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

• US 6,635,194 B2
• Filed: 08/28/2001
• Issued: 10/21/2003
• Est. Priority Date: 08/28/2001
• Status: Expired due to Term

• Current Assignee: Gentex Corporation
• Original Assignee: Gentex Corporation
• Inventors: Kloeppner, Leroy J., Guarr, Thomas F., Ash, Kevin L., Roberts, Kathy E.
• Primary Examiner(s): TUCKER, PHILIP C
• Application Number:
  US09/940,944
• Publication Number:
  US 20030042473A1
• Time in Patent Office: 784 Days
• Field of Search: 252/583, 252/586, 359/265, 359/267, 359/272, 359/273, 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 1/1525 characterised by a particular ion transporting layer, e.g. electrolyte
• CPC Class Codes: G02F 2001/1502 complementary cell

Abstract

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

Claims

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

at least one solvent;

a cathodic electroactive material;

an anodic electroactive material;

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

a self-healing cross-linked polymer gel, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 3;

1.

2. The electrochromic medium according to claim 1, wherein the self-healing cross-linked polymer gel comprises at least one cohesive functional group present in an effective concentration to, in turn, substantially diminish visual irregularities within the same.

3. The electrochromic medium according to claim 2, wherein the at least one cohesive functional group is selected from the group consisting of a hydroxyl group, acetates, thiols, amines, amides, carboxylic acids, carboxylates, phosphonates, sulfonyl halides, silicate esters, ammonium salts, sulfonyl acids, siloxyls, silyls, cyanos, and combinations thereof.

4. The electrochromic medium according to claim 3, wherein the at least one cohesive functional group consists of a hydroxyl group.

5. The electrochromic medium according to claim 2, wherein the self-healing cross-linked polymer gel includes a product of a cross-linking reactant, wherein the cross-linking reactant comprises an isocyanate.

6. The electrochromic medium according to claim 1, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 4:

1.

7. The electrochromic medium according to claim 1, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 6:

1.

8. The electrochromic medium according to claim 1, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 8:

1.

9. The electrochromic medium according to claim 1, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 13:

1.

10. The electrochromic medium according to claim 1, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 20:

1.

11. The electrochromic medium according to claim 1, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group ranges from approximately 3:

1 to approximately 100;

1.

12. The electrochromic medium according to claim 1, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group selected from the group consisting of a hydroxyl group, acetates, thiols, amines, amides, carboxylic acids, carboxylates, phosphonates, sulfonyl halides, silicate esters, ammonium salts, sulfonyl acids, siloxyls, silyls, cyanos, and combinations thereof, and a second reactant having a cross-linking functional group consisting of an isocyanate, wherein the molar ratio of the cohesive functional group to the cross-linking functional group ranges from approximately 3:

1 to approximately 100;

1.

13. The electrochromic medium according to claim 1, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group selected from the group consisting of a hydroxyl group, acetates, thiols, amines, amides, carboxylic acids, carboxylates, phosphonates, sulfonyl halides, silicate esters, ammonium salts, sulfonyl acids, siloxyls, silyls, cyanos, and combinations thereof, and a second reactant having a cross-linking functional group consisting of an isocyanate, wherein the molar ratio of the 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 self-healing cross-linked polymer gel includes a backbone selected from the group consisting of polyamides, polyimides, polycarbonates, polyesters, polyethers, polymethacrylates, polyacrylates, polysilanes, polysiloxanes, polyvinylacetates, polymethacrylonitriles, polyacrylonitriles, polyvinylphenols, polyvinylalcohols, polyvinylidenehalides, and co-polymers and combinations thereof.

15. The electrochromic medium according to claim 1, wherein the cathodic and anodic electroactive materials are linked.

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

17. The electrochromic medium according to claim 1, wherein the concentration of at least one of the cathodic and anodic electrochromic materials ranges from approximately 1 mM to approximately 1000 mM.

18. The electrochromic medium according to claim 1, wherein the concentration of at least one of the cathodic and anodic electrochromic materials ranges from approximately 5 mM to approximately 500 mM.

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

20. The electrochromic medium according to claim 1, wherein the cathodic electroactive material comprises a polymer film.

21. The electrochromic medium according to claim 1, wherein the cathodic electroactive material comprises tungsten oxide.

22. The electrochromic medium according to claim 1, wherein the anodic electroactive material comprises a heterocyclic compound.

23. The electrochromic medium according to claim 1, wherein the anodic electroactive material comprises a polymer film.

24. The electrochromic medium according to claim 1, wherein the anodic electroactive material is selected from at least one of the group consisting of 5,10-dihydro-5,10-dimethylphenazine, 10-methylphenothiazine, a metallocene, and mixtures thereof.

25. An electrochromic medium for use in an electrochromic device, comprising:

at least one solvent;

a cathodic electroactive material;

an anodic electroactive material;

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

a cross-linked polymer gel, wherein the cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 3;

1; and

means associated with the cross-linked polymer gel for substantially diminishing undesirable visual irregularities within the same.

26. The electrochromic medium according to claim 25, wherein the cross-linked polymer gel comprises at least one cohesive functional group present in an effective concentration to, in turn, substantially diminish visual irregularities within the same.

27. The electrochromic medium according to claim 26, wherein the at least one cohesive functional group is selected from the group consisting of a hydroxyl group, acetates, thiols, amines, amides, carboxylic acids, carboxylates, phosphonates, sulfonyl halides, silicate esters, ammonium salts, sulfonyl acids, siloxyls, silyls, cyanos, and combinations thereof.

28. The electrochromic medium according to claim 27, wherein the at least one cohesive functional group consists of a hydroxyl group.

29. The electrochromic medium according to claim 26, wherein the cross-linked polymer gel includes a product of a cross-linking reactant, wherein the cross-linking reactant comprises an isocyanate.

30. The electrochromic medium according to claim 25, wherein the cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 4:

1.

31. The electrochromic medium according to claim 25, wherein the cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 6:

1.

32. The electrochromic medium according to claim 25, wherein the cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 8:

1.

33. The electrochromic medium according to claim 25, wherein the cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 13:

1.

34. The electrochromic medium according to claim 25, wherein the cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 20:

1.

35. The electrochromic medium according to claim 25, wherein the cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group ranges from approximately 3:

1 to approximately 100;

1.

36. The electrochromic medium according to claim 25, wherein the cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group selected from the group consisting of a hydroxyl group, acetates, thiols, amines, amides, carboxylic acids, carboxylates, phosphonates, sulfonyl halides, silicate esters, ammonium salts, sulfonyl acids, siloxyls, silyls, cyanos, and combinations thereof, and a second reactant having a cross-linking functional group consisting of an isocyanate, wherein the molar ratio of the cohesive functional group to the cross-linking functional group ranges from approximately 3:

1 to approximately 100;

1.

37. The electrochromic medium according to claim 25, wherein the cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group selected from the group consisting of a hydroxyl group, acetates, thiols, amines, amides, carboxylic acids, carboxylates, phosphonates, sulfonyl halides, silicate esters, ammonium salts, sulfonyl acids, siloxyls, silyls, cyanos, and combinations thereof, and a second reactant having a cross-linking functional group consisting of an isocyanate, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 3:

1.

38. The electrochromic medium according to claim 25, wherein the cross-linked polymer gel includes a backbone selected from the group consisting of polyamides, polyimides, polycarbonates, polyesters, polyethers, polymethacrylates, polyacrylates, polysilanes, polysiloxanes, polyvinylacetates, polymethacrylonitriles, polyacrylonitriles, polyvinylphenols, polyvinylalcohols, polyvinylidenehalides, and co-polymers and combinations thereof.

39. The electrochromic medium according to claim 25, wherein the cathodic and anodic electroactive materials are linked.

40. The electrochromic medium according to claim 25, wherein the at least one solvent is selected from the group consisting of 3-methylsulfolane, sulfolane, glutaronitrile, dimethyl sulfoxide, dimethyl formamide, acetonitrile, polyethers, tetraglyme, alcohols, ethoxyethanol, nitriles, 3-hydroxypropionitrile, 2-methylglutaronitrile, ketones, 2-acetylbutyrolactone, cyclopentanone, cyclic esters, beta-propiolactone, gamma-butyrolactone, gamma-valerolactone, propylene carbonate, ethylene carbonate and homogenous mixtures of the same.

41. The electrochromic medium according to claim 25, wherein the concentration of at least one of the cathodic and anodic electrochromic materials ranges from approximately 1 mM to approximately 1000 mM.

42. The electrochromic medium according to claim 25, wherein the concentration of at least one of the cathodic and anodic electrochromic materials ranges from approximately 5 mM to approximately 500 mM.

43. The electrochromic medium according to claim 25, wherein the cathodic electroactive material comprises a viologen.

44. The electrochromic medium according to claim 25, wherein the cathodic electroactive material comprises a polymer film.

45. The electrochromic medium according to claim 25, wherein the cathodic electroactive material comprises tungsten oxide.

46. The electrochromic medium according to claim 25, wherein the anodic electroactive material comprises a heterocyclic compound.

47. The electrochromic medium according to claim 25, wherein the anodic electroactive material comprises a polymer film.

48. The electrochromic medium according to claim 25, wherein the anodic electroactive material is selected from at least one of the group consisting of 5,10-dihydro-5,10-dimethylphenazine, 10-methylphenothiazine, a metallocene, and mixtures thereof.

49. 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;

a cathodic electroactive material;

an anodic electroactive material;

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

a self-healing cross-linked polymeric gel, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 3;

1.

50. The electrochromic device according to claim 49, wherein the self-healing cross-linked polymer gel comprises at least one cohesive functional group present in an effective concentration to, in turn, substantially diminish visual irregularities within the same.

51. The electrochromic device according to claim 50, wherein the at least one cohesive functional group is selected from the group consisting of a hydroxyl group, acetates, thiols, amines, amides, carboxylic acids, carboxylates, phosphonates, sulfonyl halides, silicate esters, ammonium salts, sulfonyl acids, siloxyls, silyls, cyanos, and combinations thereof.

52. The electrochromic device according to claim 51, wherein the at least one cohesive functional group consists of a hydroxyl group.

53. The electrochromic device according to claim 50, wherein the self-healing cross-linked polymer gel includes a product of a cross-linking reactant, wherein the cross-linking reactant comprises an isocyanate.

54. The electrochromic device according to claim 49, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 4:

1.

55. The electrochromic device according to claim 49, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 6:

1.

56. The electrochromic device according to claim 49, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 8:

1.

57. The electrochromic device according to claim 49, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 13:

1.

58. The electrochromic device according to claim 49, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 20:

1.

59. The electrochromic device according to claim 49, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group ranges from approximately 3:

1 to approximately 100;

1.

60. The electrochromic device according to claim 49, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group selected from the group consisting of a hydroxyl group, acetates, thiols, amines, amides, carboxylic acids, carboxylates, phosphonates, sulfonyl halides, silicate esters, ammonium salts, sulfonyl acids, siloxyls, silyls, cyanos, and combinations thereof, and a second reactant having a cross-linking functional group consisting of an isocyanate, wherein the molar ratio of the cohesive functional group to the cross-linking functional group ranges from approximately 3:

1 to approximately 100;

1.

61. The electrochromic device according to claim 49, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group selected from the group consisting of a hydroxyl group, acetates, thiols, amines, amides, carboxylic acids, carboxylates, phosphonates, sulfonyl halides, silicate esters, ammonium salts, sulfonyl acids, siloxyls, silyls, cyanos, and combinations thereof, and a second reactant having a cross-linking functional group consisting of an isocyanate, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 3:

1.

62. The electrochromic device according to claim 49, wherein the self-healing cross-linked polymer gel includes a backbone selected from the group consisting of polyamides, polyimides, polycarbonates, polyesters, polyethers, polymethacrylates, polyacrylates, polysilanes, polysiloxanes, polyvinylacetates, polymethacrylonitriles, polyacrylonitriles, polyvinylphenols, polyvinylalcohols, polyvinylidenehalides, and co-polymers and combinations thereof.

63. The electrochromic device according to claim 49, wherein the cathodic and anodic electroactive materials are linked.

64. The electrochromic device according to claim 49, wherein the at least one solvent is selected from the group consisting of 3-methylsulfolane, sulfolane, glutaronitrile, dimethyl sulfoxide, dimethyl formamide, acetonitrile, polyethers, tetraglyme, alcohols, ethoxyethanol, nitriles, 3-hydroxypropionitrile, 2-methylglutaronitrile, ketones, 2-acetylbutyrolactone, cyclopentanone, cyclic esters, beta-propiolactone, gamma-butyrolactone, gamma-valerolactone, propylene carbonate, ethylene carbonate and homogenous mixtures of the same.

65. The electrochromic device according to claim 49, wherein the concentration of at least one of the cathodic and anodic electrochromic materials ranges from approximately 1 mM to approximately 1000 mM.

66. The electrochromic device according to claim 49, wherein the concentration of at least one of the cathodic and anodic electrochromic materials ranges from approximately 5 mM to approximately 500 mM.

67. The electrochromic device according to claim 49, wherein the cathodic electroactive material comprises a viologen.

68. The electrochromic device according to claim 49, wherein the cathodic electroactive material comprises a polymer film.

69. The electrochromic device according to claim 49, wherein the cathodic electroactive material comprises tungsten oxide.

70. The electrochromic device according to claim 49, wherein the anodic electroactive material comprises a heterocyclic compound.

71. The electrochromic device according to claim 49, wherein the anodic electroactive material comprises a polymer film.

72. The electrochromic device according to claim 49, wherein the anodic electroactive material is selected from at least one of the group consisting of 5,10-dihydro-5,10-dimethylphenazine, 10-methylphenothiazine, a metallocene, and mixtures thereof.

73. The electrochromic device according to claim 49, comprising a first substantially transparent substrate and a second substrate.

74. The electrochromic device according to claim 73, wherein the device is an electrochromic window.

75. The electrochromic device according to claim 73, wherein the second substrate is plated with a reflective material.

76. The electrochromic device according to claim 75, wherein the reflective material is selected from the group consisting of chromium, ruthenium, rhodium, silver, alloys of the same, and stacked layers thereof.

77. The electrochromic device according to claim 76, wherein the device is an electrochromic mirror.

78. An electrochromic device, comprising:

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

a second substantially transparent 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;

a cathodic electroactive material;

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

a self-healing cross-linked polymeric gel, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 3;

1.

79. The electrochromic device according to claim 78, wherein the self-healing cross-linked polymer gel comprises at least one cohesive functional group present in an effective concentration to, in turn, substantially diminish visual irregularities within the same.

80. The electrochromic device according to claim 79, wherein the at least one cohesive functional group is selected from the group consisting of a hydroxyl group, acetates, thiols, amines, amides, carboxylic acids, carboxylates, phosphonates, sulfonyl halides, silicate esters, ammonium salts, sulfonyl acids, siloxyls, silyls, cyanos, and combinations thereof.

81. The electrochromic device according to claim 80, wherein the at least one cohesive functional group consists of a hydroxyl group.

82. The electrochromic device according to claim 79, wherein the self-healing cross-linked polymer gel includes a product of a cross-linking reactant, wherein the cross-linking reactant comprises an isocyanate.

83. The electrochromic device according to claim 78, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 4:

1.

84. The electrochromic device according to claim 78, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 6:

1.

85. The electrochromic device according to claim 78, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 8:

1.

86. The electrochromic device according to claim 78, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 13:

1.

87. The electrochromic device according to claim 78, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 20:

1.

88. The electrochromic device according to claim 78, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group and a second reactant having a cross-linking functional group, wherein the molar ratio of the cohesive functional group to the cross-linking functional group ranges from approximately 3:

1 to approximately 100;

1.

89. The electrochromic device according to claim 78, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group selected from the group consisting of a hydroxyl group, acetates, thiols, amines, amides, carboxylic acids, carboxylates, phosphonates, sulfonyl halides, silicate esters, ammonium salts, sulfonyl acids, siloxyls, silyls, cyanos, and combinations thereof, and a second reactant having a cross-linking functional group consisting of an isocyanate, wherein the molar ratio of the cohesive functional group to the cross-linking functional group ranges from approximately 3:

1 to approximately 100;

1.

90. The electrochromic device according to claim 78, wherein the self-healing cross-linked polymer gel comprises a product of a first reactant having a cohesive functional group selected from the group consisting of a hydroxyl group, acetates, thiols, amines, amides, carboxylic acids, carboxylates, phosphonates, sulfonyl halides, silicate esters, ammonium salts, sulfonyl acids, siloxyls, silyls, cyanos, and combinations thereof, and a second reactant having a cross-linking functional group consisting of an isocyanate, wherein the molar ratio of the cohesive functional group to the cross-linking functional group is greater than approximately 3:

1.

91. The electrochromic device according to claim 78, wherein the self-healing cross-linked polymer gel includes a backbone selected from the group consisting of polyamides, polyimides, polycarbonates, polyesters, polyethers, polymethacrylates, polyacrylates, polysilanes, polysiloxanes, polyvinylacetates, polymethacrylonitriles, polyacrylonitriles, polyvinylphenols, polyvinylalcohols, polyvinylidenehalides, and co-polymers and combinations thereof.

92. The electrochromic device according to claim 78, wherein the cathodic and anodic electroactive materials are linked.

93. The electrochromic device according to claim 78, wherein the at least one solvent is selected from the group consisting of 3-methylsulfolane, sulfolane, glutaronitrile, dimethyl sulfoxide, dimethyl formamide, acetonitrile, polyethers, tetraglyme, alcohols, ethoxyethanol, nitriles, 3-hydroxypropionitrile, 2-methylglutaronitrile, ketones, 2-acetylbutyrolactone, cyclopentanone, cyclic esters, beta-propiolactone, gamma-butyrolactone, gamma-valerolactone, propylene carbonate, ethylene carbonate and homogenous mixtures of the same.

94. The electrochromic device according to claim 78, wherein the concentration of at least one of the cathodic and anodic electrochromic materials ranges from approximately 1 mM to approximately 1000 mM.

95. The electrochromic device according to claim 78, wherein the concentration of at least one of the cathodic and anodic electrochromic materials ranges from approximately 5 mM to approximately 500 mM.

96. The electrochromic device according to claim 78, wherein the cathodic electroactive material comprises a viologen.

97. The electrochromic device according to claim 78, wherein the cathodic electroactive material comprises a polymer film.

98. The electrochromic device according to claim 78, wherein the cathodic electroactive material comprises tungsten oxide.

99. The electrochromic device according to claim 78, wherein the anodic electroactive material comprises a heterocyclic compound.

100. The electrochromic device according to claim 78, wherein the anodic electroactive material comprises a polymer film.

101. The electrochromic device according to claim 78, wherein the anodic electroactive material is selected from at least one of the group consisting of 5,10-dihydro-5,10-dimethylphenazine, 10-methylphenothiazine, a metallocene, and mixtures thereof.

102. The electrochromic device according to claim 78, comprising a first substantially transparent substrate and a second substrate.

103. The electrochromic device according to claim 102, wherein the device is an electrochromic window.

104. The electrochromic device according to claim 102, wherein the second substrate is plated with a reflective material.

105. The electrochromic device according to claim 104, wherein the reflective material is selected from the group consisting of chromium, ruthenium, rhodium, silver, alloys of the same, and stacked layers thereof.

106. The electrochromic device according to claim 105, wherein the device is an electrochromic mirror.