Electrochromic medium having a self-healing, cross-linked polymer matrix and associated electrochromic device

• US 20060139726A1
• Filed: 02/16/2006
• Published: 06/29/2006
• Est. Priority Date: 08/28/2001
• Status: Abandoned Application

• Current Assignee: Gentex Corporation
• Original Assignee: Gentex Corporation
• Inventors: Kloeppner, Leroy J., Guarr, Thomas F., Ash, Kevin L., Theiste, David A., Roberts, Kathy E.
• Application Number:
  US11/356,356
• Publication Number:
  US 20060139726A1
• Time in Patent Office: Days
• US Class Current: 359/265
• 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

Abstract

An electrochromic medium for use in an electrochromic device comprising: at least one solvent; an anodic electroactive material; a cathodic electroactive material; wherein at least one of the anodic and cathodic electroactive materials is electrochromic; and a self-healing, cross-linked polymer matrix.

Claims

1. A gelled electrochromic medium for use in an electrochromic device, comprising:

at least one solvent;

an anodic electroactive material;

a cathodic electroactive material;

wherein at least one of the anodic and cathodic electroactive materials is electrochromic;

a self-healing, cross-linked polymer matrix which comprises a product of at least one of a first reactant having at least one of an adhesive/cohesive functional group and a cross-linking functional group and a second reactant having a cross-linking functional group;

wherein the following inequality is true;

f+2(log(r)/p)≧

1.00;

wherein f comprises Σ

_x/m;

wherein x comprises a value ranging from 0 to 2 for each element (A), aryl moiety (Ar), and cyclic moiety (Cy) of at least one of the first and second reactants;

wherein x comprises 0 if A or Ar is represented by one of the following structures;

wherein x comprises 0.5 if A or Cy is represented by one of the following structures;

wherein x comprises 1.0 if A is represented by one of the following structures;

wherein x comprises 1.5 if A is represented by the following structure;

wherein x comprises 2.0 if A is represented by the following structure;

 

wherein A comprises C, N, O, S, P, or Si;

 

wherein Z comprises H or F;

 

wherein R comprises any other pendent group other than Z;

wherein m comprises the number of (A) elements, (Ar) moieties, and (Cy) moieties of the at least one of the first and second reactants which define x;

wherein r comprises the molar ratio of the adhesive/cohesive functional group of the first reactant to the cross-linking functional group of at least one of the first and second reactants; and

wherein p comprises the total concentration by weight of the self-healing, cross-linked polymer matrix in the gelled electrochromic medium.

2. The electrochromic medium according to claim 1, further comprising an ultraviolet stabilizer.

3. The electrochromic medium according to claim 1, wherein the average molecular weight of at least one of the first and second reactants is greater than approximately 2,000 daltons.

4. The electrochromic medium according to claim 1, wherein the average molecular weight of at least one of the first and second reactants is greater than approximately 5,000 daltons.

5. The electrochromic medium according to claim 1, wherein the average molecular weight of at least one of the first and second reactants is greater than approximately 10,000 daltons.

6. The electrochromic medium according to claim 1, wherein at least one of the first and second reactants comprises at least approximately 1.0% of the gelled electrochromic medium.

7. The electrochromic medium according to claim 1, wherein at least one of the first and second reactants comprises at least approximately 2.0% of the gelled electrochromic medium.

8. The electrochromic medium according to claim 1, wherein the first reactant having an adhesive/cohesive functional group is present in an effective concentration to, in turn, substantially diminish visual irregularities within the same.

9. The electrochromic medium according to claim 1, wherein the adhesive/cohesive functional group is selected from the group comprising a hydroxyl group, thiols, amines, amides, carboxylic acids, carboxylates, phosphonates, sulfonyl halides, silicate esters, ammonium salts, sulfonyl acids, siloxyls, silyls, cyanos, and combinations thereof.

10. The electrochromic medium according to claim 1, wherein the adhesive/cohesive functional group comprises a hydroxyl group.

11. The electrochromic medium according to claim 1, wherein the cross-linking functional group comprises an isocyanate.

12. The electrochromic medium according to claim 1, wherein the adhesive/cohesive functional group is selected from the group comprising a hydroxyl group, thiols, amines, amides, carboxylic acids, carboxylates, phosphonates, sulfonyl halides, silicate esters, ammonium salts, sulfonyl acids, siloxyls, silyls, cyanos, and combinations thereof, and wherein the cross-linking functional group comprises an isocyanate.

13. The electrochromic medium according to claim 1, wherein the molar ratio of the adhesive/cohesive functional group to the cross-linking functional group is greater than approximately 3:

1.

14. The electrochromic medium according to claim 1, wherein the molar ratio of the adhesive/cohesive functional group to the cross-linking functional group ranges from approximately 3:

1 to approximately 100;

1.

15. The electrochromic medium according to claim 1, wherein the self-healing, cross-linked polymer matrix includes a backbone selected from the group comprising polyamides, polyimides, polycarbonates, polyesters, polyethers, polymethacrylates, polyacrylates, polysilanes, polysiloxanes, polyvinylacetates, polymethacrylonitriles, polyacrylonitriles, polyvinylphenols, polyvinylalcohols, polyvinylidenehalides, and co-polymers and combinations thereof.

16. The electrochromic medium according to claim 1, wherein the at least one solvent is selected from the group comprising 3-methylsulfolane, sulfolane, glutaronitrile, dimethyl sulfoxide, dimethyl formamide, acetonitrile, polyethers including tetraglyme, alcohols including ethoxyethanol, nitriles including 3-hydroxypropionitrile, 2-methylglutaronitrile, ketones including 2-acetylbutyrolactone, cyclopentanone, cyclic esters including beta-propiolactone, gamma-butyrolactone, gamma-valerolactone, cyclic carbonates including propylene carbonate, ethylene carbonate and homogenous mixtures of the same.

17. The electrochromic medium according to claim 1, further comprising a redox buffer.

18. The electrochromic medium according to claim 1, wherein the anodic electroactive material comprises a phenazine.

19. The electrochromic medium according to claim 1, wherein the cathodic electroactive material comprises a viologen.

20. An electrochromic device, comprising:

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

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

an electrochromic medium according to claim 1 contained within a chamber positioned between the first and second substrates.

21. The electrochromic device according to claim 20, wherein the device is an electrochromic window.

22. The electrochromic device according to claim 20, wherein the second substrate is plated with a reflective material.

23. The electrochromic device according to claim 22, wherein the reflective material is selected from the group comprising chromium, ruthenium, rhodium, silver, alloys and/or combinations of the same, and stacked layers thereof.

24. The electrochromic device according to claim 23, wherein the device is an electrochromic mirror.

25. The electrochromic device according to claim 20, wherein at least one of the first and second substrates is less than approximately 1 mm thick.

26. The electrochromic device according to claim 25, where the device is an aircraft transparency.

27. An electrochromic device, comprising:

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

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

an electrochromic medium according to claim 2 contained within a chamber positioned between the first and second substrates.

28. An electrochromic device, comprising:

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

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

an electrochromic medium according to claim 3 contained within a chamber positioned between the first and second substrates.

29. An electrochromic device, comprising:

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

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

an electrochromic medium according to claim 6 contained within a chamber positioned between the first and second substrates.

30. An electrochromic device, comprising:

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

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

an electrochromic medium according to claim 10 contained within a chamber positioned between the first and second substrates.

31. An electrochromic device, comprising:

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

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

a gelled electrochromic medium contained within a chamber positioned between the first and second substrates which comprises;

at least one solvent;

an anodic electroactive material;

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

a self-healing, cross-linked polymer matrix which comprises a product of at least one of a first reactant having at least one of an adhesive/cohesive functional group and a cross-linking functional group and a second reactant having a cross-linking functional group;

wherein the following inequality is true;

f+2(log(r)/p)≧

1.10;

wherein f comprises Σ

_x/m;

wherein x comprises a value ranging from 0 to 2 for each element (A), aryl moiety (Ar), and cyclic moiety (Cy) of at least one of the first and second reactants;

 

wherein x comprises 0 if A or Ar is represented by one of the following structures;

 

wherein x comprises 0.5 if A or Cy is represented by one of the following structures;

 

wherein x comprises 1.0 if A is represented by one of the following structures;

 

wherein x comprises 1.5 if A is represented by the following structure;

 

wherein x comprises 2.0 if A is represented by the following structure;

 

wherein A comprises C, N, O, S, P, or Si;

 

wherein Z comprises H or F;

 

wherein R comprises any other pendent group other than Z;

wherein m comprises the number of (A) elements, (Ar) moieties, and (Cy) moieties of the at least one of the first and second reactants which define x;

wherein r comprises the molar ratio of the adhesive/cohesive functional group of the first reactant to the cross-linking functional group of at least one of the first and second reactants; and

wherein p comprises the total concentration by weight of the self-healing, cross-linked polymer matrix in the gelled electrochromic medium.

32. An electrochromic device, comprising:

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

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

a gelled electrochromic medium contained within a chamber positioned between the first and second substrates which comprises;

at least one solvent;

an anodic electroactive material;

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

a self-healing, cross-linked polymer matrix which comprises a product of at least one of a first reactant having at least one of an adhesive/cohesive functional group and a cross-linking functional group, and a second reactant having a cross-linking functional group;

wherein the following inequality is true;

f+2(log(r)/p)≧

1.25;

wherein f comprises Σ

_x/m;

wherein x comprises a value ranging from 0 to 2 for each element (A), aryl moiety (Ar), and cyclic moiety (Cy) of at least one of the first and second reactants;

 

wherein x comprises 0 if A or Ar is represented by one of the following structures;

 

wherein x comprises 0.5 if A or Cy is represented by one of the following structures;

 

wherein x comprises 1.0 if A is represented by one of the following structures;

 

wherein x comprises 1.5 if A is represented by the following structure;

 

wherein x comprises 2.0 if A is represented by the following structure;

 

wherein A comprises C, N, O, S, P, or Si;

 

wherein Z comprises H or F;

 

wherein R comprises any other pendent group other than Z;

wherein m comprises the number of (A) elements, (Ar) moieties, and (Cy) moieties of the at least one of the first and second reactants which define x;

wherein r comprises the molar ratio of the adhesive/cohesive functional group of the first reactant to the cross-linking functional group of at least one of the first and second reactants; and

wherein p comprises the total concentration by weight of the self-healing, cross-linked polymer matrix in the gelled electrochromic medium.