High performance electrochemichromic solutions and devices thereof

• US 5,340,503 A
• Filed: 05/04/1992
• Issued: 08/23/1994
• Est. Priority Date: 11/29/1989
• Status: Expired due to Fees

• Current Assignee: Donnelly Corporation (Magna International Incorporated)
• Original Assignee: Donnelly Corporation (Magna International Incorporated)
• Inventors: Varaprasad, Desaraju V., Lynam, Niall R., Habibi, Hamid R., Desaraju, Padma
• Primary Examiner(s): TUCKER, PHILIP C
• Application Number:
  US07/878,176
• Time in Patent Office: 841 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 1/161 Gaskets; Spacers; Sealing of cells; Filling or closing of cells
• 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 specification discloses electrochemichromic solutions and devices based on the use of solvents comprising at least about 25% 3-hydroxypropionitrile, 3,3'"'"'-oxydipropionitrile, 2-acetylbutyrolactone, 2-methylglutaronitrile, 3-methylsulfolane and mixtures thereof. The specification also discloses vacuum backfilling techniques for filling electrochemichromic cells and enhanced UV stability through solvent self-screening.

Claims

1. An electrochemichromic solution comprising:

solvent;

a redox chemical pair in solution in said solvent which colors in the presence of an applied voltage and which bleaches to a colorless condition in the absence of an applied voltage;

said solvent including at least 25% by volume of a solvent selected from the group consisting of;

3-hydroxypropionitrile (HPN), 3,3'"'"'-oxydipropionitrile (ODPN), 2-acetylbutyrolactone (ABL), 2-methylglutaronitrile (MGNT) 3-methylsulfolane (MS) and mixtures thereof.

2. The solution of claim 1 which additionally includes an electrolyte dissolved in said solvent.

3. The electrochemichromic solution of claim 1 in which said solvent comprises:

3-hydroxypropionitrile and 3-methylsulfolane in a ratio by volume of from about 75;

25 to about 25;

75.

4. The electrochemichromic solution of claim 1 in which said solvent comprises:

propylene carbonate and 3,3'"'"'-oxydipropionitrile in a ratio by volume of from about 75;

25 to about 25;

75.

5. The electrochemichromic solution of claim 1 in which said solvent comprises:

3-hydroxypropionitrile and 2-acetylbutyrolactone in a ratio by volume of from about 75;

25 to about 25;

75.

6. The electrochemichromic solution of claim 1 in which said solvent comprises:

2-acetylbutyrolactone and 3,3'"'"'-oxydipropionitrile in a ratio by volume of from about 75;

25 to about 25;

75.

7. The electrochemichromic solution of claim 1 in which said solvent comprises:

propylene carbonate and 2-acetylbutyrolactone in a ratio by volume of from about 75;

25 to about 25;

75.

8. The electrochemichromic solution of claim 1 in which said solvent comprises:

3-hydroxypropionitrile and 3,3'"'"'-oxydipropionitrile in ratio by volume of from about 75;

25 to about 25;

75.

9. The electrochemichromic solution of claim 1 in which said redox pair comprise a cathodic material selected from the group consisting of methylviologen, ethylviologen, benzylviologen, heptylviologen and mixtures thereof;

with a counterion selected from the group consisting of perchlorate, tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate and mixtures thereof; and

an anodic material selected from the group consisting of;

DMPA--5,10-dihydro-5,10-dimethylphenazine,

DEPA--5,10-dihydro-5,10-diethylphenazine,

DOPA--5,10-dihydro-5,10-dioctylphenazine,

TMPD--N,N,N'"'"',N'"'"'-tetramethylphenylenediamine,

TMBZ--N,N,N'"'"',N'"'"'-tetramethylbenzidine,

TTF--Tetrathiafulvalene and mixtures thereof.

10. The electrochemichromic solution of claim 9 in which said anodic and cathodic materials are employed at from about 0.02 to about 0.05 molar concentrations.

11. The electrochemichromic solution of claim 9 in which said cathodic material is methylviologen, said counterion is hexafluorophosphate and said anodic material is 5,10-dihydro-5,10-dimethylphenazine.

12. The electrochemichromic solution of claim 11 in which said anodic and cathodic materials are employed at 0.025 molar concentration.

13. The electrochemichromic solution of claim 1 in which said solution additionally comprises an ultraviolet stabilizer at a concentration of up to about 5% weight by volume.

14. An electrochemichromic solution, comprising:

a redox chemical pair in solution in a solvent, wherein said redox chemical pair colors in the presence of an applied voltage and bleaches to a colorless condition in the absence of said voltage, said solvent comprising 3-hydroxypropionitrile.

15. The electrochemichromic solution of claim 14 wherein said solution further comprises a second solvent.

16. The electrochemichromic solution of claim 15 wherein said 3-hydroxypropionitrile is present in amounts of at least 50 volume percent of all solvents.

17. The electrochemichromic solution of claim 16 wherein said redox chemical pair comprises an aliphatic viologen.

18. The electrochemichromic solution of claim 17 wherein said aliphatic viologen is a C_1-7 aliphatic viologen.

19. The electrochemichromic solution of claim 18 wherein said aliphatic viologen is methylviologen or ethylviologen.

20. The electrochemichromic solution of claim 14 wherein said redox chemical pair comprises an aliphatic viologen.

21. The electrochemichromic solution of claim 20 wherein said aliphatic viologen is a C_1-7 aliphatic viologen.

22. The electrochemichromic solution of claim 21 wherein said aliphatic viologen is methylviologen or ethylviologen.

23. A method for protecting a redox chemical pair in an electrochemichromic solution from degradation due to exposure to ultraviolet radiation comprising:

using a solvent for said redox chemical pair which will transmit through a one millimeter path length no more than about 30% of the solar radiation in a 250 to 350 nm range passed through a half wave ITO coated soda lime glass substrate of a thickness of 0.063 inches.

24. The method of claim 23 in which said solvent comprises at least 25% by volume 2-acetylbutyrolactone (ABL).

25. The method of claim 24 in which said solvent comprises:

propylene carbonate and 2-acetylbutyrolactone in a ratio of from about 75;

25 to about 25;

75.

26. The method of claim 24 in which said solvent comprises:

3-hydroxypropionitrile and 2-acetylbutyrolactone in a ratio of from about 75;

25 to about 25;

75.

27. The method of claim 24 in which said solvent comprises:

3,3'"'"'-oxydipropionitrile and 2-acetylbutyrolactone in a ratio of from about 75;

25 to about 25;

75.

28. An electrochemichromic solution possessing resilience to outdoor weathering on an automobile, said solution comprising:

a solvent;

a redox chemical pair in solution in said solvent, wherein said redox chemical pair colors under the application of voltage and bleaches in the absence of an applied voltage; and

an ultraviolet stabilizer in solution in said solvent, in an amount within the range of from greater than 1.7% wt/vol up to 40.2% wt/vol, whereby the electrochemichromic solution is provided with enhanced ultraviolet stability.

29. The electrochemichromic solution of claim 28 wherein said ultraviolet stabilizer is selected from the group consisting of benzophenones and cyanoacrylates.

30. The electrochemichromic solution of claim 28 or 29 wherein said ultraviolet stabilizer has a concentration in said electrochemichromic solution of at least approximately 5% wt/vol.

31. The electrochemichromic solution of claim 28 wherein said redox chemical pair further comprises a viologen species.

32. The electrochemichromic solution of claim 28 wherein said redox chemical pair comprises a viologen species and at least one compound selected from the group consisting of phenazines, phenylenediamines, benzidenes and fulvalenes.

33. The electrochemichromic solution of claim 32 wherein said phenazine compound is selected from the group consisting of 5,10-dihydro-5,10-dimethylphenazine, 5,10-dihydro-5,10-diethylphenazine and 5,10-dihydro-5,10-dioctylphenazine.

34. The electrochemichromic solution of claim 32 wherein said phenazine compound is 5,10-dihydro-5,10-dimethylphenazine.

35. The electrochemichromic solution of claim 32 wherein said phenylenediamine compound is N,N,N'"'"',N'"'"'-tetramethyl-phenylenediamine.

36. The electrochemichromic solution of claim 32 wherein said benzidene compound is N,N,N'"'"',N'"'"'-tetramethylbenzidene.

37. The electrochemichromic solution of claim 32 wherein said fulvalene compound is tetrathiafulvalene.

38. The electrochemichromic solution of claim 29 wherein said ultraviolet stabilizer is a benzophenone.

39. The electrochemichromic solution of claim 29 wherein said ultraviolet stabilizer is a cyanoacrylate.

40. The electrochemichromic solution of claim 29 wherein said ultraviolet stabilizer is selected from the group consisting of 2,4-dihydroxy-benzophenone, 2,2'"'"'-dihydroxy-4-methoxybenzophenone, and 2-ethylhexyl-2-cyano-3,3-diphenylacrylate.

41. The electrochemichromic solution of claim 28 wherein said solvent comprises 3-hydroxypropionitrile.

42. The electrochemichromic solution of claim 41 wherein said 3-hydroxypropionitrile is present in amounts of at least about 50 volume percent.

43. The electrochemichromic solution of claim 42 wherein said solvent further comprises 3,3'"'"'-oxydipropionitrile.

44. The electrochemichromic solution of claim 28 wherein said solvent comprises 3-hydroxypropionitrile.

45. The electrochemichromic solution of claim 44 wherein said 3-hydroxypropionitrile is present in amounts of at least about 50 volume percent.

46. The electrochemichromic solution of claim 28 wherein said solvent comprises 3,3'"'"'-oxydipropionitrile.

47. The electrochemichromic solution of claim 28 wherein said redox pair further comprises a counterion selected from the group consisting of hexafluorophosphate, tetrafluoroborate, perchlorate, trifluoromethane sulfonate and mixtures thereof.

48. The electrochemichromic solution of claim 28 wherein said solution is vacuum backfilled using inert gas into an electrochemichromic cell.

49. The electrochemichromic solution of claim 48 wherein said electrochemichromic cell has spaced plates, each having an inwardly facing conductive surface, said spaced plates being sealed around the periphery by a seal, said peripheral seal enclosing an area of each of said plates, and said vacuum backfilling using inert gas of said electrochemichromic solution into said cell comprises:

introducing a small gap into said peripheral seal of said cell;

placing said cell in a chamber along with a container of an electrochemichromic solution and evacuating said chamber;

lowering said cell into said container of said electrochemichromic solution such that said gap is located under the surface of the electrochemichromic solution;

exposing said electrochemichromic solution to a source of inert gas of pressure greater than that in said cell to thereby cause said electrochemichromic solution to flow into said cell; and

sealing said gap in said peripheral seal of said cell.

50. The electrochemichromic solution of claim 49 wherein said placing said cell in a chamber and evacuating said chamber comprises:

placing said electrochemichromic cell in a vacuum chamber along with a container of an electrochemichromic solution and evacuating said chamber to a vacuum; and

wherein said exposing said electrochemichromic solution to a source of inert gas comprises subsequently venting said chamber to an atmospheric pressure; and

said vacuum backfilling using inert gas further comprises removing said electrochemichromic cell from said container prior to said sealing step.

51. The electrochemichromic solution of claim 49 wherein said area of each of said spaced plates of said electrochemichromic cell is at least 110 cm².

52. The electrochemichromic solution of claim 50 wherein said chamber is pressurized to above atmospheric pressure after it has been vented to atmospheric pressure.

53. The electrochemichromic solution of claim 49 wherein said inert gas is nitrogen.

54. The electrochemichromic solution of claim 49 wherein said electrochemichromic solution is cooled to reduce its vapor pressure.