Electrochemichromic solutions, processes for preparing and using the same, and devices manufactured with the same

• US 5,239,405 A
• Filed: 09/06/1991
• Issued: 08/24/1993
• Est. Priority Date: 09/06/1991
• Status: Expired due to Term

• Current Assignee: Donnelly Corporation (Magna International Incorporated)
• Original Assignee: Donnelly Corporation (Magna International Incorporated)
• Inventors: Varaprasad, Desaraju V., Zhao, Mingtang, Lynam, Niall R., Looman, Steven D., Habibi, Hamid R.
• Primary Examiner(s): Arnold, Bruce Y.
• Assistant Examiner(s): Lester, Evelyn A.
• Application Number:
  US07/756,342
• Time in Patent Office: 718 Days
• Field of Search: 359/270, 359/272, 359/265, 252/586, 252/583
• US Class Current: 359/272
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: E06B 2009/2464 featuring transparency control by applying voltage, e.g. LCD, electrochromic panels
• CPC Class Codes: E06B 9/24 Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blindsoperating, guiding or securing devices or arrangements for roll-type closures E06B9/56; free-hanging flexible screens A47H23/00
• CPC Class Codes: G02F 1/1503 caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
• 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 present invention relates to electrochromic solutions and devices manufactured therefrom. More precisely, the invention relates to electrochemichromic solutions, and those devices manufactured with the same, that demonstrate superior responsiveness to those solutions known heretofore when an applied potential is introduced thereto. That is, the responsiveness observed in terms of solution coloring is of a greater rapidity, intensity and uniformity than those electrochemichromic solutions of the prior art. Preparation of these solutions involve the novel process of pre-treating at least one of the electrochemichromic compounds with a redox agent prior to placing it in contact with the other electrochemichromic compound. Moreover, the present invention relates to methods of preparing such novel solutions and processes for using these solutions to provide devices that exhibit and benefit from the aforementioned superior characteristics.

Claims

1. An electrochemichromic solution capable of color change when an applied potential is introduced thereto, said electrochemichromic solution comprising:

(a) at least one anodic compound, said anodic compound having been previously contacted with a redox agent such that said anodic compound exists in a different valence state than prior to having been contacted with said redox agent;

(b) at least one cathodic compound; and

(c) a solvent

wherein the redox potential of said anodic compound in said different valence state is greater than the redox potential of said cathodic compound while each is contacted with said solvent.

2. The electrochemichromic solution according to claim 1, wherein said anodic compound is represented by the formula below:

##STR4## wherein A is O, NRR₁ ;

wherein R and R may be the same or different and each may be selected from the group consisting of H or any straight-chain or branched alkyl constituent having from about one carbon atom to about six carbon atoms, provided that when A is NRR₁, Q is H or OH;

D is O, S;

E is R , COOH, CONH₂, phenyl, 2,4-dihydroxyphenyl;

G is H;

J is phenyl, 2,4-dihydroxyphenyl;

or G and J, when taken together, represent an aromatic ring structure having six carbon ring atoms when viewed in conjunction with the ring carbon atoms to which they are attached;

L is H, OH; and

Q is H, OH, NRR₁.

3. The electrochemichromic solution according to claim 2, wherein each A of said anodic compound is NRR₁, a salt selected from the group consisting of tetrafluoroborate, perchlorate, trifluoromethane sulfonate, hexafluorophosphate and any halogen is associated therewith.

4. The electrochemical solution according to claim 2, wherein when Q of said anodic compound is OH, a salt selected from the group consisting of any alkali metal is associated therewith.

5. The electrochemichromic solution according to claim 2, wherein said anodic compound is a member selected from the class of chemical compounds consisting of the following formulae:

##STR5## and any combination thereof.

6. The electrochemichromic solution according to claim 2, wherein said anodic compound is represented by the formula below:

##STR6##

7. The electrochemichromic solution according to claim 2, wherein said anodic compound is represented by the formula below:

##STR7##

8. The electrochemichromic solution according to claim 2, wherein said anodic compound is represented by the formula below:

##STR8##

9. The electrochemichromic solution according to claim 2, wherein said anodic compound is represented by the formula below:

##STR9##

10. The electrochemichromic solution according to claim 2, wherein said anodic compound is represented by the formula below:

##STR10##

11. The electrochemichromic solution according to claim 2, wherein said anodic compound is represented by the formula below:

##STR11##

12. The electrochemichromic solution according to claim 2, wherein said anodic compound is represented by the formula below:

##STR12##

13. The electrochemichromic solution according to claim 2, wherein said anodic compound is represented by the formula below:

##STR13##

14. The electrochemichromic solution according to claim 1, wherein said cathodic compound is selected from the group of chemical compounds consisting of the following formulae:

##STR14## wherein R₂ and R₃ may be the same or different and each may be selected from the group consisting of H or any straight-chain or branched alkyl constituent having from about one carbon atom to about six carbon atoms;

X is selected from the group consisting of tetrafluoroborate, perchlorate, trifluoromethane sulfonate, hexafluorophosphate, any halogen

and any combination thereof.

15. The electrochemichromic solution according to claim 14, wherein said cathodic compound is ##STR15##

16. The electrochemichromic solution according to claim 14, wherein said cathodic compound is ##STR16##

17. The electrochemichromic solution according to claim 14, wherein said cathodic compound is ##STR17##

18. The electrochemichromic solution according to claim 1, wherein said redox agent of (a) is in a solid form.

19. The electrochemichromic solution according to claim 18, wherein said redox agent has a particle size of about 50 mesh to about 400 mesh.

20. The electrochemichromic solution according to claim 1, wherein said redox agent of (a) is a reducing agent capable of causing an electrochemichromic compound to assume a decreased valence state upon contacting therewith as compared with that valence state possessed by said electrochemichromic compound prior to having been contacted with said reducing agent.

21. The electrochemichromic solution according to claim 20, wherein said reducing agent is a member selected from the group consisting of zinc, ascorbic acid, sodium hydrosulfite, vanadium (III) chloride, chromium (II) acetate, sulfur dioxide and any combination thereof.

22. The electrochemichromic solution according to claim 21, wherein said reducing agent is zinc.

23. The electrochemichromic solution according to claim 1, wherein said redox agent of (a) is an oxidizing agent capable of causing an electrochemichromic compound to assume an increased valence state upon contacting therewith as compared with that valence state possessed by said electrochemichromic compound prior to having been contacted with said oxidizing agent.

24. The electrochemichromic solution according to claim 23, wherein said oxidizing agent is a member selected from the group consisting of air, oxygen, sodium persulfate, methylene violet (Bernthsen) and any combination thereof.

25. The electrochemichromic solution according to claim 1, wherein said solvent of (c) is a member selected from the group consisting of acetonitrile, 3-hydroxypropionitrile, methoxypropionitrile, 3-ethoxypropionitrile, propylene carbonate, 2-acetylbutyrolactone, cyanoethyl sucrose, 7-butyrolactone, 2-methylglutaronitrile, N,N'"'"'-dimethylformamide, 3,3'"'"'-ethylsulfolane, methylethyl ketone, cyclopentanone, cyclohexanone, benzoyl acetone, 4-hydroxy-4-methyl-2-pentanone, acetophenone, glutaronitrile, 3,3'"'"'-oxydipropionitrile, 2-methoxyethyl ether, triethylene glycol dimethyl ether and any combination thereof.

26. The electrochemichromic solution according to claim 1, wherein said solvent of (c) is acidic.

27. The electrochemichromic solution according to claim 26, wherein said solvent is rendered acidic by employing as a solvent component an acidic material selected from the group consisting of acetic acid, any hydrogen halide gas in solution, perchloric acid, 2-acetylbutyrolactone, 3-hydroxypropionitrile and any combination thereof.

28. The electrochemichromic solution according to claim 27, wherein said solvent component is acetic acid.

29. The electrochemichromic solution according to claim 28, wherein said solvent component is acetic acid employed in the range of about 0.01% (v/v) to about 75% (v/v).

30. The electrochemichromic solution according to claim 28, wherein said solvent component is acetic acid employed at about 1% (v/v).

31. The electrochemichromic solution according to claim 26, wherein said solvent is comprised of about 74% 3-hydroxypropionitrile, about 25% glutaronitrile and about 1% acetic acid (v/v).

32. The electrochemichromic solution according to claim 26, wherein said solvent is comprised of about 49.5% 3-hydroxypropionitrile, about 49.5% glutaronitrile and about 1% acetic acid (v/v).

33. The electrochemichromic solution according to claim 26, wherein said solvent is comprised of about 64% propylene carbonate, about 35% cyanoethyl sucrose and about 1% acetic acid (v/v).

34. The electrochemichromic solution according to claim 26, wherein said solvent is comprised of about 69% 3-hydroxypropionitrite, 30% 3,3'"'"'-oxydipropionitrile and about 1% acetic acid (v/v).

35. The electrochemichromic solution according to claim 26, wherein said solvent is comprised of about 99% propylene carbonate and about 1% acetic acid (v/v).

36. The electrochemichromic solution according to claim 1, further comprising (d) a constituent selected from the group consisting of an ultraviolet stabilizing agent, an electrolytic material and any combination thereof.

37. The electrochemichromic solution according to claim 36, wherein said ultraviolet stabilizing agent is a member selected from the group consisting of "UVINUL 400", "UVINUL D-49", TINUVIN P, "TINUVIN 327", "TINUVIN 328", "Cyasorb 24", benzotriazole, benzophenone and any combination thereof.

38. The electrochemichromic solution according to claim 37, wherein said ultraviolet stabilizing agent is "UVINUL 400".

39. The electrochemichromic solution according to claim 36, wherein said electrolytic material is a member selected from the group consisting of tetrabutylammonium hexafluorophosphate, tetraethylammonium perchlorate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium trifluoromethane sulfonate, any halogen alkali metal salt and any combination thereof.

40. The electrochemichromic solution according to claim 39, wherein said electrolytic material is tetrabutylammonium hexafluorophosphate.

41. The electrochemichromic solution according to claim 1, wherein the total concentration of said first electrochemichromic compound and said second electrochemichromic compound in said electrochemichromic solution is in the range of about 0.001M to about 0.1M.

42. The electrochemichromic solution according to claim 41, wherein the total concentration of said first electrochemichromic compound and said second electrochemichromic compound in said electrochemichromic solution is about 0.04M.

43. The electrochemichromic solution according to claim 1, wherein said applied potential is introduced to said solution in the range of about 0.001 volts to about 5 volts.

44. The electrochemichromic solution according to claim 43, wherein said applied potential is introduced at about 1 volt.

89. A process for using an electrochemichromic solution according to claim 1, said process comprises:

(a) inserting said electrochemichromic solution into a cell;

sealing said cell so that said electrochemichromic solution is prevented from escaping therefrom; and

(c) introducing an applied potential to said electrochemichromic solution contained in said cell such that a current passes therethrough to cause a color change thereof.

90. An electrochemichromic device comprising:

(a) a first substantially transparent substrate coated with a substantially transparent conductive coating on its interior face;

(b) a second substantially transparent substrate coated with a substantially transparent conductive coating on its interior face, said second substrate positioned in substantially parallel spaced-apart relationship with said first substrate and being laterally displaced therefrom;

(c) a sealing means positioned toward the peripheral edge of each of said first substrate and said second substrate and sealingly forming a cell cavity therebetween;

(d) the electrochemichromic solution according to claim 1 having been dispensed into and confined within said cell cavity; and

(e) a means for introducing an applied potential to said electrochemichromic solution to controllably cause a variation in the amount of light transmitted through said device.

91. The electrochemichromic device according to claim 90, wherein said transparent conductive coating may be constructed from a material selected from the group consisting of indium tin oxide, tin oxide, antimony-doped tin oxide, fluorine-doped tin oxide, antimony-doped zinc oxide and aluminum-doped zinc oxide.

92. The electrochemichromic device according to claim 90, wherein said device is a member selected from the group consisting of mirrors, glazings, partitions, filters, displays and lenses.

93. The electrochemichromic device according to claim 92, wherein said glazing is a window assembly.

94. The electrochemichromic device according to claim 92, wherein said glazing is a sun roof assembly.

95. The electrochemichromic device according to claim 92, wherein said device is a mirror assembly further comprising a reflective coating on a face of either one of said first substrate or said second substrate.

96. The electrochemichromic mirror assembly according to claim 95, wherein said reflective coating is constructed of a material selected from the group consisting of aluminum, silver, platinum, palladium, titanium, chromium and stainless steel.

97. The electrochemichromic device according to claim 90, wherein said first substrate of (a) is a laminate assembly comprising at least two substantially transparent panels affixed to one another by a substantially transparent adhesive layer.

98. The electrochemichromic device according to claim 90, further comprising (g) a molded casing formed about the periphery of said device.

99. The electrochemichromic device according to claim 98, wherein said molded casing is constructed of injection molded polyvinyl chloride.

100. The electrochemichromic device according to claim 98, wherein said molded casing is constructed of a moldable material that is reaction injected molded.

101. The electrochemichromic device according to claim 90, wherein said sealing means of (c) may be constructed from a member selected from the group consisting of thermosetting materials and thermoplastic materials.

102. The electrochemichromic device according to claim 101, wherein said sealing means is constructed from a thermosetting material.

103. The electrochemichromic device according to claim 101, wherein said sealing means is constructed of a thermoplastic material.

104. The electrochemichromic device according to claim 90, wherein said first substrate of (a) and said second substrate of (b) are constructed from a material selected from the group consisting of glass, optical plastics, laminated glass and tempered glass.

105. The electrochemichromic device according to claim 90, wherein said first substrate of (a) and said second substrate of (b) are each constructed of the same material.

106. The electrochemichromic device according to claim 90, wherein said first substrate of (a) and second substrate of (b) are each constructed of different materials.

110. The process for using an electrochemichromic solution according to claim 89, wherein said anodic compound of said electrochemichromic solution is a member selected from the group consisting of chemical compounds of the following formulae:

##STR32## and any combination thereof.

111. The process for using an electrochemichromic solution according to claim 89, wherein said anodic compound of said electrochemichromic solution is ##STR33##

112. The process for using an electrochemichromic solution according to claim 89, wherein said cathodic compound of said electrochemichromic solution is a member selected from the group consisting of chemical compounds of the following formulae:

##STR34## wherein R₂ and R₃ may be the same or different and each may be selected from the group consisting of H or any straight-chain or branched alkyl constituent having from about one carbon atom to about six carbon atoms; and

X is selected from the group consisting of tetrafluoroborate, perchlorate, trifluoromethane sulfonate, hexafluorophosphate, any halogen

and any combination thereof.

113. The process for using an electrochemichromic solution according to claim 89, wherein said solvent of siad electrochemichromic solution is a member selected from the group consisting of acetonitrile, 3-hydroxypropionitrile, methoxypropionitrile, 3-ethoxypropionitrile, propylene carbonate, 2-acetylbutyrolactone, cyanoethyl sucrose, γ

-butyrolactone, 2-methylglutaronitrile, N,N'"'"'-dimethylformamide, 3-methylsulfolane, methylethyl ketone, cyclopentanone, cyclohexanone, benzoyl acetone, 4-hydroxy-4-methyl-2-pentanone, acetophenone, glutaronitrile, 3,3'"'"'-oxydipropionitrile, 4-methoxyethyl ether, triethylene glycol dimethyl ether and any combination thereof.

114. The process for using an electrochemichromic solution according to claim 89, wherein said solvent of siad electrochemichromic solution is acidic.

115. The process according to claim 114, wherein said solvent is rendered acidic by employing as a solvent component an acidic material selected from the group consisting of acetic acid, any hydrogen halide gas in solution, perchloric acid, 2-acetylbutyrolactone, 3-hydroxypropionitrile and any combination thereof.

116. The process for using an electrochemichromic solution according to claim 89, wherein the total concentration of said anodic compound and said cathodic compound in said electrochemichromic solution is in the range of about 0.005M to about 0.5M.

117. The process for using an electrochemichromic solution according to claim 89, wherein said redox agent which has previously contacted said anodic compound of said electrochemichromic solution is a reducing agent capable of causing an electrochemichromic compound to assume a decreased valence state upon contacting therewith as compared with that valence state possessed by said electrochemichromic compound prior to having been contacted with said reducing agent.

118. The process according to claim 117, wherein said reducing agent is zinc.

119. The process for using an electrochemichromic solution according to claim 89, wherein said electrochemichromic solution further comprises a constituent selected from the group consisting of ultraviolet stabilizing agents, electrolytic material and any combination thereof.

120. The process of using an electrochemichromic solution according to claim 89, wherein said applied potential is introduced to said electrochemichromic solution in the range of about 0.001 volts to about 5 volts.

121. The electrochemichromic device according to claim 90, wherein said anodic compound of said electrochemichromic solution of said device is a member selected from the group consisting of chemical compounds of the following formulae:

##STR35## and any combination thereof.

122. The electrochemichromic device according to claim 90, wherein said anodic compound of said electrochemichromic solution of said device is ##STR36##

123. The electrochemichromic device according to claim 90, wherein said cathodic compound of said electrochemichromic solution of said device is a member selected from the group consisting of chemical compounds of the following formulae:

##STR37## wherein R₂ and R₃ may be the same or different and each may be selected from the group consisting of H or any straight-chain or branched alkyl constituent having from about one carbon atom to about six carbon atoms; and

X is selected from the group consisting of tetrafluoroborate, perchlorate, trifluoromethane sulfonate, hexafluorophosphate, any halogen

and any combination thereof.

124. The electrochemichromic device according to claim 90, wherein said solvent of said electrochemichromic solution of said device is member selected from the group consisting of acetonitrile, 3-hydroxypropionitrile, methoxypropionitrile, 3-ethoxypropionitrile, propylene carbonate, 2-acetylbutyrolactone, cyanoethyl sucrose, γ

-butyrolactone, 2-methylglutaronitrile, N,N'"'"'-dimethylformamide, 3-methylsulfolane, methylethyl ketone, cyclopentanone, cyclohexanone, benzoyl acetone, 4-hydroxy-4-methyl-2-pentanone, acetophenone, glutaronitrile, 3,3'"'"'-oxydipropionitrile, 2-methoxyethyl ether, triehtylene glycol dimethyl ether and any combination thereof.

125. The electrochemichromic device according to claim 90, wherein said solvent of said electrochemichromic solution of said device is acidic.

126. The electrochemichromic device according to claim 125, wherein said solvent is rendered acidic by employing as a solvent component an acidic material selected from the group consisting of acetic acid, any hydrogen halide gas in solution, perchloric acid, 2-acetylbutyrolactone, 3-hydroxypropionitrile and any combination thereof.

127. The electrochemichromic device according to claim 90, wherein the total concentration of said anodic compound and said cathodic compound in said electrochemichromic solution of said device is in the range of about 0.005M to about 0.5M.

128. The electrochemichromic device according to claim 90, wherein said redox agent which has previously contacted said anodic compound of said electrochemichromic solution of said device is a reducing agent capable of causing an electrochemichromic compound to assume a decreased valence state upon contacting therewith as compared with that valence state possessed by said electrochemichromic compound prior to having been contacted with said reducing agent.

129. The electrochemichromic device according to claim 128, wherein said reducing agent is zinc.

130. The electrochemichromic device according to claim 90, wherein said electrochemichromic solution of said device further comprises a constituent selected from the group consisting of ultraviolet stabilizing agents, electrolytic materials and any combination thereof.

131. The electrochemichromic device according to claim 90, wherein said applied potential is introduced to said electrochemichromic solution of said device in the range of about 0.002 volts to about 5 volts.

132. The process for using an electrochemichromic solution according to claim 89, wherein that quantity of said redox agent which has remained unreacted after having previously contacted said anodic compound of said electrochemichromic solution has been removed therefrom.

133. The electrochemichromic device according to claim 90, wherein that quantity of said redox agent which has remained unreacted after having previously contacted said anodic compound of said device has been removed from said electrochemichromic solution.

45. A process for preparing an electrochemichromic solution, said process comprises:

(a) solubilizing an electrochemichromic compound with a solvent;

(b) contacting said solubilized electrochemichromic compound with a redox agent to alter the valence state of said electrochemichromic compound such that an anodic compound is created in solution which has a different valence state than said solubilized electrochemichromic compound possessed prior to having been contacted with said redox agent;

(c) contacting a cathodic compound with said solubilized anodic compound of (b) to form said electrochemichromic solution; and

(d) introducing an applied potential to said electrochemichromic solution such that a current passes through said electrochemichromic solution thereby causing a color change thereof.

46. The process according to claim 45, wherein said anodic compound is represented by the formula below:

##STR18## wherein A is O, NRR₁ ;

wherein R and R₁ may be the same or different and each may be selected from the group consisting of H, any straight-chain or branched alkyl constituent having from about one carbon atom to about six carbon atoms, provided that when A is NRR₁, Q is H or OH;

D is O, S;

E is R₁, COOH, CONH₂, phenyl, 2,4-dihydroxyphenyl;

G is H;

J is phenyl, 2,4-dihydroxyphenyl;

or G and J, when taken together, represent an aromatic ring structure having six carbon ring atoms when viewed in conjunction with the ring carbon atoms to which they are attached;

L is H, OH; and

Q is OH, NRR₁.

47. The process according to claim 46, wherein when A of said anodic compound is NRR₁, a salt selected from the group consisting of tetrafluoroborate, perchlorate, trifluoromethane sulfonate, hexafluorophosphate and any halogen is associated therewith.

48. The process according to claim 46, wherein when Q of said anodic compound is OH, a salt selected from the group consisting of any alkali metal is associated therewith.

49. The process according to claim 46, wherein said anodic compound is selected from the group consisting of the chemical compounds represented by the following formulae ##STR19## and any combination thereof.

50. The process according to claim 46, wherein said anodic compound is represented by the formula below:

##STR20##

51. The process according to claim 46, wherein said anodic compound is represented by the formula below:

##STR21##

52. The process according to claim 46, wherein said anodic compound is represented by the formula below:

##STR22##

53. The process according to claim 46, wherein said anodic compound is represented by the formula below:

##STR23##

54. The process according to claim 46, wherein said anodic compound is represented by the formula below:

##STR24##

55. The process according to claim 46, wherein said anodic compound is represented by the formula below:

##STR25##

56. The process according to claim 46, wherein said anodic compound is represented by the formula below:

##STR26##

57. The process according to claim 46, wherein said anodic compound is represented by the formula below:

##STR27##

58. The process according to claim 45, wherein said cathodic compound is selected from the group consisting of the chemical compounds presented by the following formulae:

##STR28## wherein R₂ and R₃ may be the same or different and each may be selected from the group consisting of H or any straight-chain or branched alkyl constituent having from about one carbon atom to about six carbon atoms; and

X is selected from the group consisting of tetrafluoroborate, perchlorate, trifluoromethane sulfonate, hexafluorophosphate, any halogen

and any combination thereof.

59. The process according to claim 58, wherein said cathodic compound is represented by the formula below:

##STR29##

60. The process according to claim 58, wherein said cathodic compound is represented by the formula below:

##STR30##

61. The process according to claim 58, wherein said cathodic compound is represented by the formula below:

##STR31##

62. The process according to claim 45, further comprising after (b) removing that quantity of said redox agent of (b) which has remained unreacted.

63. The process according to claim 62, wherein said redox agent is removed by a means selected from the group consisting of filtering, decanting, osmosis, fractionating, precipitating, extracting, centrifuging, vacuum and any combination thereof.

64. The process according to claim 45, wherein said redox agent of (b) is in a solid form.

65. The process according to claim 64, wherein said redox agent has a particle size of about 50 mesh to about 400 mesh.

66. The process according to claim 45, wherein said redox agent of (b) is a reducing agent capable of causing an electrochemichromic compound to assume a decreased valence state upon contacting therewith as compared with that valence state possessed by said electrochemichromic compound prior to having been contacted with said reducing agent.

67. The process according to claim 66, wherein said reducing agent is a member selected from the group consisting of zinc, ascorbic acid, sodium hydrosulfite, vanadium (III) chloride, chromium (II) acetate, sulfur dioxide and any combination thereof.

68. The process according to claim 67, wherein said reducing agent is zinc.

69. The process according to claim 45, wherein said redox agent of (b) is an oxidizing agent capable of causing an electrochemichromic compound to assume an increased valence state upon contacting therewith as compared with that valence state possessed by said electrochemichromic compound prior to having been contacted with said oxidizing agent.

70. The process according to claim 69, wherein said oxidizing agent is a member selected from the group consisting of air, oxygen, sodium persulfate, methylene violet (Bernthsen) and any combination thereof.

71. The process according to claim 45, wherein said electrochemichromic solution further comprises a constituent selected from the group consisting of an ultraviolet stabilizing agent, an electrolytic material and any combination thereof.

72. The process according to claim 71, wherein said constituent is an ultraviolet stabilizing agent.

73. The process according to claim 72, wherein said ultraviolet stabilizing agent is selected from the group consisting of "UVINUL 400", "UVINUL D-49", "TINUVIN P", "TINUVIN 327", "TINUVIN 328", "Cyasorb 24", benzotriazole, benzophenone and any combination thereof.

74. The process according to claim 73, wherein said ultraviolet stabilizing agent is "UVINUL 400".

75. The process according to claim 71, wherein said constituent is an electrolytic material.

76. The process according to claim 75, wherein said electrolytic material is selected from the group consisting of tetrabutylammonium hexafluorophosphate, tetraethylammonium perchlorate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium trifluoromethane sulfonate, any halogen alkali metal salt and any combination thereof.

77. The process according to claim 76, wherein said electrolytic material is tetrabutylammonium hexafluorophosphate.

78. The process according to claim 45, wherein said solvent of (a) is a member selected from the group consisting of acetonitrile, 3-hydroxypropionitrile, methoxypropionitrile, 3-ethoxypropionitrile, propylene carbonate, 2-acetylbutyrolactone, cyanoethyl sucrose, γ

-butyrolactone, 2-methylglutaronitrile, N,N'"'"'-dimethylformamide, 3-methylsulfolane, methylethyl ketone, cyclopentanone, cyclohexanone, benzoyl acetone, 4-hydroxy-4-methyl-2-pentanone, acetophenone, glutaronitrile, 3,3'"'"'-oxydipropionitrile, 2-methoxyethyl ether, triethylene glycol dimethyl ether and any combination thereof.

79. The process according to claim 45, wherein said solvent of (a) is acidic.

80. The process according to claim 79, wherein said solvent is rendered acidic by employing as a solvent component an acidic material selected from the group consisting of acetic acid, any hydrogen halide gas in solution, perchloric acid, 2-acetylbutyrolactone, 3-hydroxypropionitrile and any combination thereof.

81. The process according to claim 80, wherein said solvent component is acetic acid.

82. The process according to claim 81, wherein said solvent component is acetic acid employed in the range of about 0.01% (v/v) to about 75% (v/v).

83. The process according to claim 82, wherein said solvent component is employed at about 1% (v/v).

84. The process according to claim 80, wherein said solvent is comprised of about 74% 3-hydroxypropionitrile, about 24% glutaronitrile and about 1% acetic acid (v/v).

85. The process according to claim 80, wherein said solvent is comprised of about 49.5% 3-hydroxypropionitrile, about 49.5% glutaronitrile and about 1% acetic acid (v/v).

86. The process according to claim 80, wherein said solvent is comprised of about 64% propylene carbonate, about 35% cyanoethyl sucrose (v/v) and about 1% acetic acid (v/v).

87. The process according to claim 80, wherein said solvent is comprised of about 69% 2-hydroxypropionitrile, about 30% 3,3'"'"'-oxydipropionitrile and about 1% acetic acid (v/v).

88. The process according to claim 80, wherein said solvent is comprised of about 99% propylene carbonate and about 1% acetic acid (v/v).

107. An electrochemichromic device comprising:

(a) a first glass substrate coated with a conductive coating on its interior face;

(b) a second glass substrate coated with a conductive coating on its interior face, said second glass substrate positioned in substantially parallel spaced-apart relationship with said first glass substrate;

(c) a sealing means positioned toward, but inward from, the peripheral edge of each of said first substrate and said second substrate and sealingly forming a cell cavity therebetween;

(d) an electrochemichromic solution capable of color change when an applied potential is introduced thereto, said electrochemichromic solution comprising;

(1) methylene violet (Bernthsen), wherein said methylene violet (Bernthsen) has previously been reduced;

(2) an alkyl-substituted viologen salt, wherein said alkyl substituent is a member-selected from the group consisting of any straight-chain or branched alkyl group having from about one carbon atom to about six carbon atoms; and

(3) a solvent, wherein said solvent is a member selected from the group consisting of the the combination of 3-hydroxypropionitrile, glutaronitrile and acetic acid, the combination of propylene carbonate and acetic acid, the combination of 3-ethoxypropionitrile and 2-acetylbutyrolactone, the combination of 3-ethoxypropionitrile, glutaronitrile and acetic acid, the combination of 3-hydroxypropionitrile, 3,3'"'"'-oxydipropionitrile and acetic acid, and the combination of propylene carbonate, cyanoethyl sucrose and acetic acid, wherein said solution has been dispensed into and confined within said cell cavity; and

(e) a means for introducing an applied potential to said electrochemichromic solution to controllably cause a variation in the amount of light transmitted through said solution.

108. The electrochemichromic device according to claim 107, wherein said device is selected from the group consisting of mirrors, glazings, partitions, filters, displays and lenses.

109. The electrochemichromic device according to claim 108, wherein said device is a mirror further comprising a reflective coating on a face of said second glass substrate.