claim 10 wherein the color-stabilizing additive is selected from the group consisting of substituted ferrocenes, substituted ferrocenyl salts, and combinations thereof.

12. The electrochromic device according to claim 10, wherein either the front surface or the rear surface of the second substrate has a reflective material disposed thereon.

13. The electrochromic device according to claim 10, wherein the cathodic material comprises tungsten oxide.

14. An electrochromic device, comprising:

(a) a first substantially transparent substrate having an electrically conductive material associated therewith;

(b) a second substrate having an electrically conductive material associated therewith; and

(c) an electrochromic medium contained within a chamber positioned between the first and second substrates which comprises;

(1) a solvent;

(2) an anodic electroactive material;

(3) a cathodic electroactive material, wherein at least one of the anodic and cathodic electroactive materials is electrochromic; and

(4) a color-stabilizing additive, wherein the color-stabilizing additive comprises a first component that is more easily reduced than the cathodic material and a second component that is more easily oxidized than the anodic material.

15. The electrochromic device according to claim 14, wherein either the front surface or the rear surface of the second substrate has a reflective material disposed thereon.

16. The electrochromic device according to claim 14, wherein the first component substantially precludes the formation of a residual reduced cathodic material and the second component substantially precludes the formation of a residual oxidized anodic material while the electrochromic medium is in a high transmission state.

17. The electrochromic device according to claim 14, wherein the first component comprises an oxidized form of the anodic material.

18. The electrochromic device according to claim 14, wherein the first component comprises an additional electroactive material present in an oxidized form.

19. The electrochromic device according to claim 14, wherein the first component is selected from the group consisting of ferrocinium salts, substituted ferrocinium salts, phenazinium salts, substituted phenazinium salts, and combinations thereof.

20. The electrochromic device according to claim 14, wherein the second component is selected from the group consisting of substituted phenazines, substituted ferrocenes, substituted ferrocenyl salts, and combinations thereof.

21. The electrochromic medium according to claim 14, wherein the cathodic material comprises a viologen.

22. An electrochromic device, comprising:

(a) a first substantially transparent substrate having an electrically conductive material associated therewith;

(b) a second substrate having an electrically conductive material associated therewith; and

(c) an electrochromic medium contained within a chamber positioned between the first and second substrates which comprises;

(1) a solvent;

(2) an anodic electroactive material;

(3) a cathodic electroactive material, wherein at least one of the anodic and cathodic electroactive materials is electrochromic;

(4) a color-stabilizing additive; and

(5) means associated with the color-stabilizing additive for maintaining a less colored electrochromic medium while the electrochromic medium is in a high transmission state relative to an electrochromic medium without the color-stabilizing additive.

23. The electrochromic device according to claim 22, wherein the less colored electrochromic medium maintaining means comprises the additive being more easily reduced than the cathodic material.

24. The electrochromic device according to claim 22, wherein the less colored electrochromic medium maintaining means comprises the additive being a reduced form of the cathodic material.

25. The electrochromic device according to claim 22, wherein the less colored electrochromic medium maintaining means comprises the additive being more easily oxidized than the anodic material.

26. The electrochromic device according to claim 22, wherein the less colored electrochromic medium maintaining means comprises the additive having a first component and a second component wherein,

the first component is more easily reduced than the cathodic material; and

the second component is more easily oxidized than the anodic material.

27. The electrochromic device according to claim 22, wherein the electrochromic medium is nearly colorless while the electrochromic medium is in a high transmission state.

28. The electrochromic device according to claim 22, wherein the electrochromic medium is not strongly colored while the electrochromic medium is in a high transmission state.

29. The electrochromic device according to claim 22, wherein either the front surface or the rear surface of the second substrate has a reflective material disposed thereon.

30. An electrochromic device, comprising:

(a) a first substantially transparent substrate having an electrically conductive material associated therewith;

(b) a second substrate having an electrically conductive material associated therewith; and

(c) an electrochromic medium contained within a chamber positioned between the first and second substrates which comprises;

(1) a solvent;

(2) an anodic electroactive material;

(3) a cathodic electroactive material, wherein at least one of the anodic and cathodic electroactive materials is electrochromic;

(4) a color-stabilizing additive; and

(5) means associated with the color-stabilizing additive for maintaining a nearly colorless electrochromic medium while the electrochromic medium is in a zero potential or open circuit state relative to an electrochromic medium without the color-stabilizing additive.

31. An electrochromic device, comprising:

(a) a first substantially transparent substrate having an electrically conductive material associated therewith;

(b) a second substrate having an electrically conductive material associated therewith; and

(c) a color-stabilized electrochromic medium contained within a chamber positioned between the first and second substrates which comprises;

(1) a solvent;

(2) an anodic electroactive material; and

(3) a cathodic electroactive material, wherein at least one of the anodic and cathodic electroactive materials is electrochromic; and

(d) wherein the electrochromic device exhibits at least two of;

(1) an absolute value of Δ

a* of less than 3.25 after being exposed to an autoclave pressurized to 400 p.s.i. with oxygen for approximately 2,000 hours at ambient temperature;

(2) an absolute value of Δ

b* of less than 6.00 after being exposed to an autoclave pressurized to 400 p.s.i. with oxygen for approximately 2,000 hours at ambient temperature;

(3) an absolute value of Δ

E of less than 9.00 after being exposed to an autoclave pressurized to 400 p.s.i. with oxygen for approximately 2,000 hours at ambient temperature; and

(4) an absolute value of Δ

Y of less than 7.50 after being exposed to an autoclave pressurized to 400 p.s.i. with oxygen for approximately 2,000 hours at ambient temperature.

32. An electrochromic device, comprising:

(a) a first substantially transparent substrate having an electrically conductive material associated therewith;

(b) a second substrate having an electrically conductive material associated therewith; and

(c) a color-stabilized electrochromic medium contained within a chamber positioned between the first and second substrates which comprises;

(1) a solvent;

(2) an anodic electroactive material; and

(3) a cathodic electroactive material, wherein at least one of the anodic and cathodic electroactive materials is electrochromic; and

(d) wherein the electrochromic device exhibits at least two of;

(1) an absolute value of Δ

a* of less than 2.00 after being exposed to an autoclave pressurized to 400 p.s.i. with oxygen for approximately 2,000 hours at ambient temperature;

(2) an absolute value of Δ

b* of less than 3.00 after being exposed to an autoclave pressurized to 400 p.s.i. with oxygen for approximately 2,000 hours at ambient temperature;

(3) an absolute value of Δ

E of less than 9.00 after being exposed to an autoclave pressurized to 400 p.s.i. with oxygen for approximately 2,000 hours at ambient temperature; and

(4) an absolute value of Δ

Y of less than 5.00 after being exposed to an autoclave pressurized to 400 p.s.i. with oxygen for approximately 2,000 hours at ambient temperature.

33. An electrochromic device, comprising:

(a) a first substantially transparent substrate having an electrically conductive material associated therewith;

(b) a second substrate having an electrically conductive material associated therewith; and

(c) a color-stabilized electrochromic medium contained within a chamber positioned between the first and second substrates which comprises;

(1) a solvent;

(2) an anodic electroactive material; and

(3) a cathodic electroactive material, wherein at least one of the anodic and cathodic electroactive materials is electrochromic; and

(d) wherein the electrochromic device exhibits at least two of;

(1) an absolute value of Δ

a* of less than 2.00 after being exposed to 85 degrees centigrade for approximately 2,000 hours;

(2) an absolute value of Δ

b* of less than 10.00 after being exposed to 85 degrees centigrade for approximately 2,000 hours;

(3) an absolute value of Δ

E of less than 12.00 after being exposed to 85 degrees centigrade for approximately 2,000 hours; and

(d) an absolute value of Δ

Y of less than 10.00 after being exposed to 85 degrees centigrade for approximately 2,000 hours.

34. An electrochromic device, comprising:

(a) a first substantially transparent substrate having an electrically conductive material associated therewith;

(b) a second substrate having an electrically conductive material associated therewith; and

(c) a color-stabilized electrochromic medium contained within a chamber positioned between the first and second substrates which comprises;

(1) a solvent;

(2) an anodic electroactive material; and

(3) a cathodic electroactive material, wherein at least one of the anodic and cathodic electroactive materials is electrochromic; and

(d) wherein the electrochromic device exhibits at least two of;

(1) an absolute value of Δ

a* of less than 2.00 after being exposed to 85 degrees centigrade for approximately 2,000 hours;

(2) an absolute value of Δ

b* of less than 1.00 after being exposed to 85 degrees centigrade for approximately 2,000 hours;

(3) an absolute value of Δ

E of less than 2.00 after being exposed to 85 degrees centigrade for approximately 2,000 hours; and

(4) an absolute value of Δ

Y of less than 1.00 after being exposed to 85 degrees centigrade for approximately 2,000 hours.