Electrochromic devices with bipyridinium salt solutions

• US 5,336,448 A
• Filed: 06/25/1991
• Issued: 08/09/1994
• Est. Priority Date: 06/25/1991
• Status: Expired due to Fees

• Current Assignee: Gentex Corporation
• Original Assignee: Gentex Corporation
• Inventors: Byker, Harlan J.
• Primary Examiner(s): TUCKER, PHILIP C
• Application Number:
  US07/720,177
• Time in Patent Office: 1,141 Days
• Field of Search: 252/583, 252/586, 252/600, 359/265, 359/272, 359/275
• US Class Current: 252/583
• 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 2001/1502 complementary cell
• CPC Class Codes: G02F 2001/15145 the electrochromic layer comprises a mixture of anodic and cathodic compounds

Abstract

The present invention provides solution-phase electrochromic devices, including such devices that are single-compartment and self-erasing, in which the media of variable transmittance are solutions comprising, as cathodic electrochromic compounds, certain 4,4'"'"'-bipyridinium salts, such as salts of 1,1'"'"'-dibenzyl-2,2'"'"',6,6'"'"'-tetraalkyl-4,4'"'"'-bipyridinium cations. Electrochromic devices of the invention are components of variable transmittance in display devices, windows and other types of light filters, and variable reflectance mirrors, such as those that can be used as dimmable rearview mirrors in motor vehicles.

Claims

1. A solution-phase electrochromic device in which the solution of variable transmittance comprises a solvent, which is a liquid at room temperature, and a salt of a cation of Formula XVII ##STR10## wherein R₃₆ and R₃₇ are independently selected from the group consisting of benzyl and alkyl of 1-20 carbon atoms;

and R₃₄, R₃₅, R₃₈ and R₃₉ are independently selected from the group consisting of alkyl groups of 1-4 carbon atoms.

2. A device of claim 1 wherein, in the cation of the salt in the solution, R₃₆ and R₃₇ are benzyl.

3. A device of claim 1 wherein, in the cation of the salt in the solution, R₃₄, R₃₅, R₃₈ and R₃₉ are methyl.

4. A device of claim 2 wherein, in the solution, the cation of the salt is 1,1 '"'"'-dibenzyl-2,2'"'"',6,6'"'"'-tetramethyl-4,4'"'"'-bipyridinium.

5. A device of claim 2 wherein, in the solution, the solvent consists essentially of propylene carbonate, gamma-butyrolactone, gamma-valerolactone, or an homogeneous mixture of any two or more of said solvents or any one or more of said solvents with ethylene carbonate.

6. A device of claim 3 wherein, in the solution, the solvent consists essentially of propylene carbonate, gamma-butyrolactone, gamma-valerolactone, or an homogeneous mixture of any two or more of said solvents or any one or more of said solvents with ethylene carbonate.

7. A device of claim 4 wherein, in the solution, the solvent consists essentially of propylene carbonate, gamma-butyrolactone, gamma-valerolactone, or an homogeneous mixture of any two or more of said solvents or any one or more of said solvents with ethylene carbonate.

8. A device of claim 5 wherein, in the solution, the solvent consists essentially of propylene carbonate.

9. A device of claim 6 wherein, in the solution, the solvent consists essentially of propylene carbonate.

10. A device of claim 7 wherein, in the solution, the solvent consists essentially of propylene carbonate.

11. A device of any of claims 1-10 wherein, in the solution, the concentration of the cation of Formula XVII is from 0.001M to 0.1M.

12. A device of claim 11 wherein, in the solution, the anions of the salt of the cation of Formula XVII are selected from the group consisting of BF₄^-, PF₆^- and ClO₄^-.

13. A device of claim 12 wherein, in the solution, the salt of the cation of Formula XVII is 1,1'"'"'-dibenzyl-2,2'"'"',6,6'"'"'-tetramethyl-4,4'"'"'-bipyridinium difluoroborate.

14. A solution-phase electrochromic device in which the solution of variable transmittance comprises a solvent;

an anodic electrochromic compound which, upon oxidation of its zero-potential equilibrium state, undergoes an increase in molar extinction coefficient at at least one wavelength in the visible range; and

a cathodic electrochromic compound which is a salt of a cation of Formula IV ##STR11## wherein R₇ and R₈ are independently selected from the group consisting of an alkyl group with 1-20 carbon atoms and benzyl; and

R₉, R₁₀, R₁₁, and R₁₂ are independently selected from the group consisting of alkyl groups with 1-4 carbon atoms.

15. A device according to claim 14 which is single-compartment and self-erasing.

16. A device according to claim 15 wherein, in the solution, the solvent consists essentially of propylene carbonate, gamma-butyrolactone, gamma-valerolactone, or an homogeneous mixture of any two or more of said solvents or any one or more of said solvents with ethylene carbonate.

17. A device according to claim 16 wherein, in the solution, the solvent consists essentially of propylene carbonate.

18. A device according to claim 14 wherein, in the solution, the cathodic compound is a salt of a cation of Formula XLV ##STR12## wherein R₁₃ is alkyl of 1-4 carbon atoms or benzyl, and R₁₄ and R₁₅ are independently selected from the group consisting of alkyl groups of 1-4 carbon atoms, and the anions of the salt are selected from the group consisting of BF₄^-, PF₆^- and ClO₄^- ;

and the anodic compound is selected from the group consisting of 5,10-dihydro-5,10-dimethylphenazine, N,N,N'"'"',N'"'"'-tetramethyl-p-phenylenediamine, N,N,N'"'"',N'"'"'-tetraphenyl-p-phenylenediamine, and bis-3,3'"'"'-diethyl-2,2'"'"'-benzothiazole azine.

19. A device according to claim 15 wherein, in the solution, the cathodic compound is a salt of a cation of Formula XLV ##STR13## wherein R₁₃ is alkyl of 1-4 carbon atoms or benzyl, and R₁₄ and R₁₅ are independently selected from the group consisting of alkyl groups of 1-4 carbon atoms, and the anions of the salt are selected from the group consisting of BF₄^-, PF₆^- and ClO₄^- ;

and the anodic compound is selected from the group consisting of 5,10-dihydro-5,10-dimethylphenazine, N,N,N'"'"',N'"'"'-tetramethyl-p-phenylenediamine, N,N,N'"'"',N'"'"'-tetraphenyl-p-phenylenediamine, and bis-3,3'"'"'-diethyl-2,2'"'"'-benzothiazole azine.

20. A device according to claim 16 wherein, in the solution, the cathodic compound is a salt of a cation of Formula XLV ##STR14## wherein R₁₃ is alkyl of 1-4 carbon atoms or benzyl, and R₁₄ and R₁₅ are independently selected from the group consisting of alkyl groups of 1-4 carbon atoms, and the anions of the salt are selected from the group consisting of BF₄^-, PF₆^- and ClO₄^- ;

and the anodic compound is selected from the group consisting of 5,10-dihydro-5,10-dimethylphenazine, N,N,N'"'"',N'"'"'-tetramethyl-p-phenylenediamine, N,N,N'"'"',N'"'"'-tetraphenyl-p-phenylenediamine, and bis-3,3'"'"'-diethyl-2,2'"'"'-benzothiazole azine.

21. A device according to claim 17 wherein, in the solution, the cathodic compound is a salt of a cation of Formula XLV ##STR15## wherein R₁₃ is alkyl of 1-4 carbon atoms or benzyl, and R₁₄ and R₁₅ are independently selected from the group consisting of alkyl groups of 1-4 carbon atoms, and the anions of the salt are selected from the group consisting of BF₄^-, PF₆^- and ClO₄^- ;

and the anodic compound is selected from the group consisting of 5,10-dihydro-5,10-dimethylphenazine, N,N,N'"'"',N'"'"'-tetramethyl-p-phenylenediamine, N,N,N'"'"',N'"'"'-tetraphenyl-p-phenylenediamine, and bis-3,3'"'"'-diethyl-2,2'"'"'-benzothiazole azine.

22. A device according to claim 18 wherein, in the solution, the anodic compound is 5,10-dihydro-5,10-dimethylphenazine.

23. A device according to claim 19 wherein, in the solution, the anodic compound is 5,10-dihydro-5,10-dimethylphenazine.

24. A device according to claim 20 wherein, in the solution, the anodic compound is 5,10-dihydro-5,10-dimethylphenazine.

25. A device according to claim 21 wherein, in the solution, the anodic compound is 5,10-dihydro-5,10-dimethylphenazine.

26. A device according to claim 22 wherein, in the solution, in the cation of Formula XLV, R₁₃ is benzyl.

27. A device according to claim 26 wherein, in the solution, in the cation of Formula XLV, R₁₄ and R₁₅ are methyl and the salt of said cation is the difluoroborate.

28. A device according to claim 23 wherein, in the solution, in the cation of Formula XLV, R₁₃ is benzyl.

29. A device according to claim 28 wherein, in the solution, in the cation of Formula XLV, R₁₄ and R₁₅ are methyl and the salt of said cation is the difluoroborate.

30. A device according to claim 24 wherein, in the solution, in the cation of Formula XLV, R₁₃ is benzyl.

31. A device according to claim 30 wherein, in the solution, in the cation of Formula XLV, R₁₄ and R₁₅ are methyl and the salt of said cation is the difluoroborate.

32. A device according to claim 25 wherein, in the solution, in the cation of Formula XLV, R₁₃ is benzyl.

33. A device according to claim 32 wherein, in the solution, in the cation of Formula XLV, R₁₄ and R₁₅ are methyl and the salt of said cation is the difluoroborate.

34. A device according to any of claims 20, 21, and 24-33 wherein, in the solution, the concentrations of the cathodic electrochromic compound and the anodic electrochromic compound are from 0.001M to 0.1M.

35. A device acccording to claim 34 wherein the solution is thickened with 1 wt. %-10 wt. % polymethymethacrylate.

36. A device according to any of claims 20, 21, and 24-33 wherein the solution comprises a UV-stabilizing compound.

37. A device according to claim 36 which comprises, in the solution at a concentration from 0.1M to 0.6M, an alkyl ester of 2-cyano-3,3-diphenyl acrylate, wherein the alkyl group has 1-10 carbon atoms.

38. A device according to claim 37 wherein the alkyl ester is ethyl 2-cyano-3,3-diphenyl acrylate.

39. A device according to claim 38 wherein the solution is thickened with 1 wt. %-10 wt. % polymethymethacrylate.

40. A device according to claim 39 which is the component of variable transmittance in a variable transmittance light filter.

41. A device according to claim 14 which is the component of variable transmittance in a variable reflectance, rearview motor-vehicle mirror.

42. A device according to claim 39 which is the component of variable transmittance in a variable reflectance, rearview motor-vehicle mirror.