Controlled diffusion coefficient electrochromic materials for use in electrochromic mediums and associated electrochromic devices

• US 20020141032A1
• Filed: 11/13/2001
• Published: 10/03/2002
• Est. Priority Date: 12/03/1999
• Status: Active Grant

• Current Assignee: Gentex Corporation
• Original Assignee: Gentex Corporation
• Inventors: Sanford, Elizabeth M., Guarr, Thomas F., Theiste, David A., Giri, Punam, Baumann, Kelvin L., Lin, Rongguang, Roberts, Kathy E.
• Granted Patent: US 6,710,906 B2
• Time in Patent Office: Days
• US Class Current: 359/265
• CPC Class Codes: C09K 2211/1007 Non-condensed systems
• CPC Class Codes: C09K 2211/1029 containing one nitrogen atom as the heteroatom
• CPC Class Codes: C09K 9/00 Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
• 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 2001/15145 the electrochromic layer comprises a mixture of anodic and cathodic compounds

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 wherein at least one of the anodic and cathodic electroactive materials is associated with a diffusion coefficient controlling moiety which serves to lower the diffusion coefficient of the associated material relative to the same without the diffusion coefficient controlling moiety.

Claims

1. 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;

wherein the anodic electroactive material comprises a diffusion coefficient less than approximately 8.00×

10<sup>−

6</sup> cm²/s in propylene carbonate at approximately 25 degrees centigrade; and

wherein the anodic electroactive material comprises a diffusion coefficient controlling moiety which is non-redox active during normal operation of an associated electrochromic device.

2. The electrochromic medium according to claim 1, wherein the anodic electroactive material comprises a diffusion coefficient less than approximately 5.00×

10<sup>−

6</sup> cm² /s in propylene carbonate at approximately 25 degrees centigrade.

3. The electrochromic medium according to claim 1, wherein the anodic electro active material comprises a diffusion coefficient less than approximately 3.00×

10<sup>−

6</sup> cm²/S in propylene carbonate at approximately 25 degrees centigrade.

4. electrochromic medium according to claim 1, wherein the at least one solvent is selected from the group comprising sulfolanes, nitriles, sulfoxides, formamides, ethers, alcohols, ketones, esters, carbonates, and homogenous mixtures of the same.

5. The electrochromic medium according to claim 1, wherein the concentration of the anodic electroactive material ranges from approximately 1 mM to approximately 500 mM.

6. The electrochromic medium according to claim 1, wherein the concentration of the anodic electro active material ranges from approximately 2 mM to approximately 100 mM.

7. The electrochromic medium according to claim 1, wherein the anodic electroactive material is represented by at least one of the formulae:

8. 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

wherein the anodic electroactive material is represented by at least one of the formulae;

wherein X₁-X₄₂ are the same or different and comprise a single bond, N, O, S or Se;

wherein m is an integer ranging from 1 to approximately 3;

wherein n is an integer ranging from 0 to approximately 10;

wherein Z_1A-E are the same or different and comprise —

[CH═

CH]_s—

, —

[C≡

C]_s—

, —

N═

N—

, or p-phenyl;

wherein s is an integer ranging from 0 to approximately 4;

wherein Z₂ comprises ═

CH—

[Z_1A]_t—

CH═

, or ═

N—

[Z_1A]_t—

N═

;

wherein t is an integer ranging from 0 to approximately 4;

wherein R₁-R₁₇₀ are the same or different and comprise a lone electron pair, H, a halogen, a straight or branched alkyl, aryl, alkaryl, aralkyl, or alkoxy group containing 1 to approximately 50 carbon atom(s), wherein the carbon atoms may be a linking group to, or part of, one or more functional groups comprising alcohols;

thiols;

thioethers;

nitriles;

nitro constituents;

sulfoxides;

sulfonates;

phosphonium constituents;

phosphonates;

phosphonites;

ammonium constituents;

carbonyls, including carbonates, carbamates;

ketones;

esters; and

amides;

ethers, including polyethers;

amines, including tertiary amines; and

mixtures thereof, and

wherein at least one of R₁-R₁₀ of A1, R ₁₁-R₂₄ of A2, R₂₅-R₃₆ of A3, R₃₇-R₄₄ of A4, R₄₅-R₅₆ of A5, R₅₇-R₆₈ of A6, R₆₉-R₈₀ of A7, R₈₁,-R₈₈ of A8, R₈₉-R₉₂ of A9, R₉₃-R₁₀₃ of A10, R₁₀₄-R₁₁₂ of A11, R₁₁₃-R₁₂₃ of A12, R₁₂₄-R₁₃₄ of A13, R₁₃₅-R₁₅₂ of A14, and R₁₅₃-R₁₇₀ of A15 comprises a diffusion coefficient controlling moiety which cooperatively interacts with the at least one solvent.

9. The electrochromic medium according to claim 8, wherein R₁-R₁₇₀ are non-redox active during normal operation of an associated electrochromic device.

10. The electrochromic medium according to claim 9, wherein at least one of R₁-R₁₇₀ comprises a diffusion coefficient controlling moiety which is ionic.

11. The electrochromic medium according to claim 10, wherein at least one of R₁-R₁₇₀ comprises a diffusion coefficient controlling moiety which is cationic.

12. The electrochromic medium according to claim 11, wherein at least two of R₁-R₁₇₀ comprise a diffusion coefficient controlling moiety which is cationic.

13. The electrochromic medium according to claim 8, wherein the anodic electroactive material comprises a diffusion coefficient less than approximately 8.00×

10<sup>−

6</sup> cm²/s in propylene carbonate at approximately 25 degrees centigrade.

14. The electrochromic medium according to claim 8, wherein the anodic electroactive material comprises a diffusion coefficient less than approximately 5.00×

10<sup>−

6</sup> cm²/s in propylene carbonate at approximately 25 degrees centigrade.

15. The electrochromic medium according to claim 8, wherein the anodic electroactive material comprises a diffusion coefficient less than approximately 3.00×

10<sup>−

6</sup> cm²/s in propylene carbonate at approximately 25 degrees centigrade.

16. The electrochromic medium according to claim 8, wherein the at least one solvent is selected from the group comprising sulfolanes, nitriles, sulfoxides, formamides, ethers, alcohols, ketones, esters, carbonates, and homogenous mixtures of the same.

17. The electrochromic medium according to claim 8, wherein the concentration of the anodic electroactive material ranges from approximately 1 mM to approximately 500 mM.

18. The electrochromic medium according to claim 8, wherein the concentration of the anodic electroactive material ranges from approximately 2 mM to approximately 100 mM.

20. The electrochromic medium according to claim 19, wherein the anodic electroactive material comprises a diffusion coefficient less than approximately 8.00×

10<sup>−

6</sup> cm²/s in propylene carbonate at approximately 25 degrees centigrade.

21. The electrochromic medium according to claim 19, wherein the anodic electroactive material comprises a diffusion coefficient less than approximately 5.00×

10<sup>−

6</sup> cm²/s in propylene carbonate at approximately 25 degrees centigrade.

22. The electrochromic medium according to claim 19, wherein the anodic electroactive material comprises a diffusion coefficient less than approximately 3.00×

10<sup>−

6</sup> cm²/s in propylene carbonate at approximately 25 degrees centigrade.

24. The electrochromic medium according to claim 23, wherein at least one of R₁-R₁₀ of C1, R₁₁-R₂₉ of C2, R₃₀-R₃₉ of C3, R₄₀-R₄₃ of C4, and R₄₄-R₄₉ of C5 comprises a diffusion coefficient controlling moiety which cooperatively interacts with the at least one solvent.

25. The electrochromic medium according to claim 23, wherein the cathodic electroactive material comprises a diffusion coefficient less than approximately 2.00×

10<sup>−

6</sup> cm²/s in propylene carbonate at approximately 25 degrees centigrade.

26. The electrochromic medium according to claim 25, wherein at least one of R₁-R₁₀ of C1, R₁₁-R₂₉ of C2, R₃₀-R₃₉ of C3, R₄₀-R₄₃ of C4, and R₄₄-R₄₉ of C5 comprises a diffusion coefficient controlling moiety which cooperatively interacts with the at least one solvent.

27. The electrochromic medium according to claim 23, wherein the at least one solvent is selected from the group comprising sulfolanes, nitriles, sulfoxides, formamides, ethers, alcohols, ketones, esters, carbonates, and homogenous mixtures of the same.

28. The electrochromic medium according to claim 23, wherein the concentration of the cathodic electroactive material ranges from approximately 1 mM to approximately 500 mM.

29. The electrochromic medium according to claim 23, wherein the concentration of the cathodic electroactive material ranges from approximately 2 mM to approximately 100 mM.

19. 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

wherein the anodic electroactive material includes;

a first moiety; and

a diffusion coefficient controlling moiety, wherein the diffusion coefficient controlling moiety comprises at least one constituent which serves to decrease the diffusion coefficient of the first moiety in the at least one solvent relative to the first moiety without the diffusion coefficient controlling moiety.

23. 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;

wherein the cathodic electroactive material comprises a diffusion coefficient less than approximately 3.00×

10<sup>−

6</sup> in propylene carbonate at approximately 25 degrees centigrade; and

wherein the cathodic electroactive material is represented by at least one of the formulae;

wherein R₁-R₄₉ are the same or different and comprise H, a halogen, a straight or branched alkyl, aryl, alkaryl, aralkyl, or alkoxy group containing 1 to approximately 50 carbon atom(s), wherein the carbon atoms may be a linking group to, or part of, one or more functional groups comprising alcohols;

thiols;

thioethers;

nitriles;

nitro constituents;

sulfoxides;

sulfonates;

phosphonium constituents;

phosphonates;

phosphonites;

ammonium constituents;

carbonyls, including carbonates, carbamates;

ketones;

esters; and

amides;

ethers, including polyethers;

amines, including tertiary amines; and

mixtures thereof; and

wherein R₁-R₄₉ are non-redox active during normal operation of an associated electrochromic device.

30. 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

wherein the cathodic electroactive material is represented by at least one of the formulae;

wherein R₁-R₄₉ are the same or different and comprise H, a halogen, a straight or branched alkyl, aryl, alkaryl, aralkyl, or alkoxy group containing 1 to approximately 50 carbon atom(s), wherein the carbon atoms may be a linking group to, or part of, one or more functional groups comprising alcohols;

thiols;

thioethers;

nitriles;

nitro constituents;

sulfoxides;

sulfonates;

phosphonium constituents;

phosphonates;

phosphonites;

ammonium constituents;

carbonyls, including carbonates, carbamates;

ketones;

esters; and

amides;

ethers, including polyethers;

amines, including tertiary amines; and

mixtures thereof;

wherein R₁R₄₉ are non-redox active during operation of an associated electrochromic device; and

wherein at least one R₁-R₁₀ of C1, R₁₁-R₂₉ of C2, R₃₀-R₃₉ of C3, R₄₀-R₄₃ of C4, and R₄₄-R₄₉ of C5 comprises a diffusion coefficient controlling moiety which cooperatively interacts with the at least one solvent.

31. The electrochromic medium according to claim 30, wherein at least one of R₁-R₄₉ comprises a diffusion coefficient controlling moiety which is ionic.

32. The electrochromic medium according to claim 31, wherein at least one of R₁-R₄₉ comprises a diffusion coefficient controlling moiety which is cationic.

33. The electrochromic medium according to claim 30, wherein at least two of R₁-R₄₉ comprise a diffusion coefficient controlling moiety which is ionic.

34. The electrochromic medium according to claim 33, wherein at least two of R₁-R₄₉ comprise a diffusion coefficient controlling moiety which is cationic.

35. The electrochromic medium according to claim 30, wherein the at least one solvent is selected from the group comprising sulfolanes, nitriles, sulfoxides, formamides, ethers, alcohols, ketones, esters, carbonates, and homogenous mixtures of the same.

36. The electrochromic medium according to claim 30, wherein the concentration of the cathodic electroactive material ranges from approximately 1 mM to approximately 500 mM.

37. The electrochromic medium according to claim 30, wherein the concentration of the cathodic electro active material ranges from approximately 2 mM to approximately 100 mM.

38. 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

wherein the cathodic electroactive material includes;

a first moiety; and

a diffusion coefficient controlling moiety, wherein the diffusion coefficient controlling moiety comprises at least one constituent which serves to decrease the diffusion coefficient of the first moiety in the at least one solvent relative to the first moiety without the diffusion coefficient controlling moiety.

39. 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

wherein at least one of the anodic and cathodic electroactive material includes;

a first moiety; and

a diffusion coefficient controlling moiety, wherein the diffusion coefficient controlling moiety comprises at least one constituent which serves to decrease the diffusion coefficient of the first moiety in the at least one solvent relative to the first moiety without the diffusion coefficient controlling moiety.

40. An electrochromic device, comprising:

at least one substantially transparent substrate having an electrically conductive material associated therewith; and

an electrochromic medium which comprises;

at least one solvent;

an anodic electroactive material;

a cathodic electro active material;

wherein at least one of the anodic and electro active materials is electrochromic; and

wherein at least one of the anodic and cathodic electroactive materials comprises a diffusion coefficient controlling moiety which enables the electrochromic device to operate at a lower current relative to an electrochromic device without the at least one anodic and cathodic electroactive material which comprises the diffusion coefficient controlling moiety.

41. 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 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 the anodic electroactive material is represented by at least one of the formulae;

wherein X₁-X₄₂ are the same or different and comprise a single bond, N, O, S or Se;

wherein m is an integer ranging from 1 to approximately 3;

wherein n is an integer ranging from 0 to approximately 10;

wherein Z_1A-E are the same or different and comprise —

[CH═

CH]_s—

, —

[C≡

C]_s—

, —

N═

N—

, or p-phenyl;

wherein s is an integer ranging from 0 to approximately 4;

wherein Z₂ comprises ═

CH—

[Z_1A]_t—

CH═

, or ═

N—

[Z_1A]_t—

N═

;

wherein t is an integer ranging from 0 to approximately 4;

wherein R₁-R₁₇₀ of A1-A15 are the same or different and comprise a lone electron pair, H, a halogen, a straight or branched alkyl, aryl, alkaryl, aralkyl, or alkoxy group containing approximately 1 to approximately 50 carbon atom(s), wherein the carbon atoms may be a linking group to, or part of, one or more functional groups comprising alcohols;

thiols;

thioethers;

nitriles;

nitro constituents;

sulfoxides;

sulfonates;

phosphonium constituents;

phosphonates;

phosphonites;

ammonium constituents;

carbonyls, including carbonates, carbamates;

ketones;

esters; and

amides;

ethers, including polyethers;

amines, including tertiary amines; and

mixtures thereof;

wherein R₁-R₁₇₀ of A1-A15 are non-redox active during normal operation of an associated electrochromic device;

wherein at least one of R₁-R₁₀ of A1, R₁₁-R₂₄ of A2, R₂₅-R₃₆ of A3, R₃₇-R₄₄ of A4, R₄₅-R₅₆ of A5, R₅₇-R₆₈ of A6, R₆₉-R₈₀ of A7, R₈₁-R₈₈ of A8, R₈₉-R₉₂ of A9, R₉₃-R₁₀₃ of A10, R₁₀₄-R₁₁₂ of A11, R₁₁₃-R₁₂₃ of A12, R₁₂₄-R₁₃₄ of A13, R₁₃₅-R₁₅₂ of A14, and R₁₅₃-R₁₇₀ of A15 comprises a diffusion coefficient controlling moiety which cooperatively interacts with the at least one solvent; and

/or wherein the cathodic electroactive material is represented by at least one of the formulae;

wherein R₁-R₄₉ of C1-C5 are the same or different and comprise H, a halogen, a straight or branched alkyl, aryl, alkaryl, aralkyl, or alkoxy group containing 1 to approximately 50 carbon atom(s), wherein the carbon atoms may be a linking group to, or part of, one or more functional groups comprising alcohols;

thiols;

thioethers;

nitriles;

nitro constituents;

sulfoxides;

sulfonates;

phosphonium constituents;

phosphonates;

phosphonites;

ammonium constituents;

carbonyls, including carbonates, carbamates;

ketones;

esters; and

amides;

ethers, including polyethers;

amines, including tertiary amines; and

mixtures thereof; and

wherein R₁-R₄₉ of C1-C5 are non-redox active during normal operation of an associated electrochromic device.

42. The electrochromic device according to claim 41, wherein the device is an electrochromic window.

43. The electrochromic device according to claim 41, wherein the second substrate is plated with a reflective material.

44. The electrochromic device according to claim 43, wherein the reflective material is selected from the group comprising chromium, ruthenium, rhodium, silver, alloys of the same, and stacked layers thereof.

45. The electrochromic device according to claim 44, wherein the device is an electrochromic mirror.