Method for filling large area electrochromic windows

• US 6,207,083 B1
• Filed: 11/08/1999
• Issued: 03/27/2001
• 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: Habibi, Hamid R., Desaraju, Padma, Varaprasad, Desaraju V., Lynam, Niall R.
• Primary Examiner(s): TUCKER, PHILIP C
• Application Number:
  US09/436,325
• Time in Patent Office: 505 Days
• Field of Search: 252/583, 359/265, 359/275, 359/272, 141/7, 141/5, 141/6
• 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. A method for filling a large area electrochromic window having an electrochromically active area of at least about 110 cm², including two spaced-apart plates, each plate having an inwardly facing transparent conductive surface, said spaced plates being separated around their peripheries by a peripheral seal having a gap therein, said peripheral seal enclosing an area of each of said plates to define a cavity within said window, said filling method comprising:

placing said window in a chamber along with a container of a liquid medium comprising electrochromic material and evacuating said chamber;

said liquid medium comprising an organic solvent having a vapor pressure of less than 3.2 mm of mercury at 25°

C.;

lowering said window into said container of liquid medium such that said gap is located under the surface of said liquid medium;

exposing said liquid medium to a source of inert gas of pressure greater than that in said cavity within said window to thereby cause said medium to flow into said cavity of said window;

removing said window from said container; and

sealing said gap in said peripheral seal of said window.

2. A method as claimed in claim 1 wherein evacuating said chamber comprises placing said window in a vacuum chamber along with said container of said liquid medium and evacuating said chamber to a vacuum.

3. A method as claimed in claim 1 wherein said chamber is pressurized to above atmospheric pressure during or after said exposure step.

4. A method as claimed in claim 1 wherein said liquid medium is cooled to reduce its vapor pressure.

5. The method of claim 1 wherein said electrochromic material comprises at least one of a cathodically coloring electrochromic material and an anodically coloring electrochromic material.

6. The method of claim 1 wherein said electrochromic material comprises a viologen species.

7. The method of claim 1 wherein said electrochromic material comprises at least one of a phenazine, a phenyldiamine, a benzidene and a fulvalene.

8. The method of claim 1 wherein said organic solvent is a solvent comprising at least 25% by volume of 3-hydroxypropionitrile (HPN), 3,3′

-oxydipropionitrile (ODPN), 2-acetylbutyrolactone (ABL), 2-methylglutaronitrile (MGNT), 3-methylsulfolane (MS), propylene carbonate (PC) or a mixture thereof.

9. The method of claim 1 wherein said electrochromic window comprises one of an architectural window and an automotive window.

10. The method of claim 1 including exposing said liquid medium to an inert gas comprising nitrogen.

11. The method of claim 1 wherein said liquid medium comprises an ultraviolet stabilizer.

12. The method of claim 1 wherein said liquid medium comprises an ultraviolet stabilizer in solution therein in an amount of at least 1.7% wt/vol.

13. The method of claim 12 wherein said liquid medium comprises an ultraviolet stabilizer in solution therein in an amount within the range of from greater than 1.7% wt/vol up to 40.2% wt/vol.

14. The method of claim 1 wherein said liquid medium comprises an ultraviolet stabilizer in solution therein in an amount of at least approximately 5% wt/vol.

15. A method for filling a large area electrochromic device having an electrochromically active area of at least about 110 cm², and including two spaced-apart plates, each plate having an inwardly facing conductive surface, said spaced plates being separated around their peripheries by a peripheral seal to form a sealed cavity, said sealed cavity containing a gaseous medium, the method comprising:

providing a pair of spaced openings in the device which are in fluid communication with said sealed cavity;

placing a first of said openings in flow communication with a liquid medium;

placing the second of said openings in flow communication with a vacuum source;

and drawing said liquid medium into said sealed cavity of the device through said first opening while said gaseous medium within said sealed cavity is evacuated by the vacuum source through said second opening.

16. A method of claim 15 wherein said liquid medium comprises at least one of a cathodically coloring electrochromic material and an anodically coloring electrochromic material.

20. The method of claim 15 wherein said liquid medium includes an electrochromic material comprising a viologen species.

22. The method of claim 15 in which said liquid medium is placed in a syringe which is tightly held to one of said openings to accomplish said step of placing said one of said openings in flow communication with said liquid medium.

26. The method of claim 15 wherein said liquid medium comprises an ultraviolet stabilizer.

27. The method of claim 15 wherein said liquid medium comprises an ultraviolet stabilizer in solution therein in an amount of at least 1.7% wt/vol.

28. The method of claim 27 wherein said liquid medium comprises an ultraviolet stabilizer in solution therein in an amount within the range of from greater than 1.7% wt/vol up to 40.2% wt/vol.

40. The method of claim 15 wherein said gaseous medium comprises air.

17. A method for filling a large area electrochromic device having an electrochromically active area of at least about 110 cm², and including two spaced-apart plates, each plate having an inwardly facing conductive surface, said spaced plates being separated around their peripheries by a peripheral seal to form a sealed cavity, the method comprising:

providing a pair of spaced openings in the device which are in fluid communication with the sealed cavity;

placing one of said openings in flow communication with a liquid medium;

placing the other of said openings in flow communication with a vacuum source whereby said liquid medium is drawn into the cavity of the device;

said liquid medium comprising at least one of a cathodically coloring electrochromic material and an anodically coloring electrochromic material;

said liquid medium including an organic solvent, said organic solvent being a solvent comprising at least 25% by volume of 3-hydroxypropionitrile (HPN), 3,3′

-oxydipropionitrile (ODPN), 2-acetylbutyrolactone (ABL), 2-methylglutaronitrile (MGNT), 3-methylsulfolane (MS), propylene carbonate (PC) or a mixture thereof.

18. A method for filling a large area electrochromic device having an electrochromically active area of at least about 110 cm², and including two spaced-apart plates, each plate having an inwardly facing conductive surface, said spaced plates being separated around their peripheries by a peripheral seal to form a sealed cavity, the method comprising:

providing a pair of spaced openings in the device which are in fluid communication with the sealed cavity;

placing one of said openings in flow communication with a liquid medium;

placing the other of said openings in flow communication with a vacuum source whereby said liquid medium is drawn into the cavity of the device;

said liquid medium including an organic solvent, said organic solvent comprising two solvents at a ratio of from 75;

25 to 25;

75 by volume.

19. A method for filling a large area electrochromic device having an electrochromically active area of at least about 110 cm², and including two spaced-apart plates, each plate having an inwardly facing conductive surface, said spaced plates being separated around their peripheries by a peripheral seal to form a sealed cavity, the method comprising:

providing a pair of spaced openings in the device which are in fluid communication with the sealed cavity;

placing one of said openings in flow communication with a liquid medium;

placing the other of said openings in flow communication with a vacuum source whereby said liquid medium is drawn into the cavity of the device;

said liquid medium including an organic solvent, said organic solvent of said liquid medium comprising at least one of the following combination of solvents;

(a) 3-hydroxypropionitrile and 2-methylglutaronitrile in a ratio by volume of from 75;

25 to 25;

75;

(b) 3-hydroxypropionitrile and 3-methylsulfolane in a ratio by volume of from 75;

25 to 25;

75;

(c) propylene carbonate and 3,3′

-oxydipropionitrile in a ratio by volume of from 75;

25 to 25;

75;

(d) 3-hydroxypropionitrile and 2-acetylbutyrolactone in a ratio by volume of from 75;

25 to 25;

75;

(e) 3-acetylbutyrolactone and 3,3′

-oxydipropionitrile in a ratio by volume of from 75;

25 to 25;

75;

(f) propylene carbonate and 2-acetylbutyrolactone in a ratio by volume of from 75;

25 to 25;

75; and

(g) 3-hydroxypropionitrile and 3,3′

-oxydipropionitrile in a ratio by volume of from 75;

25 to 25;

75.

21. A method for filling a large area electrochromic device having an electrochromically active area of at least about 110 cm², and including two spaced-apart plates, each plate having an inwardly facing conductive surface, said spaced plates being separated around their peripheries by a peripheral seal to form a sealed cavity, the method comprising:

providing a pair of spaced openings in the device which are in fluid communication with the sealed cavity;

placing one of said openings in flow communication with a liquid medium;

placing the other of said openings in flow communication with a vacuum source whereby said liquid medium is drawn into the cavity of the device;

said liquid medium including an electrochromic material comprising at least one of a phenazine, a phenyldiamine, a benzidene and a fulvalene.

23. A method for filling a large area electrochromic device having an electrochromically active area of at least about 110 cm², and including two spaced-apart plates, each plate having an inwardly facing conductive surface, said spaced plates being separated around their peripheries by a peripheral seal to form a sealed cavity, the method comprising:

providing a pair of spaced openings in the device which are in fluid communication with the sealed cavity;

placing one of said openings in flow communication with a liquid medium;

placing the other of said openings in flow communication with a vacuum source whereby said liquid medium is drawn into the cavity of the device;

said electrochromic device comprising an electrochromic window.

24. The method of claim 23 wherein said electrochromic window comprises one of an architectural window and an automotive window.

25. A method for filling a large area electrochromic device having an electrochromically active area of at least about 110 cm², and including two spaced-apart plates, each plate having an inwardly facing conductive surface, said spaced plates being separated around their peripheries by a peripheral seal to form a sealed cavity, the method comprising:

providing a pair of spaced openings in the device which are in fluid communication with the sealed cavity;

placing one of said openings in flow communication with a liquid medium;

placing the other of said openings in flow communication with a vacuum source whereby said liquid medium is drawn into the cavity of the device;

said liquid medium comprising an organic solvent having a vapor pressure of less than 3.2 mm of mercury at 25°

C.

29. A method for filling a large area electrochromic window having an electrochromically active area of at least about 110 cm², including two spaced-apart plates, each plate having an inwardly facing transparent conductive surface, said spaced plates being separated around their peripheries by a peripheral seal having a gap therein, said peripheral seal enclosing an area of each of said plates to define a cavity within said window, said filling method comprising:

providing a liquid medium comprising electrochromic material, said liquid medium comprising an organic solvent having a vapor pressure of less than 3.2 mm of mercury at 25°

C.;

evacuating said cavity of said window to a vacuum;

placing said evacuated cavity of said window in flow communication with said liquid medium;

exposing said liquid medium to a source of inert gas of pressure greater than that in said cavity within said window to thereby cause said medium to flow into said cavity of said window;

removing said window from flow communication with said liquid medium; and

sealing said gap in said peripheral seal of said window.

30. The method of claim 29 wherein said electrochromic material comprises at least one of a cathodically coloring electrochromic material and an anodically coloring electrochromic material.

31. The method of claim 29 wherein said electrochromic material comprises a viologen species.

32. The method of claim 29 wherein said electrochromic material comprises at least one of a phenazine, a phenyldiamine, a benzidene and a fulvalene.

33. The method of claim 29 wherein said organic solvent is a solvent comprising at least 25% by volume of 3-hydroxypropionitrile (HPN), 3,3′

-oxydipropionitrile (ODPN), 2-acetylbutyrolactone (ABL), 2-methylglutaronitrile (MGNT), 3-methylsulfolane (MS), propylene carbonate (PC) or a mixture thereof.

34. The method of claim 29 wherein said electrochromic window comprises one of an architectural window and an automotive window.

35. The method of claim 29 including exposing said liquid medium to inert gas comprising nitrogen.

36. The method of claim 29 wherein said liquid medium comprises an ultraviolet stabilizer.

37. The method of claim 29 wherein said liquid medium comprises an ultraviolet stabilizer in solution therein in an amount of at least 1.7% wt/vol.

38. The method of claim 37 wherein said liquid medium comprises an ultraviolet stabilizer in solution therein in an amount within the range of from greater than 1.7% wt/vol up to 40.2% wt/vol.

39. The method of claim 29 wherein said liquid medium comprises an ultraviolet stabilizer in solution therein in an amount of at least approximately 5% wt/vol.